DEMYSTIFYING PHYSICAL CHEMISTRY (A’LEVEL)

A simplified, well elaborated and illustrative approach to the

physical chemistry

Joseph Jobs Kayiira,

BSCED(Chemistry/mathematics)(Hons)
+256753247098
 PREFACE
The author has an inexorable curiosity in streamlining the chemistry concepts that
majority of the students in Uganda consider a nut to crack.
He has taught Chemistry and Mathematics in various schools in Entebbe, Kampala,
Wakiso and Butambala. This means that he has analysed the problems students at
A‟ level face in Chemistry.
This physical chemistry collation has been substantially organised and fully
compatible with the NCDC Chemistry syllabus-2013
The author is contented that this edition contains more than enough material as
regards A‟ level physical chemistry and the subject matter has been arranged and
structured so that it can be tackled by students of different abilities and the text is
in a readable font to all kinds of eyes.
Indeed this book is vital for a student to teach him/herself even in absence of a
teacher. However, the teacher is as well vital in cases where you may not well
interprete the content. The author has tried to link physical chemistry with
inorganic and organic concepts where he feels it is necessary.
Variety of examples are given, more than one methods of solving a problem
illustrated and a diversity of typical examinable revision questions in each subtopic
but no answers such that research and consultation is enhanced.

Also feel free to contact the author using contacts or social media platforms at the
back cover of the book for clarity, recommendations, guidance or advice.

This is the only book that you will not regret to have come across.
 TABLE OF CONTENTS
CHAPTER ONE ....................................................................................................................... 602
MATTER ................................................................................................................................... 602
The structure of an atom ...................................................................................................... 602
Diagrammatic illustration of an atom ............................................................................................... 603
................................................................................................................................................. 603
The sub atomic particles ....................................................................................................... 603
Fundamental particles of an atom ....................................................................................... 603
1. Electrons ................................................................................................................................... 603
2. Protons ...................................................................................................................................... 604
3. Neutrons .................................................................................................................................... 604
The Nucleus ...................................................................................................................................... 604
Isotopic notation .................................................................................................................... 605
Ionic formation ...................................................................................................................... 605
IUPAC nomenclature for cations, anions and salts ........................................................... 607
Naming monoatomic ions; cations and anions.................................................................................. 607
Naming polyatomic ions and compounds ......................................................................................... 608
The Stock system .............................................................................................................................. 610
Systemic/Correct/unambiguous name of some compounds ............................................................. 611
The selection of correct Roman numeral .......................................................................................... 611
Writing the formula of a binary compound....................................................................................... 612
MASS SPECTROMETRY ................................................................................................... 612
The essential parts and operation of a modern mass spectrometer ................................................... 612
Diagram showing the essential parts of a modern mass spectrometer .............................................. 613
613
613
613
 Hot tungsten filament ........................................................................................................................ 613
THE MOLE CONCEPT ....................................................................................................... 614
Calculating molar masses of elements and compounds .................................................................... 615
Examples ........................................................................................................................................... 615
Molar mass-mole conversions .......................................................................................................... 615
Examples ........................................................................................................................................... 616
Questions........................................................................................................................................... 617
Limiting reactants and excess reactants ............................................................................................ 617
Percentage yields in a chemical reaction .......................................................................................... 618
Experiment to demonstrate concept of limiting and excess reactants, theoretical yield, actual yield
and percentage yield.......................................................................................................................... 618
Examples ........................................................................................................................................... 619
Questions........................................................................................................................................... 621
PRIMARY AND SECONDARY STANDARDS ................................................................ 622
Preparation of standard solutions by weighing and dissolving in water ........................................... 625
VOLUMETRIC ANALYSIS ................................................................................................ 626
Common terms used in volumetric analysis ..................................................................................... 626
Set up of apparatus for volumetric analysis ...................................................................................... 627
Acid-base titrations and use of data obtained ................................................................................... 627
Exercise on dilution and standardisation........................................................................................... 630
Practical exercises on standardisation ............................................................................................... 631
Back titrations ................................................................................................................................... 633
OXIDATION NUMBER (OXIDATION STATE) ............................................................. 636
Calculating oxidation state ................................................................................................................ 637
Examples ........................................................................................................................................... 637
Questions........................................................................................................................................... 638
REDOX REACTIONS.......................................................................................................... 639
(OXIDATION-REDUCTION REACTIONS) .................................................................... 639
Deriving equations for redox reactions ............................................................................................. 643
Examples ........................................................................................................................................... 643
Balancing redox reactions in alkaline media .................................................................................... 647
Questions........................................................................................................................................... 648
Titration of redox reactions ............................................................................................................... 649
Sodium thiosulphate titrations .......................................................................................................... 650
Examples ........................................................................................................................................... 651
PHYSICAL STATES OF MATTER ................................................................................... 652
Inter-conversion between the states .................................................................................................. 652
Plasma ............................................................................................................................................... 652
The kinetic theory of matter .............................................................................................................. 652
Differences in the states of matter..................................................................................................... 653
Comparison of physical properties ................................................................................................... 653
GASEOUS STATE OF MATTER ................................................................................................... 654
The gaseous state in terms of kinetic theory of matter ...................................................................... 654
AN IDEAL GAS ............................................................................................................................... 655
Gas pressure ...................................................................................................................................... 655
Gas laws ............................................................................................................................................ 655
Examples on calculations involving gas laws ................................................................................... 657
Ideal gas law ..................................................................................................................................... 658
Examples ........................................................................................................................................... 659
Questions........................................................................................................................................... 659
Graham‟s law of gaseous diffusion ................................................................................................... 660
Examples ........................................................................................................................................... 662
Questions........................................................................................................................................... 664
Mole fraction of a gas, ................................................................................................................. 667
Dalton‟s law of partial pressure ........................................................................................................ 667
Examples ........................................................................................................................................... 668
LIQUID STATE OF MATTER ........................................................................................................ 668
The liquid state in terms of kinetic theory of matter ......................................................................... 668
Properties of a liquid ......................................................................................................................... 669
SOLID STATE OF MATTER .......................................................................................................... 672
The solid state in terms of kinetic theory of matter ......................................................................... 672
Phase changes in solids ..................................................................................................................... 673
Types of solids .................................................................................................................................. 674
Giant ionic solids .............................................................................................................................. 674
Giant covalent solids ......................................................................................................................... 675
Molecular covalent solids ................................................................................................................. 676
Giant metallic solids ......................................................................................................................... 677
EMPIRICAL FORMULA, MOLECULAR FORMULA AND PERCENTAGE
COMPOSITION BY MASS ................................................................................................. 678
The percentage composition by mass of an element or a molecule in a compound ......................... 678
 Empirical formulae and molecular formulae .................................................................................... 680
Calculations on empirical formulae and molecular formulae ........................................................... 681
Examples ........................................................................................................................................... 681
Questions........................................................................................................................................... 688
CHAPTER TWO ...................................................................................................................... 689
ATOMIC STRUCTURE AND THE PERIODIC TABLE ................................................... 689
Fundamental particles of the atoms and radioactivity ...................................................... 689
Historical development of the atomic theory .................................................................................... 689
Modern theory of the atom................................................................................................................ 689
(a) John Dalton‟s atomic theory ..................................................................................................... 689
(b) The J.J Thomson model of an atom .......................................................................................... 690
(c) Ernest Rutherford‟s atomic model ............................................................................................ 691
Fundamental particles of the atom .................................................................................................... 692
The discovery of the fundamental particles of the atom ................................................................... 692
Properties of the fundamental particles of the atom.......................................................................... 692
RADIOACTIVITY ........................................................................................................................... 692
Discovery .......................................................................................................................................... 692
Types of radiations and their discovery ............................................................................................ 694
ELECTRONIC STRUCTURE OF ATOMS ...................................................................... 694
Electromagnetic radiation ................................................................................................................. 694
Electromagnetic radiation as quanta ................................................................................................. 694
Relationship between wavelength frequency, , and energy, . ................................................. 695
Using the equation in calculations .................................................................................................... 695
Atomic spectra .................................................................................................................................. 695
Types of spectra ................................................................................................................................ 696
Emission spectrum ............................................................................................................................ 696
Absorption spectrum ......................................................................................................................... 696
A description of the hydrogen emission spectrum ............................................................................ 697
An explanation of the hydrogen spectrum ........................................................................................ 697
The application of the Rydberg equation .......................................................................................... 698
Energy level diagram for the hydrogen atom.................................................................................... 700
The significance of lines in the hydrogen spectrum.......................................................................... 701
The importance of the Convergence limit......................................................................................... 701
The Bohr‟s model of the hydrogen atom .......................................................................................... 701
Ionisation energy ............................................................................................................................... 702
 Heisenberg‟s Uncertainty principle .................................................................................................. 704
The concept of quantum numbers ..................................................................................................... 704
Differentiation between an orbit and an orbital ................................................................................ 706
The Aufbau principle ........................................................................................................................ 707
Pauli Exclusion principle .................................................................................................................. 707
Hund‟s rule........................................................................................................................................ 707
Electronic configuration of atoms ..................................................................................................... 708
Electronic configuration of ions ........................................................................................................ 709
Questions........................................................................................................................................... 710
THE PERIODIC TABLE ..................................................................................................... 712
The historical development of the Periodic Table ............................................................................ 712
Unique position of Hydrogen in the Periodic Table ......................................................................... 713
The Modern Periodic Table .............................................................................................................. 714
Periodicity of atomic properties in the Periodic Table...................................................................... 718
Atomic and Ionic radius .................................................................................................................... 719
Ionisation energy ............................................................................................................................... 722
CHAPTER THREE .................................................................................................................. 723
STRUCTURE AND BONDING .............................................................................................. 723
CHEMICAL BONDING ...................................................................................................... 723
Lewis Dot symbols ........................................................................................................................... 723
The octet rule and ions ...................................................................................................................... 726
Ionic bond formation......................................................................................................................... 727
Giant ionic structures ........................................................................................................................ 728
The properties of ionic compounds ................................................................................................... 729
Covalent character in ionic compounds ............................................................................................ 730
Covalent bond formation .................................................................................................................. 733
Types of covalent bonding ................................................................................................................ 735
Covalent bond strength ..................................................................................................................... 739
Giant covalent structures ................................................................................................................... 740
Properties of covalent compounds .................................................................................................... 740
Intermolecular forces ........................................................................................................................ 741
Van der Waals‟ forces ....................................................................................................................... 741
Examples to explain the effect of van der Waals‟ forces .................................................................. 742
The hydrogen bond ........................................................................................................................... 745
Types of hydrogen bonding .............................................................................................................. 746
 Examples to explain the effect of hydrogen bonding........................................................................ 750
Questions........................................................................................................................................... 752
Metallic bonding ............................................................................................................................... 753
Properties of metals........................................................................................................................... 754
Strength of a metallic bond ............................................................................................................... 755
VALENCE BOND THEORY .............................................................................................. 756
Sigma and pi bonds .................................................................................................................. 756
Hybridisation of atomic orbitals ....................................................................................................... 757
Geometry for different types of hybridisation .................................................................................. 760
The formation of single, double and triple bonds ............................................................................. 760
The double bond formation in benzene............................................................................................. 762
DRAWING LEWIS STRUCTURES OF MOLECULES AND POLYTATOMIC IONS
................................................................................................................................................. 762
Lewis structures ................................................................................................................................ 762
Drawing Lewis structures of some simple molecules ....................................................................... 763
Steps for writing Lewis structures for more complex molecules/ polyatomic ions .......................... 763
Exceptions of the Octet rule .............................................................................................................. 766
Formal charges .................................................................................................................................. 767
Resonance ......................................................................................................................................... 769
VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY ................. 769
Predicting the shapes of molecules and ions ..................................................................................... 770
(a) Steps followed to draw the structure of molecules and cations ................................................ 772
(b) Steps followed to draw the structure of oxy-anions and oxy-molecules................................... 774
(a) Molecules or ions with a linear shape ....................................................................................... 777
(b) Molecules or ions with a bent shape ......................................................................................... 778
(c) Molecules or ions with a trigonal planar shape ......................................................................... 779
(d) Molecules or ions with a tetrahedral shape ............................................................................... 780
(e) Molecules or ions with a trigonal pyramidal shape .................................................................. 781
(f) Molecules or ions with a trigonal bipyramidal shape ............................................................... 783
(g) Molecules or ions with an irregular tetrahedral shape .............................................................. 784
(h) Molecules or ions with an octahedral shape ............................................................................. 784
(i) Molecules with a square pyramidal shape ................................................................................ 785
(j) Molecules or ions with a square planar shape ........................................................................... 785
The effect of lone pairs on Molecular Geometry .............................................................................. 790
The effect of electronegativity on size of bond angles...................................................................... 792
 Polarity of molecules ........................................................................................................................ 794
Factors that determine the polarity of molecules .............................................................................. 794
Differences between polar and non-polar molecules ........................................................................ 795
Miscellaneous Questions................................................................................................................... 796
CHAPTER FOUR ..................................................................................................................... 798
THERMOCHEMISTRY .......................................................................................................... 798
(CHEMICAL ENERGETICS) ................................................................................................ 798
CHEMICAL ENERGY ........................................................................................................ 798
Heat content of a substance ............................................................................................................... 798
Enthalpy, ....................................................................................................................................... 799
Enthalpy change, ........................................................................................................................ 799
Standard enthalpy change, ....................................................................................................... 799
TYPES OF HEAT OF REACTIONS .................................................................................. 799
Energy level diagrams for exothermic and endothermic reactions ................................................... 800
Applications of exothermic reactions in everyday life ..................................................................... 801
Applications of endothermic reactions in everyday life ................................................................... 802
Factors affecting enthalpy of reaction ................................................................................. 802
CALORIMETRY .................................................................................................................. 803
Heat capacity of a calorimeter .......................................................................................................... 803
Experiment to determine heat capacity of a simple calorimeter/ plastic cup calorimeter ................. 803
TYPES OF ENTHALPY CHANGES ................................................................................. 804
Enthalpy of formation ....................................................................................................................... 804
Standard enthalpy of formation ........................................................................................... 804
CHAPTER FIVE ...................................................................................................................... 806
PHYSICAL EQUILIBRIA ...................................................................................................... 806
SYSTEMS, PHASES, COMPONENTS AND PHASE DIAGRAMS ............................... 806
System..................................................................................................................................... 806
Phase ................................................................................................................................................. 806
Component ........................................................................................................................................ 806
Phase diagram ................................................................................................................................... 807
COMPONENT SYSTEMS ................................................................................................... 807
One component systems.................................................................................................................... 807
The water system .............................................................................................................................. 807
Examples of solutions that deviate negatively from Raoult‟s law .................................................... 811
 Characteristic vapour pressure-composition diagram for negative deviation from Raoult‟s law ..... 812
Maximum boiling point-composition diagram ................................................................................. 812
Positive deviation from Raoult‟s law ................................................................................................ 814
Calculations involving steam distillation .......................................................................................... 814
Questions on steam distillation ......................................................................................................... 816
Limitations of colligative properties ................................................................................................. 818
Vapour pressure lowering ................................................................................................................. 819
Elevation of boiling point (Ebullioscopy) ......................................................................................... 828
Freezing point depression (Cryoscopy) ............................................................................................ 837
Osmotic pressure, .......................................................................................................................... 847
CHAPTER SIX ......................................................................................................................... 856
CHEMICAL EQUILIBRIA ..................................................................................................... 856
THE CONCEPT OF CHEMICAL EQUILIBRIUM ......................................................... 856
The characteristics of a chemical equilibrium .................................................................................. 856
Reversible and irreversible reactions ................................................................................................ 856
Dynamic equilibrium ........................................................................................................................ 857
Types of chemical equilibria ............................................................................................................. 857
THE LAW OF MASS ACTION OR EQUILIBRIUM LAW ........................................... 858
The concentration equilibrium constant, ..................................................................................... 859
The pressure equilibrium constant, ............................................................................................. 859
Using the law of mass action to write equilibrium constant expressions ( or ) and units...... 859
The relationship between and ............................................................................................. 861
EXPERIMENTS ON CHEMICAL EQUILIBRIUM ........................................................ 862
CALCULATIONS INVOLVING CONCENTRATION EQUILIBRIUM CONSTANT
AND PRESSURE EQUILIBRIUM CONSTANT .............................................................. 866
Interpretation of magnitude of or in relation to equilibrium position................................. 897
Comparing the reaction quotient (Q) and to determine direction of a chemical reaction ........ 897
L CHATELIER’S PRINCIPLE AND THE EFFECTS OF VARIOUS FACTORS ON
THE EQUILIBRIUM OF REVERSIBLE CHEMICAL REACTIONS.......................... 899
INDUSTRIAL APPLICATION OF CHEMICAL EQUILIBRIUM ............................... 908
CHAPTER SEVEN ................................................................................................................... 912
IONIC EQUILIBRIA ............................................................................................................... 912
ACIDS, BASES AND SALTS .............................................................................................. 912
Acids and bases ................................................................................................................................. 912
 The concept of acids and bases according to various theories .......................................................... 912
Conjugate acid and bases .................................................................................................................. 914
Classification of strong acids and bases, weak acids and bases ........................................................ 915
Relative strength of Bronsted-Lowry acids and bases ...................................................................... 916
Derivation of expressions for acid dissociation constant, and base dissociation constant, .. 923
Calculations involving ................................................................................................................ 923
Calculations involving ................................................................................................................ 923
The auto ionisation ( self-ionisation ) of water ................................................................................. 923
The concept of ............................................................................................................................ 923
The scale ..................................................................................................................................... 923
Calculations involving for strong acids and bases ........................................ 924
Expression of for weak acids and bases ..................................................................................... 924
calculations for weak acids and weak bases ............................................................................... 924
BUFFER SOLUTIONS ........................................................................................................ 924
-volume curves for acid-base titrations ....................................................................................... 924
Sparingly soluble salts/ electrolytes .................................................................................................. 924
Solubility product.............................................................................................................................. 925
Expressions for solubility product .................................................................................................... 925
CHAPTER NINE ...................................................................................................................... 927
ELECTROCHEMISTRY ........................................................................................................ 927
MODES OF CONDUCTION OF SUBSTANCES........................................................................... 927
ELECTROLYSIS .................................................................................................................. 927
The common terms used in electrolysis ............................................................................................ 927
Explaining the changes that take place during electrolysis ............................................................... 929
Principles of electrolysis (selective discharge of ions) ..................................................................... 929
Laws of electrolysis .......................................................................................................................... 931
Calculations of electrolysis ............................................................................................................... 933
The applications of electrolysis in industry ...................................................................................... 939
CONDUCTIVITY OF SOLUTIONS OF ELECTROLYTES .......................................... 940
The common terms used ................................................................................................................... 940
Measurement of conductivity of solutions ........................................................................................ 943
Calculations involving electrolytic conductance .............................................................................. 944
Factors affecting electrolytic conductivity of electrolytes ................................................................ 947
Factors affecting molar conductivity of electrolytes ......................................................................... 948
 Kohlrausch‟s law of independent migration of ions and its application ........................................... 953
Application of conductance (conductivity measurements) ............................................................... 963
Conductimetric titrations................................................................................................................... 964
ELECTRODE POTENTIAL AND ELECTROCHEMICAL CELLS ............................ 971
ELECTRODE POTENTIAL ............................................................................................................ 971
Electrochemical series....................................................................................................................... 973
Absolute and relative electrode potential .......................................................................................... 975
The structure and functioning of the Standard Hydrogen Electrode (SHE)...................................... 975
Standard electrode potential, ................................................................................................. 976
Experiment to measure standard electrode potential of a metal........................................................ 976
Factors affecting magnitude of electrode potential ........................................................................... 977
Variation of electrode potential in group II and period 3 .................................................................. 978
ELECTROCHEMICAL CELLS....................................................................................................... 979
Construction of a Daniel cell ............................................................................................................ 981
The cell notation/cell convention ...................................................................................................... 982
Calculation of cell emf and prediction of spontaneity/feasibility of a reaction ................................ 986
Gibb‟s free energy, , as a measure of spontaneity........................................................................ 988
Applications of electrode potentials .................................................................................................. 989
Questions........................................................................................................................................... 989
 A simplified, well elaborated and illustrative approach to Physical Chemistry

CHAPTER ONE
MATTER
Matter is anything that occupies space and has weight.
Matter is made up of very tiny particles (building blocks) known as atoms, molecules or
ions.
An atom is the smallest electrically neutral particle of an element that takes part in a
chemical reaction.
A molecule is the smallest electrically neutral particle of a compound or an element
that is formed by the combination of atoms in a whole number ratio and can exist on
its own.
In a molecule of an element, the combining atoms are the same (for example; the oxygen
molecule, )
In a molecule of a compound, different atoms combine (for example the hydrogen

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

chloride molecule, )
A molecule retains the properties of that element or compound it contains.
An ion is an atom or a group of chemically combined atoms that has either lost one or
more electrons, making it positively charged (a cation), or gained one or more electrons,
making it negatively charged (an anion).

The structure of an atom

An atom is spherical in shape and has a small region in the center called the nucleus. The
atom contains protons and neutrons, and electrons as fundamental particles.
The protons and neutrons are concentrated in a very small nucleus in the center of the
atom while the electrons are all outside the nucleus in the energy levels and are
constantly rotating around the nucleus.
The number of electrons in the energy levels (negative charges) is equal to the number of
all protons in the nucleus (positive charges) hence an atom is neutral.
The energy level closest to the nucleus is called the first energy level or the K energy
level. The second closest energy level to the nucleus is the second energy level or the L
energy level. This is followed by the third energy level or the M energy level. So, the
energy levels are named 1st, 2nd, 3rd, 4th, and so on or K, L, M, N and so on from the
energy level closest to the nucleus outwards.
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 A simplified, well elaborated and illustrative approach to Physical Chemistry

Diagrammatic illustration of an atom

Energy levels

Electrons
Nucleus (Protons and neutrons)

The sub atomic particles

Electrons, protons and neutrons were the first small particles to be discovered and many
of the properties of matter are explained in terms of them. For this reason, they are called
the fundamental, basic or elementary particles of matter. More recent research has
however shown that there are many other small particles that do exist.
A study of cosmic rays and the nature of nuclear changes have led to discovery of over
200 sub atomic particles which are classified according to the strength of the forces

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

between them, their mass and their spin.
Some of the subatomic particles are shown below
Leptons Hadrons
baryons mesons
electron proton pions

muon neutron kaons

neutrino lambda

Most of the particles have an associated anti-particle with an equal but opposite charge.
For example a positron is an anti- particle for an electron

Fundamental particles of an atom

The fundamental particles of an atom are the electron, proton and neutron.

1. Electrons
Electrons are negatively charged particles surrounding the nucleus.
The electrons are carried in circular paths known as energy levels that surround the
nucleus
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 A simplified, well elaborated and illustrative approach to Physical Chemistry

An electron has a mass of ⁄ of a proton, therefore its mass is said to be

negligible; it carries a charge of negative one (-1).

The chemical reactions of an element are determined by the number of electrons (which
is equal to the number of protons in the nucleus)

2. Protons
Protons are positively charged fundamental particles which are present in all atomic
nuclei.
Protons have a unit mass of one (1) and each proton carries a charge of positive one (+1).

3. Neutrons
Neutrons are uncharged fundamental particles in the nuclei of atoms, with the exception
of hydrogen.
Neutrons also have unit mass of one and carry no charge (they are neutral).

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Particle Charge Mass
Electron - ⁄

Proton + 1
Neutron No charge 1

The Nucleus
The nucleus of an atom consists of protons (positively charged) and neutrons (which have
no charge)
Protons and neutrons are collectively called nucleons.
The sum of the number of protons and neutrons in the nucleus of an atom is called
nucleon number or mass number (A).
The number of protons in the nucleus of an element is called the Proton number or
atomic number (Z).
The full symbol of an atom of an element is given notation where;
is the symbol of the element
is the nucleon number or mass number
is the proton number or atomic number

The atomic number provides some information about an element which may include;
(i) The position of an element in the Periodic Table
(ii) The number of protons present in the nucleus of an atom
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(iii) The total number of electrons present in the neutral atom

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 A simplified, well elaborated and illustrative approach to Physical Chemistry

Isotopic notation
Isotopes are atoms of the same element with the same number of protons but different
number of neutrons.
Isotopes therefore have different mass numbers.

Isotopy is the existence of atoms of the same element with the same number of protons
but different number of neutrons.
Isotopes of the same element have very similar chemical properties because they have the
same electronic configuration, but differ slightly in their physical properties. An unstable
isotope is termed a radioactive isotope or radioisotope.
Element Isotopic name Isotopic No. of No. of No. of
formula protons electrons neutrons
Hydrogen Protium 1 1 0
Deuterium 1 1 1

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Tritium 1 1 2
Carbon Carbon-12 6 6 6
Carbon-14 6 6 8
Oxygen Oxygen-16 8 8 8
Oxygen-17 8 8 9
Oxygen-18 8 8 10
Chlorine Chlorine-35 17 17 18
Chlorine-37 17 17 20
Uranium Uranium-234 92 92 142
Uranium-235 92 92 143
Uranium-238 92 92 146

Ionic formation
An ion is a charged particle formed from an atom or a group of chemically combined
atoms by gaining or losing one or more electrons. Ions are either negatively charged
(anions) or positively charged (cations).
a) Positive ions (cations)
These are formed when atoms or group of chemically combined atoms lose one or more
electrons. Atoms lose electrons so as to acquire a stable electronic configuration as the
noble gases. The positive ions are formed by metal atoms, in ammonium ion and
hydroxonium ion.
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 A simplified, well elaborated and illustrative approach to Physical Chemistry

(i) Formation of sodium ion

The sodium atom has 11 electrons hence electronic configuration, .
The atom therefore has one electron more than the stable configuration of a noble gas,
.
To form the sodium ion, the sodium atom loses the one electron in the outer most energy
level to form a noble gas configuration

→
(ii) Formation of Aluminium ion
The aluminium atom has 13 electrons hence electronic configuration, .
The atom therefore has three electrons more than the stable configuration of a noble gas,
.
To form the aluminium ion, the aluminium atom loses the three electrons in the outer
most energy level to form a noble gas configuration

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

→
(iii) Formation of Ammonium ion
This is an ion formed by coordination of ammonia to a hydrogen ion. The formation of
this ion is possible because the nitrogen atom in the ammonia molecule has a lone pair of
electrons which it donates to the electron deficient hydrogen ion to form a dative covalent
bond. An arrow is often used to indicate which atom has donated the lone pair and also
represents the co-ordinate bond/ dative bond.

[ ]

(iv) Formation of the oxonium ion.

This is an ion formed by coordination of water to a hydrogen ion. The formation of this
ion is possible because the oxygen atom in the water molecule has lone pairs of electrons.
It donates electrons to the electron deficient hydrogen ion to form a dative covalent bond.

[ ]

b) Negative ions (anions)

These are formed when atoms or group of chemically combined atoms gain one or more
electrons. Atoms gain electrons so as to acquire a stable electronic configuration as the
noble gases. The negative ions are formed by non-metallic atoms. Examples include the
chloride ion, oxide ion, etc.
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(i) Formation of a chloride ion.

The chlorine atom has 17 electrons hence electronic configuration, .
The atom therefore lacks an electron to gain the stable configuration of a noble gas,
.
To form the chloride ion, the chlorine atom gains one electron in the outer most energy
level to form a noble gas configuration
→
(ii) Formation of an oxide ion
The oxygen atom has 8 electrons hence electronic configuration, .
The atom therefore lacks two electrons to gain the stable configuration of a noble gas,
.
To form the oxide ion, the oxygen atom gains two electrons in the outer most energy
level to form a noble gas configuration
→

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

IUPAC nomenclature for cations, anions and salts
The International Union of Pure and applied Chemistry (IUPAC) recommends that every
inorganic compound should have a name from which an unambiguous formula can be
determined.
Naming monoatomic ions; cations and anions
The following rules are considered when naming monoatomic(single atom) ions
1. Monoatomic anions are named with a suffix ...ide
Consider the examples below
Mono atomic anion IUPAC name
Hydride
Nitride
Boride
Carbide
Silicide
Oxide
Chloride
Iodide
Bromide
Fluoride
Sulphide
Phosphide
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2. Monoatomic cations are simply given the name of corresponding element

followed by charge on the ion in parentheses and written in correct roman
numerals. For elements that are monovalent like Al, Zn, Mg, Ca, Ba, etc., the
charge may be ignored.

Monoatomic cation Name

Hydrogen ion
Sodium ion
Silver ion
Aluminium ion
Zinc ion
Magnesium ion
Calcium ion
Barium ion

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Manganese(II) ion
Tin(II) ion
Tin(IV) ion
Lead(II) ion
Lead(IV) ion
Iron(II) ion
Iron(III) ion
Chromium(III) ion
Cobalt(II) ion
Nickel(II) ion
Copper(I) ion
Copper(II) ion

Naming polyatomic ions and compounds

There exist ions that contain more than one atom. These are called polyatomic ions. Most
of the polyatomic ions contain oxygen atoms and these are called oxyanions.
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Common polyatomic ions and their names

Formula Name
Ammonium ion
̅ Hydroxide ion
̅ Ethanoate ion
Oxalate ion
Nitrate ion
Nitrite
Hydrogencarbonate ion
Hydrogensulphate ion
Peroxide ion
Carbonate
Chlorate(VII) ion

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Chlorate(V) ion
Phosphate ion
Chromate(VI) ion
Dichromate(VI) ion
Manganate(VI) ion
Manganate(VII) ion
Sulphate ion
Sulphite ion
Cyanide ion
Triiodide ion

Naming polyatomic compounds

1. The name should have the name of the cation followed by name of the anion.
2. The name of the cation is written first followed by the name of the anion
3. For cations that take on multiple charges, the charge is written using parentheses
immediately following the element name.
4. When the formula contains two or more of the same polyatomic ion, that ion is written in
parentheses with a subscript of the number of the polyatomic ions.
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The Stock system

The Stock system of nomenclature was developed by the German Chemist Alfred Stock
in 1919. In this system, the oxidation state of an element is indicated in parentheses and
in Roman numerals.
It requires that there is usually no space between the end of the element name and the
opening parentheses for example
has a correct name as copper(I) chloride and not copper (I) chloride.
Consider examples below
Formula of compound Name
Tin(II) chloride
Tin(IV) chloride
Iron(II) chloride
Iron(III) chloride

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Calcium oxide
Sodium oxide
Lead(II) bromide
Chromium(III) oxide
Aluminium oxide
Aluminium carbide

The stock system is widely used in modern chemistry to name compounds and
complexes. It has been used to develop systemic names for various compounds.
Below is the procedure for naming binary ionic compounds.
1. The name should have the name of the cation followed by name of the anion.
2. For cations that take on multiple charges, the charge is written using parentheses
immediately following the element name.

It is advisable that chemists use correct names of the compounds in their work. The other
names (trivial names) may however be acceptable in Applied Chemistry.
The names Quick lime and calcium oxide both indicate the same compound. Calcium
oxide is called a systemic name (unambiguous name) and translates the structure of
Quick lime clearly. It also provides an unambiguous reference to the compound.
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Systemic/Correct/unambiguous name of some compounds

Formula Systemic name Common name
Copper(I) chloride Cuprous chloride
Copper(II) chloride Cupric chloride
Iron(II) sulphate Ferrous sulphate
Iron(III) sulphate Ferric sulphate
Sodium chloride Brine
Sodium hydroxide Caustic soda
Sodium carbonate-10-water Washing soda
Calcium oxide Lime
Calcium carbonate Limestone
Potassium hexacyanoferrate(II) Potassium ferrocyanide
Potassium hexacyanoferrate(III) Potassium ferricyanide

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The selection of correct Roman numeral
Roman numerals should be used correctly when writing names of compounds. For
example the compound has only tin(IV) sulphate as the correct name.
Students normally write wrong names such as;
Wrong name Reason
Tin has more than one oxidation states (+2 and
Tin sulphate +4). Therefore its exact oxidation state in the
compound should be depicted
The oxidation state of +4 corresponds to tin and
Tin (IV) sulphate not the sulphate ion. It should be written
immediately after tin and not in the middle of the
compound
There should some little space between name of
Tin(IV)sulphate the cation with its charge, and name of the anion
Tin(iv) sulphate Roman numerals do not have dots (.) above them.
Tin(IIII) sulphate Roman numeral is wrong
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Writing the formula of a binary compound

At Ordinary level, the criss-cross method was used to write the formulae of compounds.
Another method may be used as follows;
Follow the steps below for formulae of Aluminium oxide and magnesium(II) chloride;
1. Write the symbol and charge of the
cation first and the anion next
2. Use a multiplier to make the total
charge on the cations and anions equal
and opposite to each other.
3. The multipliers are then used as
subscript for each ion.
4. The correct formula can then be
written, but the charges are left out
and all subscripts that are 1

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MASS SPECTROMETRY
Mass spectrometry (mass spectroscopy) is a technique used to determine relative atomic
masses and the relative abundance of isotopes, and for chemical analysis and the study of
ion reactions.
The earliest experiments of mass spectroscopy by J. J. Thomson used a stream of positive
ions from a discharge tube, which were deflected by parallel electric and magnetic fields
at right angles to the beam. Each type of ion formed a parabolic trace on a photographic
plate (a mass spectrograph). In modern instruments, the ions are produced by ionizing the
gas with electrons.

The essential parts and operation of a modern mass spectrometer

A mass spectrometer is usually used during mass spectroscopy. It is an instrument for
producing ions in a gas and analyzing them according to their charge/mass ratio.

It mainly consists of the vapourisation chamber, ionisation chamber, acceleration

chamber, deflection chamber, the detector, amplifier and recorder.
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Diagram showing the essential parts of a modern mass spectrometer

Hot tungsten filament

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1. The figure below shows a mass spectrum for chlorine.

(a) State the ions responsible for each of the peaks.

(b) State why the peaks of height 35 and 70 are relatively longer than other peaks.
(c) Use the spectrum to calculate the relative atomic mass of chlorine.
(d) When chloromethane is analysed in the mass spectrometer, two peaks are
observed having an abundance ratio of 3:1. Explain this observation.
(e) The mass spectrum of shows peaks corresponding to 1H, 2H, 12C, 13C,
35
Cl and 37Cl. Calculate the mass number of the
(i) most abundant molecular ion
(ii) heaviest molecular ion
(f) Write the formulae of all the possible ions that contribute to the peak at a mass
number 66.
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2. The mass spectrum of neon consists of three lines corresponding to relative

mass/charge ratios of 20, 21 and 22 with relative intensities in a ratio 0.91 : 0.0026 :
0.088 respectively. Calculate the relative atomic mass of neon.
3. Chlorine has two isotopes of relative atomic masses 34.97 and 36.96 respectively and
relative abundances of 75.77% and 24.23% respectively. Calculate the relative atomic
mass of chlorine.
4. Chlorine has two isotopes; chlorine-35 and chlorine-37. If the relative atomic mass of
chlorine is 35.5. Calculate the ratio of the two isotopes in a natural sample.
5. Natural oxygen consists of 99.76% of an isotope of mass 16, 0.04% of an isotope of
mass 17 and 0.20% of an isotope of mass 18. Calculate the average mass of an atom
of natural oxygen.
6. Copper, relative atomic mass 63.55 has two isotopes of mass numbers 63 and 65.
Calculate the percentage abundance of the isotopes.

THE MOLE CONCEPT

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The number of atoms in 1 mole of 12C is obtained by dividing 12g by the mass of an
individual atom of 12C . The answer has a value and is known as the
Avogadro constant (L). It is this value that is used to define an amount of a substance
known as a mole.
A mole is therefore defined as the amount of substance containing as many elementary
particles as those in 12 g of carbon-12
or
A mole is the amount of substance which contains elementary particles.
The particles may be molecules, atoms, ions, radicals, electrons or any other specified
particle.
Summary
Substance Atomic mass/ Number of particles
molecular mass
1 mole of atoms 12g atoms
1 mole of ions 24g ions
1 mole of 98g molecules
1 mole of atoms 14g atoms
1 mole of gas 28g molecules
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Calculating molar masses of elements and compounds

Molar mass is the mass of one mole of a substance.
Its unit is grams. The molar mass of carbon is 12 g. Molar mass has units but relative
molecular mass has no units.
Number of moles of a substance
Molar mass of an element relative atomic mass expressed in grams
Molar mass of a compound relative molecular mass expressed in grams

Examples
Calculate the molar masses of the following
(i) Ethanol
(ii) Carbon dioxide
(iii) Potassium iodate
(iv) Sodium thiosulphate-5-water

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A similar approach as that of O level is used. But take note that molar mass has units
Consider a compound Z whose molecular formula is , with atomic
masses

The molar mass of Z is given as

Molar mass
(i) Ethanol (ii) Carbon dioxide

(iii) Potassium iodate (iv) Sodium thiosulphate-5-

water

Molar mass-mole conversions

In order to make these conversions, molar mass should be calculated from the molecular
formula of the compound. It should be ascertained that a correct formula of the
compound in terms of number of atoms is written. If the formula is wrong, then the molar
mass cannot be correct
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1 mole of a compound weighs the relative molecular mass in grams.

Number of moles of a substance

Molar mass of a substance

Mass of a substance
Although the above formulae are well known and ease calculation work, it is advisable
to use first principles in the examination work.
Examples

(a) Calculate the number of moles in;

(i) 3.16g of potassium manganate(VII)
(ii) 0.5g of potassium persulphate

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(i) Molar mass of potassium (ii) Molar mass of potassium persulphate
manganate(VII)

( ) ( )

(b) Calculate the mass contained in moles of potassium chlorate

Molar mass of potassium chlorate

( )

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Questions
1. Work out the molar masses of each of the following

(i) Chlorine gas (x) Potassium iodate

(ii) Iodine molecule (xi) Potassium persulphate( potassium
(iii) Oxalic acid crystal peroxodisulphate)
(iv) Sodium ethanedioate (xii) Potassium dichromate(VI)
(v) Sodium carbonate decahydrate (xiii) Potassium manganate(VII)
(vi) Sodium hydrogencarbonate (xiv) Hydrochloric acid
(vii) Sodium hydroxide (xv) Hydrogen peroxide
(viii) Disodium tetraborate (xvi) Sulphuric acid
decahydrate (xvii) Iron(II) sulphate-7-water
(ix) Potassium chlorate (xviii) Diammonium iron(II) sulphate
hexahydrate

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2. Calculate the number of moles in;
(i) 1.0g of potassium iodate
(ii) 19.1g of disodium tetraborate decahydrate
(iii) 1.0g of sodium ethanedioate
(iv) 6.0g of Diammonium iron(II) sulphate-6-water
(v) 1.2g of potassium dichromate
(vi) 6.2g of copper(II) sulphate pentahydrate
3. Determine the mass of;
(i) 0.01288 moles of chlorine gas
(ii) moles of potassium iodate
(iii) moles of sodium hydrogencarbonate
(iv) 0.025 mole of sodium ethanedioate
(v) 0.00833 mole of copper(II) ions

Limiting reactants and excess reactants

In a perfect reaction, we would have exactly as much of each reactant that we need to
convert everything to a product. However in real practice, it is much more likely that we
have non-stoichiometric amounts of reactants.
Consider a scenario where we are making grilled cheese sandwiches.
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Stoichiometric amounts of cheese and bread required are in a ratio 1:2. If we are provided
with 28 slices of bread and 11 slices of cheese, one would prepare 11 sandwiches using
all the provided cheese and 22 slices of bread. This leaves six slices of bread not used. In
this scenario, the number of sandwiches prepared is limited by the number of cheese
slices and the bread slices have been provided in excess.
A limiting reactant is that reactant which is completely used up in a chemical reaction
and limits the quantities of the products formed.
An excess reactant is that reactant that remains after a chemical reaction due to the
limiting reactant being used up.
Percentage yields in a chemical reaction
The amount of product that may be produced by a chemical reaction under specified
conditions, as calculated per the stoichiometry of an appropriate balanced chemical
equation is called theoretical yield of the reaction. In practice, the amount of product
obtained is called the actual yield, and is often less than the theoretical yield for a

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

number of reasons. This is because some reactions are inherently inefficient, being
accompanied by side reactions which produce other products. Others by nature are
incomplete. Some products are difficult to collect without some loss, and so less than
perfect recovery will reduce the actual yield.
The extent to which a reaction‟s theoretical yield is expressed as percentage yield.

( )

Experiment to demonstrate concept of limiting and excess reactants,

theoretical yield, actual yield and percentage yield.

Weigh a beaker and record its mass ( ).

Then weigh accurately 1.00g of iron powder into the beaker.
Measure 30cm3 of 1.0M copper(II) sulphate solution using a measuring cylinder and
slowly add it to the beaker above.
Stir the solution until the solution has completely turned colour from blue and a brown
copper solid formed.

Decant off the resultant solution carefully and do not lose any copper formed.
The copper formed is washed several times with distilled water, and then with acetone,
and dried.
The beaker together with dried copper is weighed ( ).
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Treatment of results;

⁄
⁄

( )

( )

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Examples
1. What mass of aluminium chloride can be formed from 34.0g of aluminium and
12320 cm3 of chlorine gas?
( 1 mole of a gas occupies 22.4 litres at s.t.p; )
⁄
⁄

( )

( )

( )
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2. Sodium carbonate reacts with calcium chloride to form calcium carbonate and
sodium chloride. In an experiment, 53g of sodium carbonate and 44.4 g of
calcium chloride were mixed forming 23.6g of calcium carbonate.
(i) What is the limiting reagent of the reaction?
(ii) Calculate the percentage yield of calcium carbonate.

⁄
⁄

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The limiting reagent is used to calculate percentage yield.

( )

( )

3. 0.50g of a fertilizer containing ammonium sulphate was warmed with sodium

hydroxide solution to expel all ammonia gas which was trapped and absorbed in
100cm3 of 0.10M hydrochloric acid solution. The excess acid required 55.90 cm3
of 0.1M sodium hydroxide solution for neutralisation. Calculate the percentage
of ammonium sulphate in the sample.
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Theory; Warming any ammonium salt with an alkali liberates ammonia gas. All the
ammonia formed reacted with hydrochloric acid but the acid was as excess reactant and
ammonia was limiting. So the excess hydrochloric acid(that did not react with ammonia)
was neutralized with sodium hydroxide.
Moles of that reacted with excess acid

( )

Original number of moles of hydrochloric acid

( )
Number of moles of hydrochloric acid that reacted with ammonia

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

( )

( )

Questions
1. What is the limiting reagent when 5.00g of hydrogen and 10.0g of oxygen react to
form water?
2. Toluene is oxidised by air under carefully controlled conditions to benzoic acid.
Benzoic acid is used to prepare the food preservative, sodium benzoate. What is the
percentage yield of a reaction that converts 1.000 kg of toluene to 1.21kg of benzoic
acid?
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3. In a laboratory experiment, the reaction of 3 moles of hydrogen with 2 moles of

iodine produced 1 mole of hydrogen iodide. Determine the theoretical yield in grams
and percentage yield.
4. 1.274g of copper(II) sulphate was reacted with excess zinc metal to produce 0.392g of
copper. Calculate the percentage yield.
5. 1.07g of anhydrous sodium carbonate was dissolved in 50cm3 of an acid solution. The
resultant solution required 24.6cm3 of 0.237M sodium hydroxide for complete
neutralisation. Calculate the molarity of the acid solution.
6. 27.825g of a normal carbonate of a univalent metal Y, was dissolved in 320.0cm3 of a
2.5M monobasic acid solution. The resultant solution was boiled, cooled and diluted
to one litre of solution. 25cm3 of this solution required 34.375cm3 of 0.2M potassium
hydroxide for complete neutralisation. Calculate the relative atomic mass of Y.
7. 50cm3 of a concentrated solution of hydrochloric acid was added to 200cm3 of 0.5M
sodium hydroxide solution. The excess base required 35.0cm3 of 0.2M nitric acid

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

solution for complete neutralisation. Calculate the molarity of the concentrated
hydrochloric acid solution.
8. 50cm3 of concentrated potassium hydroxide solution was diluted to 250cm3. 25cm3 of
this solution was reacted with 100cm3 of 0.5M hydrochloric acid. If 26.42cm3 of
0.125M sodium hydroxide solution was needed to neutralise the excess acid.
Determine the molarity of the potassium hydroxide in the original 50cm3.

PRIMARY AND SECONDARY STANDARDS

A primary standard is a substance that is analytically pure and chemically stable such
that a known mass of it when weighed is the exact mass that dissolves in water to form
a standard solution.
A standard solution is a solution whose concentration is accurately known i.e. one that
contains a known amount of solute in a known volume of solution.
A primary standard can be used directly for the preparation of standard solutions without
reference to some other concentration standard.
A primary standard has the following characteristics;
1. Readily soluble in water at room temperature such that all the weighed mass goes into
solution.
2. It should have a fairly high molar mass such that weighing errors are minimized.
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3. It should be obtainable in a pure state such that the quantity weighed indicates the
actual mass present in the standard solution prepared.
4. It should not be deliquescent, efflorescent or hygroscopic such that the mass weighed
is exactly that of the pure sample
5. It must be stable at ordinary temperatures (should not decompose easily) such that its
chemical nature is not altered.
6. It should be able to undergo stoichiometric and instantaneous reactions such that
titration errors are minimized.

Examples of common primary standards include;

Name of primary standard Formula
Anhydrous sodium carbonate
Sodium hydrogencarbonate
Ethane-1,2-dioic acid(Oxalic acid)

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Sodium oxalate
Butane-1,4-dioic acid
Disodium tetraborate decahydrate
(Borax)
Potassium iodate
Sodium bromate
Most of the other substances make solutions of approximately known concentrations
which must be standardized against a primary standard. These are called secondary
standards.
A secondary standard is a substance that is not analytically pure and chemically
unstable such that a known mass of it when weighed and dissolved in water makes
solutions of approximate concentrations hence must be standardized by titration.
Examples of secondary standards include
Name of secondary standard Formula Suitable substance(s) to standardise
the secondary standard
Sodium hydroxide Oxalic acid
Sulphuric acid Anhydrous sodium carbonate
Hydrochloric acid Disodium tetraborate decahydrate
(Borax)
Anhydrous sodium carbonate
Nitric acid Anhydrous sodium carbonate
Potassium manganate(VII) Sodium oxalate
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Oxalic acid
Sodium thiosulphate pentahydrate Potassium iodate
Potassium bromate
Sodium hydroxide which cannot be used to make a standard solution because;
1. During weighing, it absorbs water vapour from the air.
2. It also reacts with carbon dioxide in the air to form sodium carbonate.

Sulphuric acid and hydrochloric acid are not suitable for use as primary standards
because the concentrations of their concentrated solutions are not accurately known.
Nitric acid is not a suitable primary standard because it always contain a little nitrous
acid which has a destructive action on so many acid-base indicators.
Potassium manganate(VII) is commonly used in volumetric analysis because;
1. It forms coloured solutions so it acts as own indicator
2. It oxidises a wide range of substances
3. It is not affected by the atmosphere while being weighed

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

4. It is fairly soluble in water
5. Has a high molecular mass hence minimising weighing errors
However, it is not a good primary standard because;
 It is never obtained free from manganese(IV) oxide impurity
 It is easily reduced by even weak reducing agents since it is a strong oxidising
agents
Potassium manganate(VII) can be acidified by sulphuric acid but neither acidified with
hydrochloric acid nor nitric acid during titration because;

It oxidises hydrochloric acid to chlorine as it is reduced to manganese(II) ions.

Nitric acid is itself an oxidising agent hence interferes with the oxidising ability of
manganate(VII) ions.
Sodium thiosulphate cannot be used as a primary standard because;
1. It is efflorescent
2. When its solution is left in air it forms a yellow solid deposit and bubbles of a
colourless gas.

This is because a solution of sodium thiosulphate absorbs carbon dioxide from the air
which dissolves to form a weak carbonic acid. The acidic medium promotes
disproportionation of thiosulphate ions into sulphur dioxide and sulphur, which is
insoluble.
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Preparation of standard solutions by weighing and dissolving in water

Preparing a standard solution of anhydrous sodium carbonate (for example 250cm 3 of
0.2M sodium carbonate solution)
(i) Calculate the mass of anhydrous sodium carbonate needed to make the
standard solution.
250cm3 of 0.2M sodium carbonate solution

( )

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(ii) Weigh a clean weighing bottle, and record its mass (to 1 or 2 decimal places). Use
a clean spatula and add pure anhydrous sodium carbonate to the weighing bottle
until the mass is the total mass of the weighing bottle and that of anhydrous
sodium carbonate required.
Sample Results:
Mass of anhydrous sodium carbonate + weighing bottle 45.30 g
Mass of empty weighing bottle 40.00 g
Mass of anhydrous sodium carbonate used 5.30 g
(iii) Transfer the weighed mass of anhydrous sodium carbonate carefully into a clean
beaker. Using a wash bottle of distilled water, add a small volume of water so that
all the washings run into the beaker. Add about 100 cm3 of and stir with a glass
rod until all the solid has dissolved.
(iv) Pour all the solution carefully through a filter funnel into a graduated flask
(volumetric flask). Wash all the solution out of the beaker and off the glass rod to
the volumetric flask.
(v) Add distilled water until the level of the solution is about 2 cm below the
graduation mark (in this case 250cm3). Add the rest of the distilled water drop by
drop from a dropping pipette until the bottom of the meniscus is level with the
graduation mark when viewed at eye level.
(vi) Label the solution as required.
Questions;

(a) Why is sodium hydrogencarbonate a suitable substance for preparing standard

solutions?
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(b) Calculate the mass of sodium hydrogencarbonate required to prepare 500cm3 of a

0.01M solution.
(c) Describe how you would prepare the solution in (b) above as accurately as possible.

VOLUMETRIC ANALYSIS
Common terms used in volumetric analysis
Titrant
This is a reagent of known concentration that is added to another solution to determine
the concentration of the second chemical species.
Titrand/ Analyte
This is a reagent whose concentration is not known and has to be determined by
titration.
Equivalence point

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This is the point when the number of moles titrant is equal to number of moles of
analyte. It occurs before end point, which signals the completion of the reaction.
End point
A point in a titration at which the reaction is complete, observed by the colour change
of an indicator and occurs when small amount of solution of known concentration is
added to a solution whose concentration is to be determined. It occurs after
equivalence point.

Standard solution
A standard solution is a solution whose concentration is accurately known i.e. one that
contains a known amount of solute in a known volume of solution.
Volumetric analysis is a means of finding the concentration of a solution. In this method,
a solution of an acid is added to a solution of a base until there is just enough of the acid
to neutralize the base. This is done by titration.
The concentration of one of the two solutions should be known, and the volumes of both
the solutions must be measured.
A standard solution of a base may be used to find the concentration of the solution of an
acid. The volume of the acid solution of unknown concentration required to neutralise a
known volume, usually 25.0 cm3 of a standard solution of the base is determined. An
indicator is used to determine when the right volume of a solution has been added to
another solution for complete neutralisation.
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Set up of apparatus for volumetric analysis

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Acid-base titrations and use of data obtained
Acid-base titrations may involve one- indicator titrations or double indicator titrations.
Double indicator titrations will be exploited more in practical lessons by your teacher.
One indicator titrations involve standardizing an acid or base using a standard solution of
a base or acid with the aid of a suitable indicator. Calculation problems involving
standardisation involve the following steps;
(i) Calculating the moles of the standard solution in the total volume of solution(
commonly the total volume is 250cm3 of the solution but can be any other value)
(ii) Calculating the moles of the standard solution used during the reaction (usually
25.0, 20.0 or can be 10.0cm3)
(iii) Calculating moles of the solution that is standardized using equation of the
reaction(mole ratio)
(iv) Determining the molarity of the solution that is standardized.

Examples
1. Standardization of hydrochloric acid using Borax

5.7g of disodium tetraborate decahydrate(Borax) were dissolved

3 3
in 100 cm distilled water in a 250cm volumetric flask, shaken to dissolve and the
mixture made up to the mark with distilled water. 25.0 cm3 of the resultant solution
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is pipetted into a clean conical flask and titrated against dilute hydrochloric acid
solution which was approximately 0.1M using phenolphthalein indicator. 18.0 cm3
of the acid was required for complete neutralisation. Calculate the molarity of the
hydrochloric acid solution used.
(i) Moles of in the 250cm3 of the solution

(ii) moles of used during the reaction (moles in 25.0cm3)

( )
(iii) moles of the solution that is standardized using equation of the reaction(mole ratio)
Equation;

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( ) ( )

(iv) molarity of hydrochloric acid

( )

( )

Note; The concentration of the acid given in the question is approximate hence used
nowhere in the calculation. Remember standardizing means we are ascertaining the
actual concentration of the acid.
Over rounding should be avoided before getting the final answer to minimize errors in
calculation.
2. Standardisation of hydrochloric using anhydrous sodium carbonate.

You are provided with the following:

FA1 which is 60 cm3 of hydrochloric acid solution
Solid Y which is anhydrous sodium carbonate
Methyl orange indicator
You are required to determine the molarity of FA1 using a standard solution of
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anhydrous sodium carbonate.

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PROCEDURE:
Accurately measure 40 cm3 of FA1 and add exactly 60 cm3 of distilled water. Label the
resultant solution FA3.
Weigh accurately 1.5g of solid Y into a clean 250cm3 volumetric flask and add about 100
cm3 of distilled water. Shake well to dissolve. Add more distilled water to fill up to the
mark and label the resultant solution FA2
Pipette 25.0 cm3 (or 20.0 cm3) of FA2 into a clean conical flask. Add 2 or 3 drops of
methyl orange indicator.
Titrate the resultant mixture against FA3 from the burette until the endpoint is reached.
Repeat the titration until you obtain consistent results.
Record your results in the table below.

Sample Results:
Mass of Y and weighing bottle 41.50 g

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Mass of empty weighing bottle 40.00 g
Mass of Y used 1.50 g
Volume of pipette used 20.0 cm3
Final burette reading(cm3) 27.50 37.40 32.50
Initial burette reading(cm3) 0.00 10.00 5.00
Volume of FA3 used(cm3) 27.50 27.40 27.50

Record the titre values used to calculate the average volume of FA3 used.
cm3
Average volume of FA3 used cm3
Questions:
Calculate the molarity of hydrochloric acid in FA1.
We should begin the treatment of results with the standard solution which is in this case
FA2.
(i) Moles of solid Y in the 250cm3 of FA2.
Since the same mass of Y(1.5g) in 100cm3 of FA2 is also in the 250cm3 of FA2, the
moles of anhydrous sodium carbonate in both volumes is the same.

(ii) moles of used during the reaction (moles in 20.0cm3)

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( )
(iii) moles of hydrochloric acid in FA3 that reacted with in FA2 Equation;

( ) ( )

(iv) molarity of FA1

Note that in the experiment, FA1 is not directly used but instead the diluted solution which is
FA3. Moles of HCl in the volume used of FA3 should be calculated first. Then moles of the acid
in the diluted solution (60+40)cm3

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( )

( )

Dilution does not change number of moles in a given solution. Therefore moles of HCl in 100cm3
of FA3 are the same as those in 40cm3 of FA1

( )

( )

Exercise on dilution and standardisation

1. During a titration, 20cm3 of 0.2M sodium hydrogencarbonate solution reacted
completely with 32.80cm3 of a solution of nitric acid. Calculate the molarity of nitric
acid.
2. 30 cm3 of sodium hydroxide solution reacted completely with 25.0 cm3 of 0.5M
hydrochloric acid solution. Determine the molarity of sodium hydroxide solution.
3. 25.0 cm3 of 0.2M sodium ethanedioate solution was warmed up to 65℃ and titrated
against a solution of potassium manganate(VII). Calculate the molarity of potassium
manganate(VII) if 17.20 cm3 of the oxidant was used.
4. 1.50g of anhydrous sodium carbonate were dissolved in 100 cm3 distilled water in a
250cm3 volumetric flask, shaken to dissolve and the mixture made up to the mark
with distilled water. 20.0 cm3 of the resultant solution is pipetted into a clean conical
flask and titrated against dilute hydrochloric acid solution using methyl orange
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indicator. 27.50 cm3 of the acid was required for complete neutralisation. Calculate
the molarity of the hydrochloric acid solution used.

Practical exercises on standardisation

1. You are provided with:
FA1 which is approximately 0.1M hydrochloric acid solution
Solid Q which is hydrated disodium tetraborate (Borax)
Phenolphthalein indicator
You are required to standardise hydrochloric acid in FA1 using a standard solution of
Borax.
PROCEDURE:
Weigh accurately 4.7g of solid Q into a clean 250cm3 volumetric flask and add about 100
cm3 of distilled water. Shake well to dissolve. Add more distilled water to fill up to the
mark and label the resultant solution FA3
Pipette 25.0 cm3 (or 20.0 cm3) of FA3 into a clean conical flask. Add 2 or 3 drops of

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phenolphthalein indicator and shake the flask carefully.
Titrate the solution carefully against FA1 from the burette until the endpoint is reached.
Repeat the titration until you obtain consistent results.
Record your results in the table below.

Results:
Mass of Q and weighing bottle.................................................................................g
Mass of empty weighing bottle.................................................................................g
Mass of Q used.........................................................................................................g
Volume of pipette used..........................................................................................cm3
Final burette reading(cm3)
Initial burette reading(cm3)
Volume of FA1 used(cm3)
Record the titre values used to calculate the average volume of FA1 used.
...............................................................................................................................cm3
Average volume of FA1 used............................................................................... cm3
Questions:
Calculate the concentration of hydrochloric acid in FA1 per litre of solution.
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
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................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
2. You are provided with:
FA1 which is approximately 0.2M hydrochloric acid solution
Solid M which is anhydrous sodium carbonate
Methyl orange indicator
You are required to standardise hydrochloric acid in FA1 using a standard solution of
anhydrous sodium carbonate.

PROCEDURE:
Weigh accurately 2.7g of solid M into a clean 250cm3 volumetric flask and add about
100 cm3 of distilled water. Shake well to dissolve. Add more distilled water to fill up to
the mark. Label this solution FA2
Pipette 25.0 cm3 (or 20.0 cm3) of FA2 into a clean conical flask. Add 2 or 3 drops of

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methyl orange indicator and shake the flask carefully.
Titrate the solution against FA1 from the burette until the solution just turns orange.
Repeat the titration until you obtain consistent results.
Record your results in the table below.

Results:
Mass of M and weighing bottle.................................................................................g
Mass of empty weighing bottle.................................................................................g
Mass of M used.........................................................................................................g
Volume of pipette used..........................................................................................cm3
Final burette reading(cm3)
Initial burette reading(cm3)
Volume of FA1 used(cm3)
Record the titre values used to calculate the average volume of FA1 used.
...............................................................................................................................cm3
Average volume of FA1 used............................................................................... cm3

Questions:
Calculate the percentage error in the concentration of hydrochloric acid in FA1.
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
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................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
................................................................................................................................................
NOTE:
(i) Volume of pipette is recorded to 1 decimal place.
(ii) Titre values in the table must be recorded to 2 decimal places
(iii) Titre values chosen to obtain average volume should be within difference
(iv) All steps in your calculations should be shown and strictly use first principles.

Back titrations
Back titration is a technique in volumetric analysis in which a known volume of an
excess standard solution is added to the solution to be analysed. The amount of the
unreacted standard solution is then determined by titration with another standard solution.

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For example an excess of a solution of iron(II) ions of known concentration can be added
to a solution of potassium peroxodisulphate or potassium chlorate(V). Some of the
iron(II) ions are oxidised to iron(III) ions as shown by the equations below;

The resultant solution which then contains unreacted iron(II) ions can then be titrated
against a standardised potassium manganate(VII) solution in acidic medium or any other
oxidising agent.

The analysis usually flows by the steps below;

(i) Calculate the number of moles of permanganate that reacted with the excess
iron(II) ions.
(ii) Use mole ratio to determine the number of moles of excess moles of iron(II)
ions. (moles of iron(II) ions that did not react with
peroxodisulphate/chlorate(V).
(iii) Calculate the number of moles of iron(II) ions in the original solution
(iv) By subtraction, obtain the number of moles that reacted with the
peroxodisulphate/ chlorate(V)
(v) Moles ratio of the reaction, percentage purity or formula mass can then be
determined using the usual approaches.

Example
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(a) A solution was made by dissolving 39.2g of ammonium ferrous sulphate,

in a litre of distilled water. 25.0cm3 of this solution
was pipetted into a conical flask. To it was added 20 cm3 of 2M sulphuric acid
and titrated against potassium manganate(VII) solution. 25.00cm3 of the
permanganate was required for complete reaction. Calculate the concentration
of manganate(VII) ions in moles per litre.
(b) 0.5g of a solid was accurately weighed and put in a beaker. 50 cm3 of
distilled water was added and the mixture stirred to dissolve. The resultant
solution was transferred into a 250cm3 volumetric flask and 150 cm3 of the same
ammonium ferrous sulphate used in (a) was added. The solution in the flask was
made up to the mark with distilled water, shaken and allowed to stand for about
5 minutes. 25.0cm3 of this solution was pipetted into a conical flask and to it was
added 10cm3 of 2M sulphuric acid and titrated with the same potassium
manganate(VII) solution used in (a). 11.30 cm3 of the permanganate was

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required for complete reaction. Calculate the number of moles of:
(i) excess iron(II) ions in 250cm3 of the solution in the volumetric flask
(ii) iron(II) ions that reacted with
(iii) molar mass of
(iv) formula mass of
(a)

( )

The sulphuric acid is just used to provide acidic medium for the redox reaction but its
volume and concentration is not used anywhere in the calculation.

( )
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( )

(b)
(i) number of moles of excess iron(II) ions in 250cm3 of the solution in the volumetric
flask

( )

( )

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Note that are the moles of excess iron(II) ions that reacted with
manganate(VII) ions but they are the excess moles in 25.0cm3 of solution.

( )

(ii) number of moles of iron(II) ions that reacted with

( )

Note that of iron(II) ions were added to the persulphate solution. Some of
these reacted with the persulphate and the excess moles calculated above did not react.
(iii) molar mass of

( )
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( )

(iv) formula mass of

Question
3
(a) 10.0cm of a solution of ammonium iron(II) sulphate-6-water, of unknown
concentration was pipetted into a conical flask. To it was added an equal volume of

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2M sulphuric acid and then titrated against a solution made by dissolving of
3
potassium manganate(VII) in a litre of distilled water. 9.90cm of the permanganate
solution was required for complete reaction. Calculate the molar concentration of the
solution of ammonium iron(II) sulphate-6-water.

(b) 0.5g of an impure solid potassium chlorate was accurately weighed and put in a
beaker. 100 cm3 of distilled water was added and the mixture stirred to dissolve. The
resultant solution was transferred into a 250cm3 volumetric flask and the solution was
made up to the mark with distilled water. 10.0cm3 of this solution was pipetted into a
conical flask and to it was added 35.0 cm3 of the same ammonium iron(II) sulphate-6-
water solution used in (a) followed by an equal volume of 2M sulphuric acid. The
mixture was heated to about 85℃ and then cooled in cold water for 3 minutes and the
cold mixture titrated with the same permanganate solution used in (a). 25.20 cm3 of
the permanganate was required for complete reaction. Calculate the number of moles
of:
(i) excess iron(II) ions that reacted with manganate(VII) ions.
(ii) iron(II) ions that reacted with the 10 cm3 of chlorate(V) ions.
(iii) Percentage purity of the potassium chlorate.

OXIDATION NUMBER (OXIDATION STATE)

Oxidation number the net charge that would remain on an atom in a given compound
when all the other atoms bonded to it are removed one by one, each in its normal
valency state.
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Oxidation number can also mean the combining power of a substance with oxygen.

Calculating oxidation state

Rules to consider
 Oxidation numbers must be written with symbols (+ or -) to distinguish them from
valency. Superscripts (+3), subscripts (+3), and mere numbers (3) or words(three) are
not allowed
 Atoms in the elementary state have an oxidation number of zero.
 The molecules such as are assigned an oxidation number of
zero.
 In the case of simple atoms but in the combined state, the element has an oxidation
number with the same size and sign of the charge on its ion. For example
have oxidation numbers of +1, +2 and +3 respectively and have
oxidation number of -1.
 Atoms that are monoatomic can be assigned an oxidation number equal to their

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charge
 The oxidation number of H is +1 in most of its compounds but -1 in metallic hydrides.
 When two or more atoms of the same element occur in a compound, the oxidation
number of the element is an average of the oxidation number of the group.
 The oxidation state of the atom that is required is assigned an unknown letter say, x,
and the sum of the oxidation numbers on all atoms in the species is equated to the
overall charge on the species.

Examples
Calculate the oxidation state of the stated atom in the following species.
(i) Oxygen in
(ii) Oxygen in
(iii) Chorine in
(iv) Manganese in
(v) Chromium in
(vi) Sulphur in
(vii) Iron in [ ]
(viii) Cobalt in [ ]
(i) Let the oxidation state of O in be x. (v) Let the oxidation state of Cr in
be t.
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The oxidation state of O is therefore -2.

The oxidation state of Cr is therefore +6.
(ii) Let the oxidation state of O in be m. (vi) Let the oxidation state of S in
be a.

The oxidation state of O is therefore -1.

The oxidation state of S is therefore +7.

(iii) Let the oxidation state of Cl in be n. (vii) Let the oxidation state of Fe in
[ ] be y.

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The oxidation state of Cl is therefore +5.

The oxidation state of Fe is therefore +3.

(iv) Let the oxidation state of Mn in be (viii) Let the oxidation state of Co in
p. [ ] be q

The oxidation state of Mn is therefore +6.

The oxidation state of Co is therefore +3.

Questions
Calculate the oxidation state of the stated atom in the following species.
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REDOX REACTIONS
(OXIDATION-REDUCTION REACTIONS)
Oxidation numbers are very important in deciding whether a reaction is reduction,
oxidation and therefore a redox one.
Consider the half reactions below

In the first half reaction, copper(II) ions are converted to copper. The subsequent change
in oxidation number is therefore from +2 to 0. This is evident that the oxidation number
has decreased. Electrons are also gained in the reaction. This is therefore a reduction
reaction.
Reduction is therefore a reaction in which the oxidation number of an element is
decreased
or

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A reaction in which electrons are gained

In the second half reaction, zinc is converted to zinc ions. The subsequent change in
oxidation number is therefore from 0 to +2. This is evident that the oxidation number
has increased. Electrons are also lost in the reaction. This is therefore an oxidation
reaction.

Oxidation is a reaction in which the oxidation number of an element is increased

or
A reaction in which electrons are lost
When the combined cell of the two reactions and is made, an overall reaction can
be generated by crossing out the electrons.

This reaction involves ; oxidation number 0 , being converted to ; oxidation

number +2. ; oxidation number +2 is converted to ; oxidation number, 0
Zinc has been oxidised and copper has been reduced. This is therefore a redox reaction.
A redox reaction is a reaction in which oxidation and reduction take place
simultaneously.
The zinc metal loses (donates) the electrons that are gained (accepted) by copper(II) ions.
Any substance that donates electrons is a reducing agent and any substance that accepts
electrons is an oxidizing agent.
An oxidizing agent is an acceptor of electrons
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A reducing agent is a donor of electrons

The mnemonics below can be used to remember the concepts well.
OIL RIG – Oxidation is loss of electrons, Reduction is gain of electrons
LEORA says GEROA- loss of electrons is oxidation (Reducing agent). Gain of electrons
is reduction (Oxidising agent)

Oxidizing species and their reduction products

No. Oxidizing agent Colour Reduction product Colour
1 Purple solution Colourless
2 Orange solution Green
3 Black solid Colourless
4 Yellow solution
5 Yellow solution
6 Dark brown solid Colourless
7 Colourless Brown

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8 Colourless Colourless gas
9 Colourless Brown fumes
10 Colourless Colourless
11 Yellow or brown Green
solution
12 Colourless Colourless
13 Brown
14 Reddish brown
15 Greenish yellow gas

 The first ten species act as oxidizing agents in acidic medium and the species 11-15
gain electrons in the redox reactions in which they behave as oxidizing agents.
 The colours of some species in solutions have not been indicated because the colour
of solutions in which they exist depend on the colour of cations present.
 Below are half-cell reactions for some of the species showing the electron gain. In
each of the reactions, the electrons balance the total charge on the left hand side and
on the right hand side.

Try to write out half-cell reactions for the other species on your own in the provided
space below.
1.
2.
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3.
4.

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Reducing agents and their oxidation products
No. Reducing agent Colour Oxidation Colour
product
1
2
3 Orange solution Blue solution
4 Yellow solution Blue solution
5 Pale pink solution Purple solution
6 Greenish yellow gas
7 Reddish brown solution
8 Brown solution
9 Colourless gas with a Yellow solid
rotten egg smell
10 Colourless solution Colourless gas
11 Colourless liquid Colourless gas
12 Brown solid Blue solution
13 Green solution Yellow or Brown solution
14 Colourless solution Colourless solution
15 Colourless solution Colourless solution

 The first five species act as reducing agents in solution (presence of water)
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 The colour of some species in solutions have not been indicated because the colour of
solutions in which they exist depend on the colour of cations present.
 Below are half-cell reactions for some of the species showing the electron loss. In
each of the reactions, the electrons balance the total charge on the left hand side and
on the right hand side.

Try to write out half-cell reactions for the other species on your own in the provided
space below.
1.
2.
3.
4.

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Deriving equations for redox reactions

General steps taken
1. Identify the reducing and oxidizing species in the redox reaction. The oxidizing species is
normally that one whose central atom is in the highest oxidation state such that it is
reduced to a lower oxidation state. The reducing agent is that one whose central atom
exists in the lowest oxidation state such that is oxidised to a higher oxidation state.
2. Write well balanced half-cell reactions for both the oxidation and reduction processes.
Make sure the equations are balanced both in terms of atoms and charge.
The atoms are balanced the usual way of balancing any equation and the charge is
balanced in terms of electrons.
You should note that in the reduction half equation, electrons are always on the left hand
side and in the oxidation half equation they are on the right hand side.
3. Multiply each of the half equations by suitable factors so as to make the number of
electrons in each equation equal.
4. Cross out everything that appears on the left hand side of one equation and on the right

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hand side of the other. Species to always consider for this step are electrons, and .
The hydrogen ions or water species in one equation are normally more than those in the
other. Subtraction is done and the remaining hydrogen ions or water molecules written on
the side which originally had more of the species. Once electrons still appear in this
equation, then something is not correct
5. The overall equation is now written with all the species on the left hand side maintained
there as well as those on the right hand side.
6. Note that for examination purposes space is not enough to do all this hence side work is
done and only overall equation written in the space provided. Writing other equations
other than overall equation may lead to loss of marks. Half equations can only be written
if required by examiner.
If the observation is as well required, then it is written first before the general equation.

Examples
State what would be observed and explain your observation when;
1. Concentrated hydrochloric acid was added to potassium manganate(VII)
solution
Step 1; Oxidizing species is from potassium manganate(VII) and
reducing species is from hydrochloric acid.
Step 2;
Reduction half equation;

Oxidation half equation;

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Step 3;

The first equation is mutiplied by 2 and the second equation by 5. This is intended to
make the number of electrons in each equation the same (10). Also note that these
factors do not multipy only the electrons but also every other species in the equation.

This now gives;

Step 4;
The electrons are equal and crossed out.

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Step 5;
Observation; The purple solution turns colourless and bubbles of a greenish yellow gas
evolved.
Explanation;
Potassium manganate(VII) oxidises hydrochloric acid to chlorine as it is reduced to
manganese(II) ions.

2. Hydrogen sulphide gas was bubbled through acidified potassium dichromate(VI)

solution.
Step 1; Oxidizing species is from potassium dichromate and reducing
species is
Step 2;
Reduction half equation;

Oxidation half equation;

Step 3;
The first equation is left as it is but the second equation multiplied by 3. This is
intended to make the number of electrons in each equation the same (6). If you choose
to multiply the first equation by 2 and the second by 6. Then you will have to divide
the stoichiometric coefficients in the final equation by a given factor through out.
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This now gives;

Step 4;
The electrons are equal and crossed out. The are subtracted from the to
give on the left hand side.

Step 5;
Observation; The orange solution turns green and a yellow solid deposited.
Explanation;
In acidic medium, dichromate ions oxidise hydrogen sulphide to Sulphur as they are
reduced to chromium(III) ions.

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3. Hydrazine was added to acidified potassium manganate(VII) solution
Step 1; Oxidizing species is from potassium manganate(VII) and
reducing species is .
Step 2;
Reduction half equation;

Oxidation half equation;

Step 3;
The first equation is multiplied by 4 and the second equation multiplied by 5. This is
intended to make the number of electrons in each equation the same (20).
This now gives;

Step 4;
The electrons are equal and crossed out. The are subtracted from the to
give on the left hand side.

Step 5;
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Observation; The purple solution turns colourless and bubbles of a colourless gas
evolved.
Explanation;
Manganate(VII) ions oxidise hydrazine to nitrogen gas as they are reduced to
manganese(II) ions.

4. Chlorine was bubbled through potassium nitrite solution.

Step 1; Oxidizing species is and reducing species is .
Step 2;
Reduction half equation;

Oxidation half equation;

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Step 3;
Since the number of electrons in both equations is the same, the overall equation can be
written right away
Step 4;
The electrons are equal and crossed out.

Step 5;
Observation; Greenish yellow gas dissolved and a colourless solution is formed.

Explanation;
Chlorine oxidises nitrate ions to nitrite ions and itself reduced to chloride ions.

5. Manganese(IV) oxide was added to acidified solution of sodium oxalate and the
mixture heated

Step 1; Oxidizing species is and reducing species is .

Step 2;
Reduction half equation;

Oxidation half equation;

Step 3;
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Since the number of electrons in both equations is the same, the overall equation can be
written right away
Step 4;
The electrons are equal and crossed out.

Step 5;
Observation; Black solid dissolved forming a colourless solution and bubbles of a
colourless gas
Explanation;
Manganese(IV) oxide oxidises oxalate ions to carbon dioxide and itself reduced to
manganese(II) ions.

Balancing redox reactions in alkaline media

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Although manganate(VII) ions are strongly oxidizing in acidic medium, they can also
oxidise in neutral or weakly alkaline medium, in which the half reaction is;
̅
It oxidises potassium iodide to potassium iodate in the alkaline medium
Qn. State what would be observed and write an equation for the reaction when
potassium iodide was added to an alkaline solution of potassium manganate(VII)

Then;
̅

On crossing out the electrons and combining the two equations we have;
̅
The on the right hand side are as a result of complete neutralisation of the
by 6 of the ̅ leaving a remainder of ̅ . Subtraction leaves
only one water molecule on the reactant side.
Observation;
Purple solution forms a colourless solution and black solid deposited.
Equation
̅
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Although hydrogen peroxide is a strong oxidizing agent in acidic medium, it sometimes

shows reducing properties depending on the conditions. Thus in alkaline conditions,
hydrogen peroxide reduces iron(III) ions to iron(II) ions.
The half reaction is;
̅
Qn. State what would be observed and write an equation for the reaction when
Iron(III) chloride was added to an alkaline solution of hydrogen peroxide.
̅

Then;
̅

Observation; Brown solution turns green and bubbles of a colourless gas.

Equation;
̅

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Questions
State what would be observed and write equation for the reaction when;
1. Sodium bromide solution was added to tin(IV) chloride solution
2. Potassium iodide was added tin(IV) chloride solution
3. Concentrated hydrochloric acid was added to potassium manganate(VII) solution
4. Manganese(IV) oxide was added to hot concentrated hydrochloric acid
5. An acidified solution of hydrogen peroxide was added to manganese(IV) oxide.
6. Concentrated hydrochloric acid was added to lead(IV) oxide and the mixture heated
7. Tin(II) sulphate solution was added to acidified potassium permanganate solution
8. Chlorine was bubbled through iron(II) chloride solution.
9. Hydrogen sulphide gas was bubbled through acidified potassium dichromate(VI)
solution.
10. Bromine water was added to iron(II) chloride solution.
11. Hydrazine was added to acidified potassium manganate(VII) solution
12. Tin(II) sulphate solution was added to iron(III) sulphate solution
13. Chlorine was bubbled through potassium nitrite solution.
14. Chlorine gas was bubbled through sodium sulphite.
15. Limited chlorine gas was bubbled through sodium thiosulphate solution.
16. Excess chlorine gas was bubbled through sodium thiosulphate solution.
17. Sulphur dioxide was bubbled through acidified potassium manganate(VII) solution.
18. Sodium sulphite was added to acidified potassium manganate(VII) solution.
19. Iodine solution was added to sodium thiosulphate solution.
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20. Chlorine was bubbled through potassium bromide solution

21. Concentrated sulphuric acid was added to solid sodium iodide
22. Hydrogen sulphide gas was bubbled through acidified potassium permanganate
solution.
23. Hydrogen peroxide was added to an acidified solution potassium dichromate(VI)
solution.
24. Potassium bromide solution was added to concentrated sulphuric acid
25. Sodium iodide was added to acidified potassium chlorate(I) solution.
26. Potassium iodide solution was added to acidified hydrogen peroxide solution.
27. Tin(II) sulphate solution was added to acidified potassium dichromate(VI) solution
28. Potassium sulphite was added to acidified potassium dichromate(VI) solution.
29. Zinc powder was added to iron(III) sulphate solution.
30. Potassium nitrite solution was added to acidified potassium dichromate(VI)
solution.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

31. Iron(II) sulphate solution was added to acidified potassium dichromate(VI)
solution
32. Manganese(IV) oxide was added to acidified solution of sodium oxalate and the
mixture heated
33. Iron(II) sulphate solution was added to acidified potassium manganate(VII)
solution
34. Acidified potassium peroxodisulphate solution was added to iron(II) sulphate
solution
35. Lead(IV) oxide was added to manganese(II) sulphate solution followed by dilute
nitric acid and the mixture heated
36. Hydrogen peroxide was added to an acidified solution of iron(II) sulphate.
37. Iron(III) chloride was added to an alkaline solution of hydrogen peroxide.
38. Potassium iodide solution was added to acidified potassium dichromate solution.
39. Potassium iodide was added to an alkaline solution of potassium manganate(VII)
40. Potassium nitrite was added to acidified potassium permanganate solution.

Titration of redox reactions

Redox reactions are used in titrimetric analysis. A solution of unknown concentration of a
reducing agent is titrated against a standard solution of an oxidizing agent. From the
volumes of the two solutions used and the overall equation of the reaction, the unknown
concentration of one of the solutions can be determined. The process involves transfer of
electrons from the reducing agent to the oxidizing agent. The half-cell reactions may be
given to generate the overall reaction or the student may be required to derive it oneself
during practical assignments and examinations. It is very important to check the overall
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equation to make sure it is well balanced by both mass and charge. When the equation is
not balanced, many marks are lost because the mole ratio is important in the subsequent
calculation work.
Common redox titrimetric reactions include;
1. Potassium manganate(VII) titrations in acidic medium
2. Sodium thiosulphate titrations

Sodium thiosulphate titrations

Sodium thiosulphate is a reducing agent. If it is standardized, it is used
in titrimetric analysis for reducing iodine to iodide ions as it is oxidised to sodium
tetrathionate. Starch indicator is used to give an intense blue colour in presence of iodine.
At the end point when all the iodine has been converted to iodide ions, the blue colour
varnishes. Sodium thiosulphate cannot be used as a primary standard because it is
efflorescent.
The reactions occur by the two half reaction equations shown below and therefore the overall

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

equation.

The thiosulphate can be titrated with aqueous iodine directly or the iodine can be obtained
commonly be the redox reactions involving oxidation of potassium iodide by the reducing agents
to iodine shown below:
(i) Reaction between potassium manganate(VII) in acidic medium with excess potassium
iodide.

(ii) Reaction between potassium dichromate(VI) in acidic medium with excess potassium
iodide.

(iii) Reaction between potassium iodate(V) in acidic medium with excess potassium iodide.

(iv) Reaction between sodium chlorate(I) (usually from domestic bleach or Jik) in acidic
medium with excess potassium iodide solution.

During this process, a dilute acid is added to Jik. Jik is a mixture of sodium hypochlorite and
sodium chloride. When a dilute acid is added to jik, chlorine is given off.

The chlorine can then oxidise the iodide ions in potassium iodide to iodine as it is reduced to
chloride ions.

The two equations (i) and (ii) when combined give the overall equation above.
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Chlorine can also be obtained by adding a dilute acid to bleaching powder (calcium
hypochlorite)

(v) Addition of copper(II) ions to excess potassium iodide solution.

Examples
1. 1.185g of potassium dichromate(VI) was dissolved in water to make 250cm3 of
solution. 25.0cm3 of this solution was acidified and added to excess potassium
iodide solution. The resultant solution was titrated against sodium thiosulphate
and 17.50cm3 of the thiosulphate was required. Find the concentration of the
thiosulphate solution in grams per litre.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

( )

( ) ( )

( ) ( )

( )
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PHYSICAL STATES OF MATTER

There are three states of matter, i.e. solids, liquids and gases. The states can also be
referred to as phases. However, at very high temperatures, matter exists as plasma which
has its own strange characteristics.

Inter-conversion between the states

A
SOLID LIQUID
B

C D E F

GAS

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A. Melting
B. Freezing or solidification
C. Sublimation
D. Deposition
E. Condensation
F. Evaporation or vapourisation

Plasma
As a gas is heated to about 10,000K, the intermolecular and interatomic collisions
become more and more violent until the molecules disintegrate into electrons and
positively charged particles. A mixture of these is what is called plasma. Plasmas are
neutral overall but the strong forces between charged particles are different from those
between the neutral molecules or atoms in a gas. This makes plasmas very different from
gases. External magnetic and electric fields affect the charged particles in plasma but
have little or no effect on neutral particles in a gas. Plasmas also emit a lot of light and
other electromagnetic radiation at such high temperatures. More modern research is
taking place to fully understand the characteristics of plasmas in detail.

The kinetic theory of matter

The kinetic theory was developed between 1860 and 1890, mainly by R.J. Clausius,
J.C. Maxwell and Boltzmann. It accounts for the known properties of gases, but it also
clarifies many problems concerned with liquids and solids.
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The theory can be summarized as follows;

(a) Matter is made up of particles which may be small groups of atoms (molecules) or
single atoms in monoatomic gases.
(b) The particles in a gas are in continual, rapid, random motion in straight lines in every
direction and collide with each and with the walls of the container in which they are.
The pressure exerted by the gas on the walls of the container is due to bombardment
by the moving particles. The random motion also applies to liquids but greatly
decreased and also further decreased in a solid.
(c) The particles in a gas are separated from each other by distances which are large
compared to the size of the particles. In a liquid, the particles are closer together, and
they are still closer in a solid.
(d) The particles are regarded as being perfectly elastic so that the collisions they undergo
in a gas do not result in any change in the total amount of kinetic energy of the gas.
(e) Increase in temperature causes the motion of the particles to increase, the average

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

kinetic energy of the particles in a gas being proportional to the absolute temperature
of the gas.

Differences in the states of matter

Parameter State of matter
Gas Liquid Solid
The particles are closely
The particles are far The particles are packed and orderly
Particle apart and are not orderly closer to each other arranged, fixed in three
arrangement arranged and are not orderly dimensional structures.
arranged
Forces of Forces of attraction Intermolecular forces Attraction between the
attraction between the molecules of attraction are molecules is even more
are negligible weaker than those in dominant
solids
Movement The particles are mobile Particles randomly Movement of the particles
with different speeds in move, as in a gas, but is restricted to vibration
various directions not as fast as in gases about mean/fixed positions

Comparison of physical properties

Physical property State of matter
Gas Liquid Solid
Gases are highly
compressible.
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Increasing the
pressure on a gas
decreases its volume Liquids are only Solids are
Compressibility and decreasing the slightly compressed incompressible.
pressure will increase
its volume

Gases have low Densities of liquids Solids have very high

Density densities. When a gas are higher than gases densities.
is cooled, its density but lower than those
increases. of solids
Gases have no
definite volume. They Liquids have definite Solids have definite
Volume take up volume of volumes volumes.
containers they

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occupy.

Gases have no Liquids have no Solids have definite

Shape definite shape. They shape, they take up shapes.
take up shape of the shape of the
container they containers they
occupy. occupy.

GASEOUS STATE OF MATTER

A gas is predicted as a random movement of atoms or molecules, not closely packed,
with very weak forces between them so that they can move about quite freely.
That is why gases have low densities, they expand to occupy any container and are easily
compressed.

The gaseous state in terms of kinetic theory of matter

According to the kinetic theory;
1. The gas molecules occupy only a tiny fraction of the volume of the container in which
they are contained. The intermolecular distance is many times larger than the diameter
of the molecules. A sample of a gas is nearly empty space and the molecules are
scattered throughout this space.
2. The gas molecules are constantly moving in straight lines until they collide with each
other and with the walls of the container, exerting no force upon one another. The
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collisions made are perfectly elastic, meaning that the molecules bounce apart with no
loss of energy.
3. The average kinetic energy of the molecules is proportional to absolute temperature,
therefore at a certain temperature; all gases have the same average kinetic energy.

AN IDEAL GAS
An ideal gas is also called a perfect gas.
An ideal gas is a gas that obeys all gas laws accurately at all temperatures and
pressures, has no intermolecular forces of attraction and occupies a negligible volume.
However there are known examples of ideal gases and the concept is just a theoretical
one.
Gas pressure
This is the pressure exerted by a gas per unit area. The main unit of pressure is
.
is called a .

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Other units of pressure are and
.

Gas laws
Boyle’s law
Boyle‟s law states that; at a constant temperature, the volume of a given mass of a gas
is inversely proportional to the pressure.
Or at a constant temperature, the pressure of a given mass of a gas is inversely
proportional to the volume.

Therefore if a gas has a volume at a pressure and the pressure is changed to , the new
volume , , at a constant temperature is given by the equation;
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Real gases do not fully obey Boyle‟s law. The deviations from the law particularly occur
at high pressures and low temperatures, and for gases which are easily liquefied.
The deviations from the law occur due to interactions between the molecules in a gas. If
such interactions did not exist, then a gas would obey Boyle‟s law (would be ideal or
perfect)
Real gases approach the ideal or perfect behaviour at low pressures and high
temperatures.
Charles’ law
Charles‟ law states that; at a constant pressure, the volume of a given mass of a gas is
directly proportional to the temperature in Kelvin.
Or at a constant pressure, the volume of a given mass of a gas is directly proportional
to the absolute temperature.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Therefore if a gas has a volume at a temperature and the temperature is changed to , the
new volume , , at a constant pressure is given by the equation;

Real gases also deviate from Charles‟ law as they do for Boyle‟s law.
Combined gas laws
When Boyle‟s law and Charles‟ law are combined, one equation is obtained. This is
called the equation of state for an ideal gas. The equation relates pressure, volume and
the temperature of a gas.
From Boyle’s law;
If a given mass of a gas has a volume of at a pressure of , it will a volume at a
pressure at a constant temperature.

From Charles’ law;

If now the temperature at which the volume of the gas, is measured is changed from to
, the new volume will be given by;
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Equating equations and yields;

Multiplying through by yields;

and in a more general form, this can be expressed as

and the temperature expressed in Kelvin.
The equation of state of an ideal gas helps us to calculate the effect of a change in
temperature and pressure on the volume of a gas. We cannot compare gas volumes unless
they are stated at the same temperature and pressure. Gas volumes are usually compared
at 273K and 101325Pa (standard temperature and pressure).
Examples on calculations involving gas laws

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

In these calculations, it is very crucial to remember to change the temperature to the
Kelvin scale. The pressure may be left in its units so long as they are the same on both
sides throughout the calculation.
1. If the volume of a gas at standard temperature and pressure is 51 , calculate
the volume of the gas if it is collected at 60 and 105 kPa.

( )

2. A closed bulb contains a certain volume of a gas at 21 and 755mmHg.

Calculate the pressure of the gas if the temperature is raised to 51 .
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( )

Ideal gas law

Boyle‟s law and Charles‟ law can be combined to form a single equation which
represents the relationship between pressure, volume and kelvin temperature of a given
mass of a gas under different conditions.

By combining the two gas laws;

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

When the quantity of gas is one mole, the constant in this equation is called the molar gas
constant, represented by .
Therefore for 1 mole of a gas;
And for moles of a gas;

The above equation is known as the ideal gas equation because it only holds when gases behave
as ideal or perfect gases.
The molar gas constant is commonly used as when the units of pressure,
volume and temperature are and Kelvin respectively.
Recall that;

( )
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Examples
1. Calculate the volume occupied by 200g of carbon dioxide gas at a temperature
30 and a pressure of 98.65 kPa.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. 0.539g of a vapourised sample of gas X occupies 200 at a temperature of
373K and a pressure of 0.938 atm. Calculate the relative molecular mass of X.

Questions
1. A certain mass of a gas has a volume of 241 at 18 and a pressure of 100400 Pa.
determine its volume at s.t.p.
2. A gas occupies a volume of 1500 at 27 and 102,700 pressure. What
would be its volume at s.t.p?
3. A certain gas has a volume of 75 at 15 and 104 kPa. What would be its
volume at 27 and ?
4. A sealed flask contains oxygen at 17 and 99.3 . What would be the
pressure of the oxygen if the temperature was lowered to ?
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5. At s.t.p, a certain mass of a gas has a volume of 1 litre. At 30 atm, the volume is 31.2
and at 60 atm, the volume is 14.9 . Explain whether the gas shows ideal
behaviour.
6. (a) 1 mole of hydrogen iodide gas at 25 was introduced into a container of volume
20 litres. Calculate the pressure of the gas assuming ideal behaviour.( 1 mole of an
ideal gas occupies 22.4 litres under standard conditions)
(b) The sample of hydrogen iodide, considered above was raised to a temperature of
300 and it decomposed into hydrogen and iodine. Calculate the pressure of the
equilibrium mixture at 300 assuming no change in volume.
7. Calculate the volume occupied by 200g of chlorine gas at a temperature 15 and a
pressure of 54.71 kPa.
8. 1212.5 of a gas J has a mass of 0.88g at 50 and a pressure of 115000 .
Calculate the relative molecular mass of the gas.
9. A gas Q contains 30.43% nitrogen and the rest being oxygen. 0.23g of Q occupied

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

154.11cm3 at 150 and 840mmHg. Determine the;
(i) Empirical formula of Q
(ii) Molecular formula of Q.

More of the application of this concept is covered in empirical and molecular

formula.
Graham’s law of gaseous diffusion
The concept of diffusion is not a new one to us at this level since you already have an
idea from Ordinary level.
The rates at which different gases diffuse are not equal. A lighter gas diffuses more
rapidly than a heavier one. After carrying out a number of experiments on the rates at
which gases mix together, Graham(1832) came up with Graham‟s law which states that;
At constant temperature and pressure, the rate of diffusion of a gas is inversely
proportional to the square root of its density.

√
Consider two gases and which diffuse at rates and respectively. If the densities of the
gases are and respectively;

√ √

√ √
Dividing equation (i) by equation (ii) yields;
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√
√
√ √
√
√
√
√
If the volume is kept constant, then density is directly
proportional to the relative molecular mass of the gas. We then have;

√ √

√ √

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Dividing equation (i) by equation (ii) yields;
√
√
√
√
√
√
Graham‟s law can therefore also be stated as; at constant temperature and pressure, the
rate of diffusion of a gas is inversely proportional to the square root of its relative
molecular mass.
Rate of diffusion of a gas can also be expressed as a reciprocal of the time taken for the
gas to diffuse. Therefore;
√
√
√ Similarly;
√ √
√ √
⁄
√

Rate of diffusion of a gas can also be expressed in terms of volume of the gas and time
taken by the gas to diffuse.
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Avoid the common mistake done by students during most of these calculations by
forgetting that most gases are diatomic. This should be observed when calculating molar
masses of gases.
Examples
1. A given volume of gas W diffuses through a hole in 14.1 seconds while the same
volume of carbon dioxide diffuses through the same hole in 10 seconds. Calculate the
molecular mass of gas W.

√
√
( ) √
( ) √

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

2. A given volume of a gas X diffuses in two thirds of the time taken by an equal
volume of hydrogen chloride under the same physical conditions. Calculate the
relative molecular mass of the X.

( ) √
⁄
( ) √

√
( )
√
( ) ( )
( )

√
√

3. Oxygen diffuses 0.9 times faster than a hydrocarbon Y. Calculate the relative
molecular mass of Y.
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√
√
( )

√
√

4. The time taken for of oxygen to diffuse through a porous partition is

10 seconds. Another gas Z at the same conditions of temperature and pressure
diffuses through the partition at the rate of in 20s. Determine the
relative molecular mass of gas Z.
( ) √
⁄
( ) √

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( ) ( )
√
( )
√

5. Two pieces of cotton wool were each soaked separately in concentrated ammonia
solution and concentrated hydrochloric acid respectively and simultaneously
inserted into opposite ends of a horizontal wide glass tube. After a short time a
white ring was across the tube. If the distance between the inner surfaces of the
cotton wool plugs is 50cm.
(i) Name the white ring
(ii) Write the equation leading to formation of the white ring.
(iii) Determine how far from the ammonia plug the white ring is formed.

(i) Ammonium chloride

(ii)
(iii)
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Since ammonia gas from concentrated ammonia solution diffuses faster than hydrogen chloride
gas from hydrochloric acid, the white ring is formed nearer the cotton wool soaked in
hydrochloric acid. White ring

50cm
50-x x
Cotton wool soaked Cotton wool soaked
in concentrated in concentrated
hydrochloric acid ammonia solution

( ) √
⁄
( ) √

( ) ( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

√ √( )
√

6. Oxygen diffuses 2.3 times as fast as a compound Z with the formula; .

Determine the molecular formula of Z.

( )

√
√
√
√

Questions
1. Calculate the ratio of diffusion of a gas at 91 and 0 at a constant pressure.
2. A gas Q diffuses 4 times as rapidly as sulphur dioxide under the same conditions. If
the density of sulphur dioxide under the same conditions of temperature and pressure
is , calculate the density of Q.
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3. 100 of oxygen diffused through a membrane in 5 minutes. 120 of an

unknown gas under the same conditions, diffused through the membrane in 10
minutes. Calculate the molecular mass of the unknown gas.
4. Oxygen diffuses 1.19 times faster than an amine, .
(i) Determine the molecular formula of the amine.
(ii) Deduce the structural formulae and names of all possible isomers of the
amine.
5. 250 of an alkene diffuse through a porous medium in 10 seconds and 716 of
oxygen diffuse through the same medium in 25 seconds under the same conditions.
Calculate the molecular mass of the alkene and deduce its structural formula.
6. Oxygen diffused through a porous partition in 1.87 minutes. Under similar conditions,
the same volume of an alkene, T diffused in 2.15 minutes.
(a) Determine the formula of T
(b) Write equation and outline mechanism for the reaction between T and benzene.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Indicate the conditions for the reaction.
7. 141.4 of an inert gas diffused through a porous plug in the same time as it took
50 oxygen to diffuse through the same plug under the same conditions. Calculate
the relative atomic mass of the inert gas.
8. Two pieces of cotton wool were each soaked separately in concentrated amine Q and
concentrated hydrochloric acid respectively and placed at opposite ends of a 2m long
glass tube. After some time a white ring was formed at 0.96m from the end
containing concentrated hydrochloric acid. Determine the relative molecular mass of
amine Q.
9. Two pieces of cotton wool were each soaked separately in concentrated amine Y and
concentrated hydrochloric acid respectively and placed at opposite ends of a 1m long
glass tube. After some time a white ring was formed at 0.52m from the end
containing the concentrated ammine. Determine the relative molecular mass of amine
Y.
10. of gas L diffuses through a porous partition in 5s. of oxygen
diffuses through the same partition in the same time. Calculate the molecular mass of
L.
11. Nitrogen gas diffuses 1.25times faster than gas X. calculate the relative molecular
mass of gas X.
12. 25 of gas Q diffuse through a small aperture in 48 seconds while 25 of an
alkane diffuse through the same aperture in 40 seconds.
(i) Deduce the molecular formula of the alkane.
(ii) Write equations to show how the alkane can be synthesized from
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Pent-2-yne.
13. Gas X diffuses through a membrane in 20.5 minutes and under the same conditions,
an equal volume of hydrogen diffuses through the same membrane in 3 minutes.
Calculate the molecular mass of X.
14. 141.4 of gas X diffused through a porous plug in the same time it took 50
of oxygen to diffuse through the same plug under identical conditions. Calculate
the relative molecular mass of X.

15. State Graham‟s law of gaseous diffusion.

(b) Nickel forms a gaseous carbonyl; . Deduce the value of n if carbon
monoxide diffuses 2.46 times faster than the carbonyl compound.
(c) State the ;
(i) name of the nickel carbonyl
(ii) coordination number of nickel in the compound.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

16. (a) State Graham‟s law of gaseous diffusion.
(b) A hydride of silicon contains 9.65% by mass of hydrogen and was found to
diffuse through a porous plug at two thirds of the rate of diffusion of nitrogen.
Determine the molecular formula of the hydride.
17. A gaseous compound X contained 46.1% carbon and 53.9% nitrogen. In 20 seconds,
50 of X diffused through a porous plug and the same volume of oxygen diffused
in 15.7 seconds.
(i) Determine the molecular formula of X.
(ii) Calculate the volume of carbon dioxide that diffuses in 20 seconds under
the same conditions.
18. A compound, B has an empirical formula of . Oxygen gas diffuses 1.345 times
faster than B.
(a) (i) Determine the molecular formula of B
(ii) Write the structural formulae of all the possible isomers of B.
(b) (i) B does not Fehling‟s solution. Using equations, show how B can be formed
from propene
(ii) Write an equation for the reaction of B with sodium hydrogen sulphite
and write the mechanism.
19. A gaseous oxide of sulphur, diffused through a porous partition in 2.68 minutes
while equal volume methane at the same temperature diffused in 1.1985 minutes.
(a) Determine the value of in the oxide
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(b) The oxide in (a) above reacts with benzene via an electrophilic substitution
mechanism.
(i) State whether the oxide in (a) above acts as an electrophile or nucleophile.
Give a reason for your answer.
(ii) Write equation for the reaction with benzene and outline the mechanism.

Mole fraction of a gas,

Mole fraction of a gas is the ratio of the number of moles of the gas present to the total
number of moles of all the gases in the mixture.

Therefore for a mixture of two gases and . The mole fractions of gases and are
given respectively as

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Also from Avogadro‟s hypothesis, it follows that;

Dalton’s law of partial pressure

In a mixture of gases, each gas behaves as if it was the only gas present assuming there
are no chemical interactions between the gases. In a container in which a mixture of
gases, that not react are enclosed, the total pressure exerted is a result of the individual
pressures of each of the gases. Each of these pressures is called partial pressure.
Partial pressure of a gas is the pressure which that gas exerts if it occupies a vessel
alone which was initially occupied by a mixture of gases.
In 1801, Dalton came up with Dalton‟s law of partial pressure which states that; in a
mixture of gases which do not react chemically, the total pressure is the sum of the
partial pressures of the components.
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Let us now consider a mixture of three gases and and placed in a vessel each having
partial pressures , and respectively.
According to Dalton‟s law of partial pressures; the total pressure exerted by the gases is;

and if each of the gases has the number of moles as and and respectively,
Then the mole fractions of the gases and and are given by;

The partial pressures of each of the gases respectively are given as a product of
their respective mole fractions and the total pressure,
( )

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )
Dalton came with his law experimentally but it can be deduced from the ideal gas
equation. Therefore if each of the gases has the number of moles as and and
respectively and occupy a volume V, then, the pressures of each of the gases
respectively are given as;

The total pressure can then be expressed as

Examples
1. (a) State Dalton’s law of partial pressures.
(b) Explain why a mixture of ammonia and hydrogen chloride does not hold for
Dalton’s law of partial pressures.
(c) A mixture of 20% ammonia, 55% hydrogen and 25% nitrogen by volume has
a pressure of . Calculate the partial pressure of each gas.

LIQUID STATE OF MATTER

The liquid state in terms of kinetic theory of matter
Most liquids are miscible like all gases. Liquids can be compressed although to a smaller
extent than gases.
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According to the kinetic theory, molecules in a liquid are in a state of random motion, as
in a gas, but the motion is very much less than it is in a gas and the molecules in a liquid
are very much closer.
Liquids actually lie midway between the disorderly, scattered distribution found in a gas
and the orderly compact arrangement found in a crystalline solid.
The random distribution of molecules found in a liquid is shown by a phenomenon of
Brownian motion. Brownian motion was first observed by a botanist Robert Brown in
1827, who found out that very small pollen grains immersed in water undergo an
irregular motion when observed under a microscope. Such motion is due to bombardment
of the pollen grains by molecules of the liquid in which the grains are suspended.
Properties of a liquid
1. Compressibility
Compressibility of a liquid ( )is the fractional change in its volume per unit increase in
pressure. Liquids have low compressibility because the particles are closer to each other

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

and the intermolecular forces of attraction are weaker than those in solids hence the
particles can randomly move although not as fast as in gases.
The property of compressibility of liquids is applied in;
(i) Hydraulic breaks. In a hydraulic break, there is a brake fluid whose compressibility is
affected by temperature and the presence of trapped air and moisture. When the brake
pedal is pressed, force is exerted on the pistons causing the brake fluid to flow into a
pressure chamber. This increases the pressure in the entire hydraulic system. This
pressure effect is also exerted on the brake pads to reduce the vehicle speed.
(ii) Hydraulic car jack. The car jack is used to lift even the heaviest cars using a small
force that is applied to a fluid from one piston of the car jack. This force builds up
pressure in the fluid that then forces another piston to rise. This generated pressure lifts
the car up.
2. Viscosity
The viscosity of a liquid is the resistance to flow of a liquid. Edible oil has a greater
viscosity than water. Viscosity may be thought of as internal friction between the
molecules. Viscosity is a major factor in determining the forces that must be overcome
when fluids are used in lubrication and transported in pipelines. It controls the liquid flow
in processes like spraying, injection moulding and surface coating. The viscosity of
liquids decreases rapidly with an increase in temperature. That is why upon heating,
liquids flow more easily. The viscosities of water at 27℃ and 77℃ are
and respectively.
3. Surface tension
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Molecules in the interior of a liquid are attracted equally on all sides by the molecules
around them. Molecules on the surface are only attracted inwards and sideways. As a
result, the liquid surface is always under tension and tends to contract so as to reduce the
surface area to a minimum. The mutual attraction of the molecules in the liquid surface
produces a resistance to penetration since work has to be done to force the molecules
apart. The surface has a certain amount of “hardness” which is basically similar to the
hardness of a solid metal surface. Therefore small metal objects such as a greased steel
needle can float on water and certain insects can move freely on a water surface without
getting wet. The values of surface tension decrease with increase in temperature.
Surface tension of a liquid, , is the force in newtons acting parallel to the surface
along a line of one metre in length in the surface and at right angles to the line.
4. Diffusion
Like gases, liquids also diffuse since their molecules are also moving. The diffusion in
liquids is however slower than in gases because the molecules are more closer together
than in gases. When two miscible liquids are added together, they diffuse throughout the

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

whole mixture until it is homogeneous. Solids can also diffuse in liquids to form
solutions. For example copper(II) sulphate and potassium manganate(VII) crystals can
diffuse in water.
5. Vapourisation/ Evaporation
Evaporation is the change of state from liquid to gas (or vapour) at a temperature below
the boiling point of the liquid. Evaporation can take place at any temperature, the rate
increasing with increase in temperature. Some molecules in the liquid have enough
energy to escape into the gas phase (if they are near the surface and moving in the right
direction). Because these are the molecules with higher kinetic energies, evaporation
results in a cooling of the liquid. Evaporation is an endothermic process.
The rate of evaporation of a liquid depends on a number of factors which include its
vapour pressure(which is most important), molar heat of vapourisation, molar heat
capacity and other factors. Liquids with a high vapour pressure evaporate easily than
those with a lower vapour pressure
6. Condensation
The change of a vapour or gas into a liquid. The change of phase is accompanied by the
evolution of heat i.e. it is exothermic.
The evaporation of a liquid seen above can continue until no liquid remains. However, if
the liquid is in a closed container, the molecules in the vapour state collide with the walls
of the container and some fall back into the liquid(condense). Equilibrium will be reached
when the rate at which molecules condense is equal to the rate at which molecules of
vapour condense.
7. Boiling
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When a liquid is heated, its temperature increases until there are molecules with sufficient
energy to escape from the liquid surface. The temperature reaches a high enough value
and the saturated vapour pressure becomes equal to the external pressure. At this point
the liquid changes rapidly and completely into vapour. This process is called boiling and
the temperature at which it occurs is the boiling point. The boiling point of a liquid
depends on the cohesive forces in the liquid. If the cohesive forces are weak, the boiling
point is low. When the cohesive forces increase in strength, the boiling point increases.
Boiling therefore occurs when the vapour pressure is equal to the external pressure
exerted on the liquid.
Boiling point of a liquid is the constant temperature at which its saturated vapour
pressure becomes equal to the external pressure on the liquid.
8. Vapour pressure
Vapour pressure of a pure liquid is the pressure exerted by the vapour over the liquid
surface. The vapour pressure of a liquid depends on;

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(i) The temperature of the liquid
When the temperature of a liquid is raised, its molecules move more rapidly. This results
into an increase in the average kinetic energies of the molecules. At higher temperatures,
a greater number of molecules possess energy greater than the escape energy and
therefore a greater number of molecules escape as vapour. This increases the vapour
pressure of the liquid.
(ii) External pressure
The boiling point of a liquid depends on the external pressure. At a given temperature,
vapour pressure of a liquid is equal to the external pressure. Therefore the vapour
pressure of the liquid at a given temperature increases with increase in external pressure.
A liquid therefore boils at a higher temperature than its normal boiling point when the
external pressure is increased.
(iii) Intermolecular forces
The vapour pressure of a liquid depends on the strength of its intermolecular forces. A
liquid with weak intermolecular forces acting between its molecules has a higher
tendency to escape as a vapour hence a higher vapour pressure, said to be volatile. A
liquid with stronger intermolecular forces acting between its molecules has a lower
tendency to escape as a vapour hence a lower vapour pressure, said to be less volatile or
non-volatile.
Question;
The table below shows the boiling points of different pure liquids.
Compound Boiling point( )
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(a) Arrange the compound in order of increasing vapour pressure.

(b) Explain your answer in (a) above.

(a) Vapour pressure increases in the order;

(b) The vapour pressure increases from water to ethanol to ethoxyethane to nitrogen to
hydrogen, since boiling point decreases in the same order.
The vapour pressure of a liquid depends on the strength of its intermolecular forces.
Water molecules interact through strong intermolecular hydrogen bonds which
require a high amount of energy to break. This reduces escaping tendency of water

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

molecules into the vapour phase hence a low vapour pressure. Ethanol has a higher
vapour pressure than water because the intermolecular hydrogen bonds in it are
weaker than in water. This is because each ethanol molecule has only one hydrogen
atom that is sufficiently partial positive hence forms only two hydrogen bonds unlike
each water molecule that forms four hydrogen bonds. Ethanol molecules therefore
have a higher escaping tendency than water molecules. Ethoxyethane molecules,
liquid nitrogen molecules and liquid hydrogen molecules all interact through weak
van der Waals forces of attraction whose strength decrease with decrease in molecular
size and molecular weight and can easily be broken. Since molecular mass and
molecular size decreases from ethoxyethane to nitrogen to hydrogen, strength of van
der Waals forces decreases in the same order, amount of energy required to break the
forces decreases in the same order, escaping tendency of the molecules into vapour
phase increases in the same order, hence increasing the vapour pressure.
(also refer to the topic; bonding and structure)

SOLID STATE OF MATTER

A solid is a substance of definite shape, high density and with strong intermolecular
forces of attraction between its molecules.

The solid state in terms of kinetic theory of matter

According to the kinetic theory, the molecules, atoms or ions in a solid are closely packed
and orderly arranged. Movement of the particles is restricted to vibration or oscillation
about mean/fixed positions. This makes solids incompressible. Attraction between the
particles is even more dominant.
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The slight motion observed in a solid at ordinary temperatures is shown by the fact that
two solids when placed in close contact may diffuse very slightly into each other and also
by the fact that solids can exert a vapour pressure. The vapour pressure of a solid at
normal temperature is so small to be negligible but some solids like iodine and
naphthalene exert considerable vapour pressures at temperatures below their melting
points. On heating, they sublime (change directly to gas) and on cooling, the vapour
formed condenses into a solid.
Majority of solids melt into liquid when heated because the cohesive forces between their
molecules are broken and can no longer hold them together.

Phase changes in solids

1. Melting point
Melting point of a solid is the constant temperature at which the solid and liquid
phases are in equilibrium at a given external pressure.
In a solid, the particles are in a constant state of vibration. When a solid is heated, energy
is absorbed and the amplitude of vibration increases. The solid melts and the heat energy

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of its particles increases sufficiently to overcome the cohesive forces which hold them
together. The process is a gradual one and the temperature remains constant even though
heat is being supplied. Solids which have covalent and ionic bonds usually require a
higher amount of energy to melt than those held by hydrogen bonds or van der Waals
forces.
2. Freezing point
Freezing point is the constant temperature at which the liquid and solid phases are in
equilibrium at a given external pressure.
The freezing point of a substance in its liquid form is the same as the melting point of its
solid form and depends on factors such as purity of the substance and its external
pressure.
3. Sublimation
A solid which when heated changes directly into vapours without an intermediate liquid
stage, is said to have undergone sublimation. Every solid exerts a vapour pressure
although it is usually very small. The vapour pressure of solids increases with increase in
temperature. When the vapour pressure of a solid reaches the external pressure before it
melts, then the solid will vapourise before it melts (it sublimes). Such substances include
iodine, solid carbon dioxide (dry ice), naphthalene, camphor, etc.
4. Deposition
Under certain conditions, a gas can transform directly into a solid without passing
through the liquid phase by a process called deposition. Examples are conversion of
water vapour to ice and soot deposition on the walls of chimneys
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Types of solids
Giant ionic solids
Ionic compounds are formed when metallic elements combine with non-metallic
elements. The ionic bonds formed in these compounds are strong electrostatic attractions
between the ions of opposite charges (cations and anions).
Each ion is surrounded by the greatest number of oppositely charged ions called the
coordination number. Examples of giant ionic solids include sodium chloride, caesium
chloride and zinc blende.
In sodium chloride, each sodium ion is surrounded octahedrally by six chloride ions,
and each chloride ion is surrounded by six sodium ions.

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In caesium chloride, each caesium ion is surrounded by eight chloride ions, and each
chloride ion is surrounded by eight caesium ions.

In zinc blende, each zinc atom is surrounded tetrahedrally by four Sulphur atoms, and
each Sulphur atom is surrounded by four zinc atoms. The structure is similar to that of
diamond
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Giant ionic solids have the following properties;

(a) They have high melting and high boiling points due to the strong electrostatic
attractions between the ions that require a high amount of energy to break.
(b) They are strong electrolytes in molten state or when dissolved in solution because
ions become free to move.
(c) Soluble in polar solvents like water because they consist of oppositely charged ions

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but insoluble in organic solvents like ether and benzene.
(d) Very hard and brittle.

Giant covalent solids

Covalent bonds are formed between atoms of non-metallic elements. When many very
strong covalent bonds link one atom to another to form an extensive three dimensional
lattice, a giant covalent structure is formed.
Examples of giant covalent solids include diamond, graphite, silicon and fullerene.
In diamond, each carbon atom is covalently bonded to four other carbon atoms to form a
tetrahedral structure which is continuous to form a 3-dimensional giant covalent
structure. The giant covalent structure has very many strong covalent bonds between
carbon atoms which require a high amount of energy to break. This is why diamond is
very hard and strong. All the four valence electrons of each carbon atom are used for
bonding and none is delocalized. This makes diamond a non-conductor.

Carbon atoms

Strong covalent bonds

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In graphite, each carbon atom is covalently bonded to three other carbon atoms to form
two dimensional layers of hexagonal rings of carbon atoms. The hexagonal layers held
together by weak Van-der-Waals‟ forces of attraction which allow the layers to slide over
each other, a reason as to why graphite is soft and slippery, hence acts as a solid
lubricant. For each carbon atom, one electron is not used for bonding. These electrons,
one per carbon atom, are delocalized and used by graphite to conduct electricity.

Strong covalent bond

Layer one
Weak van der Waals forces
Carbon atoms
Layer two

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Silicon also has a giant covalent diamond like structure. Each silicon atom is covalently
bonded to four other silicon atoms to form a tetrahedral structure which is continuous to
form a giant covalent structure.

Fullerene
Fullerene is an allotrope of carbon whose molecule contains a range of 30-70 carbon
atoms. The carbon atoms are joined by single and double covalent bonds to form a closed
mesh like structure, which is also a giant covalent structure with fused rings of five to
seven carbon atoms each. The molecule can be a hollow sphere or in form of many other
shapes and sizes. The most common fullerene is .

Giant covalent solids have high melting points and are non-volatile due to the strong
covalent bonds holding the atoms together.

Molecular covalent solids

Iodine and phosphorus are molecular covalent solids.
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Iodine is a diatomic molecule ( ) in which the iodine atoms are held by strong covalent
bonds. However, the diatomic iodine molecules interact through weak van der Waals
forces of attraction. When iodine is heated, the weak van der Waals forces are broken and
the molecules are set free, making iodine to sublime.

Covalent bond between two Van der Waals forces holding iodine molecules
iodine atoms in the iodine
molecule

Both white phosphorus and red phosphorus exist a tetratomic molecule ( ). They are
molecular covalent solids. White phosphorus has the four phosphorus atoms joined by
covalent bonds but the tetratomic molecules are held by weak van der Waals forces
which require a low amount of energy to break. This is why white phosphorus has a low

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

melting point. Red phosphorus has the four phosphorus atoms joined by covalent bonds
and the tetratomic molecules are also held by strong covalent bonds which require a low
amount of energy to break. This is why red phosphorus has a high melting point

White phosphorus Red phosphorus

Giant metallic solids

A metallic solid consists of a lattice of ions with the outer most electrons forming a “sea”
of delocalized electrons. The delocalized electrons freely move throughout the structure
and can conduct electricity. Electrostatic attractions exist between the delocalized
electrons and the metal ions. The giant metallic structures occur in metals such as iron,
copper, titanium, etc.
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Solid copper has a giant metallic structure which consists of a lattice of copper ions
surrounded by a sea of delocalized electrons moving randomly throughout the lattice of
regularly spaced positive ions. Strong metallic bonds hold the crystal together. Copper
has a face centred cubic close packed structure. Iron has a body centred cubic structure
and titanium has a hexagonal close packed structure.
Giant metallic solids have the following properties;
1. High melting and boiling points because a high amount of energy is required to break
the strong metallic bonds. Melting point increases as the number of electrons
contributed per atom of a metal towards metallic bonding increases.
2. Good conductors of electricity and heat due to presence of free mobile electrons
throughout the lattice. They conduct heat due to exchange of kinetic energy between
free mobile electrons in the lattice.
3. Strong but malleable and ductile.
4. Insoluble in polar and non-polar solvents. The metal-metal attractions are much

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

stronger than the metal-metal attractions or the metal-solvent attractions. The solvent
molecules cannot penetrate the metal lattice.

EMPIRICAL FORMULA, MOLECULAR FORMULA AND

PERCENTAGE COMPOSITION BY MASS
The percentage composition by mass of an element or a molecule in a
compound

From the formula of a compound and the relative atomic masses of the elements in it, the
percentage of each element or molecule in the compound can be determined. This is
called percentage composition by mass.

Examples

1. The Single Superphosphate(SSP) fertilizer is common phosphatic fertilizer

chemically known as calcium dihydrogenphosphate. Calculate the percentage of
phosphorus in the fertilizer.
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2. State the element with the highest percentage by mass in one mole of copper(II)
sulphate-5-water.

Therefore oxygen has the highest percentage by mass in copper(II) sulphate-5-water.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

3. Calculate the percentage by mass of water of crystallization in diammonium
iron(II) sulphate-6-water, .

4. A hydrated aluminium sulphate contains 8.1% by mass of aluminium. Calculate

the percentage by mass of the water of crystallization in it.

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Exercise
1. Calculate the percentage by mass of the named element in each of the following
compounds
(a) nitrogen in Sodium nitrate
(b) nitrogen in Ammonium sulphate
(c) magnesium in magnesium nitride
(d) bromine in calcium bromide
2. Calculate the percentage of water of crystallization in;
(a) sodium carbonate decahydrate
(b) Iron(II) sulphate heptahydrate

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

3. A metal sulphate, contains 28% by mass of metal Y. Determine the relative
atomic mass of Y and the relative molecular mass of
4. Hydrated iron(III) sulphate, contains 19.9% by mass of iron. Find
the value of Y.

Empirical formulae and molecular formulae

The empirical formula is the simplest formula that expresses the simplest ratio of the
atoms present in a given compound. It is the formula obtained by experimental analysis
of a compound and it can be related to a molecular formula only if the molecular weight
is known.
The molecular formula simply gives the types and numbers of atoms present. The
formula of a compound showing the number and types of the atoms present in one
molecule of the compound, but not the arrangement of the atoms. For example,
represents the molecular formula both of ethanol and methoxymethane
. The molecular formula can be determined only if the molecular mass is
known. The molecular mass can be obtained from the following known formulae;
(i)

(ii)
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(iii)
(iv)
(v) Data from colligative properties.
The molecular formula can be got from the empirical formula using the relationship;

Molecular formula can be the same as empirical formula if

Name of compound Empirical formula Simplest ratio Molecular formula Value of

Ethanoic acid 1:2:1
Glucose 1:2:1
Water 2:1
Ethene 1:2

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Benzene 1:1
Phosphorus(V) oxide 2:5

The table above shows the empirical formula-molecular formula relationship for some
compounds.
Note; during the process of obtaining the empirical formula, the simplest ratio is obtained
as a decimal fraction. This ratio should have whole numbers only. Therefore figures of
the type 1.1, 1.2, 2.7, 3.8 and 4.9, can be rounded off to 1,1,3,4 and 5 respectively.
However, values of the type; 1.333, 2.4, 1.5, and 3.666 should not be rounded off.
Rounding them off creates a very big error. They must be multiplied by a factor to make
them whole numbers as summarized below.
Sample calculated ratio Factor Correct ratio
1 : 1.333 3 3 : 4
1.5 : 2 2 3 : 4
2 : 2.499 2 4 : 5
1 : 3.666 : 3 3 3 : 11 : 9
3 : 2.4 2 6 : 5
Calculations on empirical formulae and molecular formulae
Examples
(a) From percentage composition
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1. An organic compound Y contains 66.7% carbon, 11.1% hydrogen and the rest
being oxygen. If the vapour density of Y is 36, determine its molecular formula.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. A compound Q contains 54.5% carbon, 9.09% hydrogen and the rest being
oxygen.
(a) Calculate the empirical formula
(b) 0.542g of Q occupies 148cm3 at a temperature of 20 and a 740mmHg
pressure. Determine the molecular formula of Q.
(c) If Q which produces effervescence with magnesium powder, deduce its
structural formula.

(a)

(b)
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( )

(c) Hint; its carboxylic acids that form hydrogen

when reacted with magnesium.
( )

3. A compound J contains 62.1% carbon, 10.3% hydrogen and the rest being
oxygen. If J has a density of at s.t.p;
(a) Determine the empirical formula of J

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(b) Molecular formula of J
(a)

(b)
( )

(b) From combustion data

4. When a hydrocarbon L was burnt in excess air, 14.4g of water and 13.44dm3 of
carbon dioxide were obtained at s.t.p.
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(a) Determine the empirical formula of L.

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(b) If the vapour density of L is 22. Determine the molecular formula of L.

(a)

( )

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(b)

5. When 0.236g of organic compound Q on combustion gave 0.528g of carbon

dioxide and 0.324g of water. If the same mass of Q at s.t.p gave 44.8cm3 of
nitrogen gas, determine the molecular formula of Q if its relative molecular mass
is 59.
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( )

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(c) From other experimental data
One analytical method for determination of molecular formula of a hydrocarbon is
Eudiometry which uses Avogadro’s hypothesis, “equal volumes of different gases at
the same temperature and pressure contain the same number of molecules”. i.e. doubling
the number of molecules present doubles the volume at constant pressure. In this process,
an unknown volume of a gaseous hydrocarbon is exploded with excess oxygen. The
hydrocarbon completely burns to form carbon dioxide and water as the only products.
The vapour is then cooled and contraction in volume occurs due to condensation of water
vapour. The resultant volume (residual gas) left is due to carbon dioxide formed and the
unreacted oxygen. The volume of carbon dioxide is determined by adding aqueous
sodium hydroxide or potassium hydroxide. All the carbon dioxide formed is absorbed
and the diminution (reduction) in the volume of the gases is due to carbon dioxide. The
volume of gas that remains at this point is the unreacted oxygen. The volume of water
formed is regarded as negligible.

( )
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Assume J cm3 of hydrocarbon was exploded in Q cm3 of excess oxygen to form V cm3 of gas. On
addition of concentrated potassium hydroxide, the volume reduced to W cm3.
Volume of carbon dioxide formed is
Volume of oxygen that reacts is
From the above equation,
Relating the volumes;

Similarly; ( )
Relating the volumes;
( )
6. 20 cm3 of a hydrocarbon Z was exploded with 200 cm3 of oxygen. On cooling to
room temperature, the residual gases occupied 160 cm3. When the residual gases
were passed through sodium hydroxide solution, the volume reduced to 20 cm3.

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(a) Write equation for the reaction between Z and oxygen.
(b) Determine the molecular formula of Z.
(c) Compound Z burns with a sooty flame. When Z was treated with hot
alkaline potassium manganate(VII) solution followed by dilute
hydrochloric acid, compound T was formed. T reacts with magnesium
ribbon liberating hydrogen gas.
(a) Identify Z and T
(b) Write equation to show how Z can be obtained from an alkyne.

(a) ( )

(b) Volume of carbon dioxide formed is

Volume of oxygen that reacted
From the above equation,

Similarly; ( )

( )

( )
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(c) Hint; burning with a sooty flame indicates Z is aromatic. On reacting it with
alkaline potassium manganate(VII) solution followed by dilute hydrochloric
acid, the compound T formed is a carboxylic acid since it liberates hydrogen
gas when reacted with magnesium.
(i) Z is
and T is

(ii) Try this on your own (convert ethyne to methylbenzene)

7. 15 dm3 of gaseous hydrocarbon X was exploded with 105dm3 of excess oxygen.

The residual gas occupied 75dm3. On addition of concentrated potassium
hydroxide, the volume reduced by 45dm3. Determine the molecular formula of X.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )
Volume of carbon dioxide formed
Volume of unreacted oxygen
Volume of oxygen that reacted
From the above equation,

Similarly; ( )

( )

( )

( )

8. When 142cm3 of a hydrocarbon Y, of formula, and molecular mass 58g

was exploded with excess oxygen and cooled to room temperature, the volume of
the residual gas was 694cm3. On treatment with concentrated potassium
hydroxide solution, the volume decreased to 126cm3.
(i) Determine the molecular formula of Y.
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(ii) Write the structural formula and IUPAC name of all possible isomers
of Y.

( )

(i) Volume of carbon dioxide formed is

From the above equation,

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(ii)
Structural formula of isomer Name of isomer
Butane
2-Methypropane

Questions
Note; some of the questions in this exercise will require you to apply knowledge
from either other topics or branches of chemistry. Feel free to consult those topics
or consult your teacher or wait for them to be covered and revisit the questions.

Questions 22, 26 and 27 will be simpler after covering colligative properties in Phase
equilibria and gaining more knowledge of organic chemistry.
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CHAPTER TWO
ATOMIC STRUCTURE AND THE PERIODIC

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TABLE
Fundamental particles of the atoms and radioactivity
Historical development of the atomic theory
It was the Greek philosophers Democritus and Leucippus who first considered the idea
that matter is made up of particles in about 400BC. This was later supported by Boyle
and Newton. The idea was however not accepted because there was no experimental
evidence for it.

In 1808, a Manchester school teacher, John Dalton restated and extended the older
concepts. He gathered experimental evidence with which people were convinced. In his
Atomic Theory, Dalton said that “matter is made up of atoms”. Dalton, however never
dreamt that anyone would be able to see an atom.

Modern instruments like X-ray diffraction and advanced microscopes have provided
direct evidence for existence of atoms

Modern theory of the atom

(a) John Dalton’s atomic theory
The main points in Dalton‟s Atomic theory can be summarized as follows;

 All matter is made up of tiny particles called atoms.

 The atoms are chemically indivisible, indestructible and cannot be created.
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 All the atoms of any one element are identical i.e. they have the same mass, same
volume and the same chemical properties.
 Atoms of different elements have different mass, volume and chemical properties.
 Chemical combination occurs between elements by atoms joining in small whole
numbers to form a small group of atoms chemically combined together. Dalton
called such a group “a compound atom”. It is now called a molecule.
By using Dalton‟s theory, we can clearly understand that;

When a reaction occurs in a closed vessel, all the atoms present before the reaction are
still present after the reaction. They just merely become rearranged. Since the masses of
the atoms are constant, the total masses of the substances before and after the reaction
should be the same.

Point of thought; What can make us disagree with Dalton on the

question whether atoms can be created or destroyed or split?

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(b) The J.J Thomson model of an atom
Although John Dalton had thought that the atom could not be broken down into anything
simpler, physicists further investigated whether atoms could be made of smaller particles.
In 1895, Crookes, through his experiments on the discharge of electricity through gases at
low pressure, he discovered that a beam of rays was given off by the cathode (the
negative electrode). He called them cathode rays. He also showed that cathode rays
behave like negatively charged particles.

In 1897, Sir Joseph John Thomson, as a result of experimental work still on the
conduction of electricity through gases at low pressure, measured the velocity of cathode
rays and the value of charge to mass ratio of the cathode rays. He obtained the same value
of ⁄ regardless of which gas he used.

 J.J. Thomson therefore deduced that negatively charged particles were present in
all matter.
 The negatively charged particles were named electrons and were recognized as
particles of which an electric current is composed
 He described an atom as a sphere of positive electricity in which negative electrons
are embedded

Point of thought; What is the main difference between this J.J.Thomson’s

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model and Dalton’s model?

J.J. Thomson‟s atomic model is popularly known as the plum pudding model. However,
it had to be abandoned in 1911 on both theoretical and experimental grounds in favour of
Rutherford‟s atomic model.

(c) Ernest Rutherford’s atomic model

In 1909, Rutherford and colleagues found out that when particles from a Radium
source were directed to a very thin sheet of gold or platinum foil;

 The particles penetrated the gold foil

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 A great majority of the particles passed through the foil without change in
direction.
 A small fraction (about 1 in 20,000) of the particles were scattered deflected
through large angles( as high as or more)
Scattered particles

Undeflected particle

Nucleus

To explain the above facts; Rutherford deduced that;

 Since particles are positively charged, the few deflections that occurred were
because the protons of the atom are collected in a heavy, small positively charged
central nucleus which makes up just a tiny fraction of the atom.
 Since most of the particles passed through the gold foil undeflected, most of the
atom is empty space and the electrons rotate in this space around the nucleus in the
in the same way planets rotate around the sun
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The analysis led Rutherford to propose a model in which an atom consists of a very small
positively charged nucleus, in which most of the mass of the atom is concentrated,
surrounded by negatively charged electrons, so that the atom is electrically neutral.

Fundamental particles of the atom

The fundamental particles of an atom include the; protons, neutrons and electrons.

The discovery of the fundamental particles of the atom

The existence of electrons in atoms was first suggested by J.J.Thomson, as a result of
experimental work on the conduction of electricity through gases at low pressures which
produces cathode rays and X-rays, and a study of radioactivity.

An atom is electrically neutral. This means that if it contains negatively charged

electrons, it must also contain some positively charged particles. These positively
charged particles are the protons and they were discovered after Rutherford‟s
experiments after bombardment of elements with and rays given off by

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radioactive elements.

The neutron was discovered by Sir James Chadwick in 1932, by bombarding beryllium
with rays. Chadwick found out that particles which had properties quite different
from those of protons and electrons were given off. They were not deflected at all by
electric and magnetic fields and therefore possessed no charge. The particles had almost
the same mass as a proton. Since they were neutral particles, they were called neutrons.
Later experiments showed that all atoms contain neutrons apart from that of hydrogen.

Properties of the fundamental particles of the atom

Property Electron Proton Neutron
Approximate relative charge
Have equal but opposite charges
Approximate relative mass ⁄
Actual mass (kg)
Have almost equal masses
Charge (C)

RADIOACTIVITY
Discovery
The discovery of radioactivity took place over several years beginning with the discovery
of X-rays in 1895 by Wilhelm Conrad Roentgen. The work continued with Henri
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Becquerel who had learnt of Roentgen‟s discovery of X-rays through the fluorescence of
some materials.
In 1896, a year following the discovery of X-rays, A.H. Becquerel found out that
Uranium and Uranium compounds would also emit a penetrating radiation capable of
affecting wrapped photographic plates. He was experimenting on salts which fluoresced(
glowed in the dark). One day he developed a photographic plate which had been left
wrapped in a drawer of his working table to be used the next day. To his surprise, he
found that the plate had been exposed. Since he knew that no light could penetrate the
wrapping, he perhaps thought the plate was penetrated by some rays coming from the
Uranium salts. He though it wise to investigate this mysterious radiation and gave the
problem to a young research worker called Marie Curie.
Marie Curie later found out that this strange effect happened with all Uranium salts and it
depended on the amount of Uranium present in the compound. She realized that the
ability to give off the radiation was a property of the atoms of uranium and that it was a

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completely new type of property quite different from a chemical reaction. Marie Curie
called this property of the Uranium atom radioactivity.
In 1898, Marie Curie‟s husband left his own research work and joined her with this
exciting discovery. They discovered two new radioactive elements. They called one
Polonium, after Marie‟s native country Poland and the other as Radium.
The naturally occurring elements now known to be radioactive are polonium, radon,
radium, actinium, thorium, protactinium, francium and uranium. Elements that are not
naturally radioactive can also be induced to undergo artificial radioactivity.
In 1903, Rutherford put forward the theory that radioactivity was caused by
disintegration or decay of the large heavy atoms of Radium, Uranium etc., into simpler
atoms of other elements.
Definition;

Radioactivity is the spontaneous disintegration of heavier unstable nuclei to form

lighter stable nuclei with emission of radioactive particles such as alpha particles, beta
particles and gamma rays.
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Types of radiations and their discovery

ELECTRONIC STRUCTURE OF ATOMS

Electronic structure is the state of motion of electrons in an electrostatic field created by
stationary nuclei. The term encompasses both the wave functions of the electrons and the
energies associated with them. In Rutherford‟s “planetary” model, it was proposed that
electrons rotated around the nucleus and could not fall into the nucleus by centrifugal
force. However, it was found out that a charged particle like the electron should radiate
energy, causing a decrease in its velocity and would fall into the nucleus. For this reason,
the electron part of Rutherford‟s model was soon rejected but his concept of the nucleus
remained.

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The modern ideas on electronic distribution in atoms originated from the model of the
hydrogen atom by Bohr. Bohr‟s theory was based on the spectrum of the hydrogen atom.

Electromagnetic radiation
Electromagnetic radiation is the energy resulting from the acceleration of electric charge
and the associated electric fields and magnetic fields. The energy can be regarded as
waves propagated through space involving oscillating electric and magnetic fields at right
angles to each other and to the direction of propagation.

Alternatively, the energy can be regarded as a stream of photons (which are bundles of
light energy) travelling at the speed of light as quantized harmonic waves.

Electromagnetic radiation as quanta

Planck, in his quantum theory of absorption and emission of radiation, proposed that all
material systems can absorb or give off electromagnetic radiation only in “chunks” of
energy called quanta . Quanta are described as discrete packets of energy because it
requires a certain amount of energy to be released by an atom when an electron goes from
a higher energy level to a lower energy level.

The quanta are proportional to the frequency of the radiation, .

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Relationship between wavelength frequency, , and energy, .

The energy of an electromagnetic radiation is directly proportional to its frequency but
inversely proportional to its wave length.

Using the equation in calculations

Examples

1. Find the energy of a photon with wavelength 415nm.

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2. Calculate the energy of a photon with frequency .

Atomic spectra
Atoms of different elements can be made to absorb or emit energy when they are excited.
The emission spectra from the vapours of the elements are known as atomic or line
spectra. They consist of a series of lines, each corresponding to a particular wavelength,
and indicating that the number of possible energy changes that can take place within the
atom of the element is in some way limited. Each element produces a unique set of
spectral lines and no two elements can emit the same series of spectral lines. This means
that an element can be identified by its line spectrum.

The word spectrum was first used in optics to describe the rainbow of colours in visible
light after passing through a prism. After advancement in the understanding of light, the
concept came to apply to the entire electromagnetic spectrum.
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A spectrum can be defined as a range of electromagnetic energies arranged in order of

increasing or decreasing wavelength or frequency of electromagnetic radiation emitted
or absorbed by an atom or molecule.
An electromagnetic spectrum is the entire range of wave length or frequency of
electromagnetic radiation extending from gamma rays to the longest radio waves and
including visible light.

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The emission of radiation may be induced by a variety of methods; for example, by high
temperature, bombardment by electrons, absorption of higher-frequency radiation, etc.

Types of spectra
Emission spectrum
If atoms are heated to sufficiently high temperatures, they emit light of certain wave
lengths. The emission of energy occurs as a result of electrons moving from higher
energy levels to lower energy levels. The observed spectrum consists of a number of
coloured lines on a black background. The spectrum is called an atomic emission
spectrum. The emission spectra of atoms provide evidence that the electrons are
distributed around the nucleus in various energy levels.

Absorption spectrum
If atoms absorb light of a certain wave length, black lines appear in the spectrum where
light of some wave length has been absorbed. The absorbed energy by the atoms causes
energy changes from lower to higher energy levels. The observed spectrum is called an
absorption spectrum.
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A description of the hydrogen emission spectrum

When electricity is passed through a discharge tube containing hydrogen at low

pressure, the hydrogen molecules break up to form single hydrogen atoms. The
hydrogen atoms emit radiations in the and ultraviolet, visible and infrared part of the
spectrum. When the radiations are analysed by a spectrograph, a line spectrum is
formed. Each line in the spectrum represents a definite wavelength of a radiation.
The wave length is given by the Rydberg equation, ( ) where is

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Rydberg constant, and being simple whole numbers and is the wavelength.
A series of lines in the ultra violet region is called the Lyman series. The series of lines
in the visible region is the Balmer series and there is a series of lines in the infra-red
region. The series in the infra-red region consist of the Paschen, Brackett and Pfund
series.
In each series, the intervals between the frequencies of the lines become smaller and
smaller towards the low wave length or high frequency end of the spectrum until the
lines run together or converge to form a continuum of light.

An explanation of the hydrogen spectrum

When the hydrogen atom absorbs energy, it causes the electron to experience a
transition from a lower to a higher energy level. The observed lines in the spectrum are
due to electronic transitions from the higher energy levels to the lower energy levels in
the atom with emission of energy. When an electron from jumps from a higher energy
level to a lower energy level, it emits energy equal to the difference between the
energy of the two energy levels in the form of small packets of light known as photons.
For every transition of the electron, there is a line in the spectrum and there are different
types of spectral series formed.

The Lyman Series is formed when the electron jumps from any higher energy level to
first energy level .
The Balmer Series is formed when the electron jumps from any higher energy level to
the second energy level .
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The Paschen Series is formed when the electron jumps from any higher energy level to
the third energy level .
The Brackett series is formed when the electron jumps from any higher energy level to
the fourth energy level .
The Pfund series is formed when the electron jumps from any higher energy level to the
fifth energy level .
The observed convergence between the lines towards the high frequency end in each
series is because the differences in energy between successive energy levels in atoms
become smaller and smaller with increasing distance of the energy levels from the
nucleus until they finally merge to form a continuum of light (continuous band of
radiation)

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Red Green Violet Ultraviolet

The Balmer series of hydrogen

The application of the Rydberg equation

The Rydberg equation is the equation ;
( )

where is Rydberg constant,

and being simple whole numbers and
is the wavelength.
For the Lyman Series, the electron jumps to from
For the Balmer Series, the electron jumps from from
For the Paschen Series, the electron jumps to from
For the Brackett series, the electron jumps to from
For the Pfund series, the electron jumps to from
Examples
1. If an electron falls from an energy level to an energy level . Calculate
the;
(i) wavelength in nanometers of the emitted radiation.
(ii) the frequency
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(iii) change in energy of the radiation .

(ii)

(i) ( )

( )
(iii)

2. Use the Rydberg equation to calculate the wavelength in of the light emitted
when the electron in a hydrogen atom undergoes a transition from to
. Determine the region of light emitted.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

( )

Note; The units in which the Rydberg constant is given determine the way in which you
carry out the calculation. Also note that to convert from m to nm, a multiplication
factor of is used.

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Energy level diagram for the hydrogen atom

Pfund series

Bracket series

Paschen series

Balmer series

Principal quantum

number(n) Ionisation

energy

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Lyman series Lowest(innermost) energy level

The principle quantum number ( ) only takes on integral values from 1 to infinity( ).
As frequency increases in each of the series of lines, each line becomes closer to the
previous line until the lines converge and the spectrum becomes continuous. The
Lyman series arises from electron transition to the ground state from higher energy
levels. The ground state occurs when the electron is at the lowest energy level ,
and the atom is most stable in this state. The electron normally occupies this energy level
unless given sufficient energy to move up to a higher energy level.
The highest frequency lines relate to the highest energy levels. The limit of the Lyman
series(the convergence of the lines) corresponds to a transition from the to the
energy level. The is the energy level where the electron has escaped from
the atom and the atom has ionised.
The atom is said to be in an excited state when the electron is found in the higher energy
levels. When an electron is excited from the ground state to a higher energy, it becomes
unstable and falls back to one of the lower energy levels by emitting
photon(s)/electromagnetic radiation
By convention, the energy level is usually assigned an energy value of .
The lower the energy level, the more negative the energy value associated with that level.
Thus, the more negative energy states correspond to more stable states. Negative value of
energy indicates that the electron is bound to the nucleus and there exists an attractive
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force between the electron and the nucleus. Also, since the potential at infinity is defined
as zero, energy levels at a distance below infinity are negative.
The energy difference between any two adjacent levels gets smaller as n increases, which
results in the higher energy levels getting very close and crowded together just below
.
The ionization energy of an atom is the energy required to remove the electron
completely from the atom (transition from ground state to infinity ). For
hydrogen, the ionization energy

The significance of lines in the hydrogen spectrum

Explain the significance of lines in the hydrogen spectrum

The spectrum consists of a series of lines, each corresponding to a particular wavelength,

and indicating that the number of possible energy changes that can take place within the
atom of the element is in some way limited. The observed lines in the spectrum are due to

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

electrons making transitions from the higher energy levels to the lower energy levels in
the atom with emission of energy.

The importance of the Convergence limit

State the importance of the Convergence limit

The convergence limit is reached when the electron is completely removed from the atom
and corresponds to a transition from the to the energy level. The transition
happens when an electron collides with an ion and returns to the ground state. The
convergence frequency can be used to calculate the ionisation energy.

The Bohr’s model of the hydrogen atom

Rutherford‟s model of an atom could not explain that facts as to why the atomic spectra
consisted of separate lines. The model did not explain why atoms absorb or emit light
of certain frequencies. In his model too, Rutherford could not explain why the spectral
lines converge to form a continuum.

In 1913, Niels Bohr put forward his theory that explained these facts. He based on
Planck‟s quantum theory which fundamentally proposed that matter cannot absorb or
emit energy in continuous amounts, but only in small discrete units called quanta.
According to Bohr’s theory;
 The single hydrogen electron could travel around the nucleus in various possible
orbits but only certain orbits in which the electron possessed a whole number of
quanta of energy were permissible.
 No energy was radiated while the electron was rotating in a permissible orbit.
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 The permissible orbits were called stationary states or energy levels.

 The atom could be excited by an electric discharge or strong heat.
 The electron could absorb energy and jump to one of the higher energy levels.
 The excited state was however unstable and the electron could fall back to the
ground state.
 As the electron falls back to the lower energy level, it gives out some of its energy in
the form of radiation. The wavelength of the radiation emitted was determined by
the energy difference of the electron in the two energy levels.
Bohr deduced that if was the energy of the electron in the higher energy level and that
is that in the lower energy level, then is the energy difference for an electron
falling from the higher energy level to a lower energy level and was proportional to
wavelength, . If is the frequency, then;

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Bohr assigned quantum numbers to the orbits or energy levels . He gave the orbit of
lowest energy(nearest to the nucleus) the quantum number 1. The next energy levels
quantum numbers and so on.
The weaknesses of Bohr’s atomic model

 Bohr’s theory cannot explain the atomic spectra of atoms with more than one
electron.
 Bohr’s model could not explain the hydrogen atomic spectrum under the influence
of external magnetic field i.e. the Zeeman effect, when the spectral line is split into
several components in the presence of a magnetic field.
 It could not explain the hydrogen spectrum under the influence of an external
electric field. i.e. the Stark effect, when the spectral line gets split into fine lines in
the presence of an electric field.

Ionisation energy
Energy is required to remove an electron from a free gaseous atom against the attraction
of the nucleus. For a single atom, the energy required to remove one electron from the
atom in its ground state is called the first ionisation energy.

The first ionisation energy results into formation of a free gaseous ion from a free
gaseous atom and not formation of an ion of an element in its normal state. Successive
ionisation energies refer to the loss of a second, third,...... th electron.
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Ionisation energy is quoted in units as ionisation potentials in

The value of first ionisation energy for hydrogen can be found by the formula relating the
wavelengths of the lines in the various spectral lines; ( ).

When an electron is removed from the Lyman series( ) to ,

( )

( )
To convert this value to , multiply the
ionisation energy of one electron by Avogadro‟s
number.

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Calculations involving ionisation energies

1. The limits of the spectral lines formed by transitions from ground state occur at
229.9nm for lithium and 285.6nm for potassium. Calculate the molar ionisation
energies of the two elements.
For lithium; For Sodium;

If it’s the frequency, given, then use the formula . Your answer may be left in
Joules.

2. If the ionisation energy of sodium is 496 . Calculate the wavelength of

the convergence limit for sodium.
From ,
( )
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Heisenberg’s Uncertainty principle

According to De Broglie, moving electrons had waves of definite wavelength associated
with them. Further experiments showed that a stream of electrons could be diffracted just
as X-rays can. Since it is only possible to account for diffraction in terms of waves, it was
necessary to assume that a stream of electrons behaves as a wave-like radiation.
As far as atomic structure is concerned, the idea of tiny, negatively charged particles
existing in fixed orbits around the nucleus of an atom is replaced by the idea of charge
clouds of varying charge density existing in a wave like pattern around the nucleus.
An electron can no longer be considered to occupy a specific, limited orbit but instead it
exists in a much more diffuse region known as atomic orbital.

An electron is different from a larger particle in a way that its wave-like nature is of
much greater significance than the wave-like nature of the larger particle.
The other difference is that both the position and the velocity of a large particle like a

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planet can be measured with reasonable accuracy. However, there is no way of measuring
the velocity of an electron exactly and locating it exactly at any one time. This is because
any method used affects the electron being measured.
The information which can be obtained about an individual electron is therefore far from
precise. This an example of application of the Heisenberg Uncertainty Principle in
1927 which states that;

The more accurately the position of a particle is defined, the less accurately is its
velocity known, and the more accurately the velocity is defined, the less accurately is its
position known.

The concept of quantum numbers

The term quantum number is used to label the various energy levels. A set of four
quantum numbers are used to describe completely the movement and trajectories of each
electron within an atom. Each electron in an atom has a unique set of quantum numbers
and no two electrons can share the same combination of the four quantum numbers.
Quantum numbers are important in determining the electronic configuration of an atom
and the location of the electrons in the atom. They are also used to understand other
characteristics of atoms such as ionisation energy and atomic radius.

Quantum numbers are a set of four integers which are necessary to locate the energy
level or position of an electron and to specify the size, shape and orientation of orbital.

In atoms, there are a total of four quantum numbers. These include;

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1. The Principal quantum number

2. The Azimuthal quantum number or angular momentum quantum number
3. The magnetic quantum number
4. The electron spin quantum number
Principal quantum number, .

This specifies the energy level of an electron and its distance from the nucleus. The
first orbital nearest to the nucleus has principal quantum number, and is also called
the ground state. The second principal quantum number, and is called the excited
state and so on. As increases, the size of the orbit increases and the electron is far away
from the nucleus. An increase in also means that the electron has higher energy and is
therefore less bound to the nucleus. Energy levels closer to the nucleus have lower
energy. All the orbitals having the same value of are said to be in the same level. The
total number of electrons that can occupy any energy level is given by where
principal quantum number.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Principal quantum Maximum number of
number electrons
2
8
18
32
Azimuthal quantum number (angular momentum quantum number),

This determines the shape of an orbital and the angular distribution. It represents the
various sub energy levels within an energy level. Each value of indicates a specific
or subenergy level.

Azimuthal quantum Sub energy level

number

p
d
f
g
The values of are in a range of to for each value of . If an electron has a
principal quantum number and an angular momentum quantum number ,
then it is said to be a electron. The different combinations of the two quantum
numbers and are shown in the table below.
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Principal quantum Azimuthal quantum Possible combination of n

number number and l

Magnetic quantum number,

This gives the maximum number of orbitals for the different values of the azimuthal
quantum number, and their orientation in space within a sub energy level. This
quantum number accounts for the splitting of the spectral lines in the line spectrum of
elements. For each value of , there are subdivisions. These m values range
from – .
Azimuthal No. of
quantum Sub energy level subdivisions Values of m
number

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1 0
p 3 -1,0,+1
d 5 -2,-1,0,+1,+2
f 7 -3,-2,-1,0,+1,+2,+3
Electron spin quantum number,

It represents the spin of an electron on its own axis, which can be clockwise or
anticlockwise relative to the orbital of the electron. The electron spin quantum number
does not depend on any other quantum number. It designates the direction of the electron
spin. An electron may have a spin of (represented as ) or (represented as ).
Because an electron spins, it creates a magnetic field which can be oriented in one of the
two directions.

Differentiation between an orbit and an orbital

Orbit Orbital
An orbit is a path traced by an electron An orbital is a region of space around the
revolving around the nucleus of an atom nucleus in which there is maximum probability
of finding an electron of a particular energy
level
The distance of the orbit from the nucleus for a It is impossible to know the exact trajectory of
given electron is fixed an electron in an atom
An orbit is a one dimensional path of an An orbital is a three dimensional space around
electron the nucleus
The movement of an electron in an orbit is It is in accordance with Heisenberg
known definitely which is against Heisenberg Uncertainty Principle
Uncertainty Principle
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The Aufbau principle

“Aufbau” is a German word meaning „building up‟. Aufbau principle is a principle that
gives the order in which orbitals are filled in successive elements in the periodic table.

It states that electrons enter orbitals of lowest energy first. The electrons are added to
atomic orbitals starting with the lowest energy orbitals and building up to higher energy
orbitals

The order is as follows:

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The filling proceeds as

Pauli Exclusion principle

It states that all the electrons in any atom must be distinguishable or that no two
electrons in a single atom can have all their quantum numbers alike. It follows that if
two electrons in an atom have the same values of n, l and m, they must have different
values of s. Their spins must be opposed. One must spin up and the other spins down.

Hund’s rule
It is also called Hund’s Multiplicity Rule. According to the rule, when electrons occupy
orbitals of equal energy, they do not pair up in an orbital until all the other orbitals in
the sub energy level have been occupied by a single electron.

The filling shown first is acceptable but not the second case
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Electronic configuration of atoms

The Hund‟s rule, Pauli Exclusion principle and the Aufbau principle are all applied in
writing of electronic configurations of atoms.

The notation is used and the subenergy levels contain a maximum number of
electrons as shown. The atomic number is used to write the configuration.

The table below shows the first 20 elements with their electronic configurations. Some
configurations are written and others are not. Complete the table

Element Symbol Atomic number Electronic configuration

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Hydrogen H 1
Helium He 2
Lithium Li 3
Beryllium Be 4
Boron B 5
Carbon C 6
Nitrogen N 7
Oxygen O 8
Fluorine F 9
Neon Ne 10
Sodium Na 11
Magnesium Mg 12
Aluminium Al 13
Silicon Si 14
Phosphorus P 15
Sulphur S 16
Chlorine Cl 17
Argon Ar 18
Potassium K 19
Calcium Ca 20
Below is another table for the electronic configurations of the first transition series for
elements scandium to zinc.
An atom of an element is only stable if its outermost sub energy level is either completely
filled or half filled with electrons. In this series, this affects the electronic configuration
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of chromium and copper. An electron that would be in the 4s sub energy level is filled
in the 3d sub energy level do make it half-filled for copper and completely filled for
chromium. Complete the table too to show the electronic configurations of the other
elements.
Scandium 21
Titanium 22
Vanadium 23
Chromium 24
Manganese 25
Iron 26
Cobalt 27
Nickel 28
Copper 29
Zinc 30
More other elements with atomic numbers greater than 30 are shown below with some

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

electronic configurations filled. Follow the same procedure to complete the electronic
configurations for the other elements.

Germanium Ge 32
Bromine Br 35
Strontium Sr 38
Silver Ag 47
Tin Sn 50
Iodine I 53
Barium Ba 56
Lead Pb 82

Electronic configuration of ions

Ions are formed by gaining electrons (anions) or losing electrons (cations). When writing
their electronic configurations, electrons are either removed or added to the outer most
sub energy levels depending on the charge on the ion. For cations of the elements in the
first transition series (scandium to zinc), electrons in the 4s sub energy level are removed
first before those in the 3d sub energy level. Similarly, we can subtract or add electrons to
the atomic number of the neutral atom and use the remaining electrons to write the
configuration. Write configurations for the following ions.
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Ion Electronic configuration

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Questions
1. What is meant by the terms?
(i) Orbital
(ii) Pauli‟s exclusion principle
(iii) Ionisation energy

2. (a) Describe and explain the atomic spectrum of hydrogen

(b) Explain how the hydrogen spectrum is related to the idea of quantized energy
levels in atoms and ionisation energy.

3. (a) (i) What is meant by stability of a nucleus?

(ii) State and explain the factors that affect stability of a nucleus.
(b) The graph below shows how the number of neutrons varies with that of
protons.
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Number of neutrons B

80 P ⁄

60

20

0 20 60 80 83 Number of protons

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(i) State what line A and region B represent.
(ii) State why nuclei in the following regions P, Q and R are unstable
(iii) Briefly explain how nuclei in the regions P and R can gain stability

4. The diagram below shows the Lyman series part of a hydrogen emission spectrum.
A B C D EFG

(a) State;
(i) the information obtained from the separate lines about the electronic
structure of hydrogen
(ii) the direction in which energy increases
(iii) the direction in which frequency increases
(iv) the direction in which wavelength increases
(v) how the emission spectrum arises
(b) Briefly explain why the lines get closer together from left to right
(c) State what is meant by the term “principal quantum number”
5. (a) What is meant by the term quantum number?
(b) State the significance each of these quantum numbers on information about an
atom.
(i) the spin quantum number
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(ii) the angular momentum quantum number

(iii) the magnetic quantum number
(iv) the principal quantum number
6. (a) Write the electronic configuration of:
(i) nitrogen
(ii) phosphorus
(b) Explain why nitrogen only forms nitrogen trichloride while phosphorus forms
both phosphorus trichloride and phosphorus pentachloride.

THE PERIODIC TABLE

The historical development of the Periodic Table
Prout, an Englishman, made the earliest attempt to show a connection between atoms of
different elements. This was in 1815, seven years after the publication of the atomic
theory.

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He found out that the many atomic weights determined by Dalton, Berzelius and others
were approximately whole number multiples of the atomic weight of hydrogen. Prout
therefore suggested that atoms of different elements were composed of hydrogen atoms
in various numbers. This whole number rule as however abandoned soon.
In 1858, Cannizzaro introduced a method of finding relative atomic masses. Chemists
soon observed a periodic relationship between the properties of elements and their
relative atomic masses.
In 1864, Newlands showed that if elements were arranged in order of their atomic
weights, elements with similar properties appeared in intervals. Part of his table is shown
below.

Elements that were chemically similar such as lithium, sodium and potassium usually
occurred in every eighth position. From his observation, Newland put forward the
following periodic law; the properties of elements are a periodic function of their
atomic weights.
Newlands‟ law however did not convince majority of the chemists. This is because some
elements were placed in the table but assigned incorrect relative atomic masses. In
addition, no allowance was given for the possibility of the undiscovered elements.
In 1869, the Russian chemist, Demitri Mendeleeff, used Newlands basic idea to devise a
new kind of table. He arranged all the known elements in order of their relative atomic
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masses to show the relationships between the elements more clearly. He improved
Newlands‟ table by;
1. Leaving gaps in the Periodic Table on a prediction the new elements would be
discovered to fill the gaps. He predicted the properties of the undiscovered elements.
When the elements were discovered and found to have relative atomic mass and the
physical and chemical properties Mendeleeff predicted, chemists strongly believed in
his Periodic Table.
2. Introducing long rows periods for the elements now called transition elements. This
implied that the elements were not placed under nonmetals as in
Newlands‟ system.
Below is part of Mendeleef‟s Periodic Table;

1 2 3 4 5 6 7 8
1

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2
3
4 ... ... ... ... ...
5 ... ...
More elements were soon discovered including the noble gases which now make the
Modern Periodic Table.

Unique position of Hydrogen in the Periodic Table

The position of hydrogen in the Periodic Table is a great source of argument. Whereas
some authors place it above lithium in group I, others place it above fluorine in group
VII. Others place isolate it to a central position to indicate that it is unique and has no
genuine analogues.

From its electronic structure, , hydrogen resembles group I elements which have one
electron in the outermost sub energy level. Hydrogen is also similar to group I elements
in being electropositive because it is liberated at the cathode when aqueous solutions of
acids are electrolyzed.

Also just like group VII elements, the hydrogen atom is one electron short of a noble gas
configuration. Therefore hydrogen resembles elements in both groups in being
consistently monovalent when combining with other elements.

The properties of hydrogen relate it much more to the halogens than alkali metals. It has a
much higher ionisation energy and electronegativity than alkali metal. This gives it a
nonmetallic character. It also resembles halogens by existing as diatomic molecules. Just
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like salts of halogens, when fused metallic hydrides liberate hydrogen at the anode on
electrolysis.

The Modern Periodic Table

The structure of the Modern Periodic Table

In the modern Periodic Table, elements are arranged in order of increasing atomic
numbers instead of atomic mass. Atomic numbers increase from left to right and from
top to bottom in the table. The modern Periodic Table has more elements than
Mendeleef‟s table because many elements have been discovered since his time. The
elements can be classified in three classes; metals, metalloids and non-metals.
In the modern Periodic Table, each element is represented by its chemical symbol, atomic
mass and mass number. The rows in the table are called Periods and the columns are the
groups. The table has a total of 18 groups and 7 periods.
The first period has only 2 elements. The second and third periods have 8 elements each.

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The fourth and fifth have 18 elements each. The sixth has 32 elements. The seventh
period has 32 elements including Nihonium-113, Moscovium-115, Tennesine-117 and
Oganeson-118. These new elements were approved in 2015 by IUPAC and added to the
table to complete the seventh period to 32 elements.
There is a separate group of elements at the bottom of the table. It consists of 14 elements
of the sixth period called the lanthanides and 14 elements of the seventh period called
the actinides.
Elements in the same group have similar chemical properties and the same outermost
configuration.
GROUPS
IA IIA IIIA IVA VA VIA VIIA VIII IB IIB IIIB IVB VB VIB VIIB O
1
2
PERIODS

3
4
5
6
7

Lanthanum series
Actinium series
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Classification of elements based on the electronic configuration as s, p, d and f

blocks.

The Periodic Table is divided into four main blocks; these blocks are s-block, p-block, d-
block and f-block
s-block elements
They are placed in the left hand block of the table. The s-block contains the elements
whose outermost electrons occupy the s sub-energy level. The s-block consists of two
groups of elements;
IA whose electronic configuration ends with ,
IIA whose electronic configuration ends with .
p-block elements
These occupy the right hand block of table. The p-block contains the elements whose
outermost electrons occupy the p sub-energy level except helium.

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All elements placed in groups IIIB, IVB, VB, VIB, VIIB and O are p-block elements.
d-block elements
They occupy the middle block of the table. The d-block contains the elements with the
outermost electrons in the d sub-energy level after the s sub-energy level is filled. The d-
block elements are classified according to the outer energy sub-energy level and the
period number into three series which are:
1. The first transition series:
It includes the elements in which the 3d sub-energy level is filled successively. It
lies in the fourth period and includes the elements from scandium ( 21Sc ) to
zinc ( 30Zn ) .
2. The second transition series:
It includes the elements in which the 4d sub-energy level is filled successively. It
lies in the fifth period and includes the elements from yttrium (39Y) to
cadmium ( 48Cd ) .
3. The third transition series:
It includes the elements in which the 5d sub-energy level is filled successively. It lies
in the sixth period and includes the elements from lanthanum ( 57La ) to
mercury ( 80Hg ) , excluding the lanthanides.
f-block elements
They are separated down the Periodic table , to avoid being a very wide table , In which
the f sub-energy level is filled successively , The f-block is divided into 2 series, each
with 14 elements. These are:
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1. The lanthanides
These are in the sixth period, in which the 4f sub-energy level is filled successively.
The elements of this series are quite similar in behaviour and very difficult to be
separated as the outermost energy level for all of them is 6s² .
2. The actinides
These are placed in seventh period, in which the 5f sub-energy level is filled
successively. All the elements of this series are radioactive and their nuclei are
unstable.

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The table below shows the common elements. Use their electronic configurations to
classify them into groups, periods and the s, p, d and f blocks

Element Atomic Electronic configuration Group Period Periodic

number Block
H 1
He 2
Li 3
Be 4
B 5
C 6
N 7
O 8
F 9
Ne 10
Na 11
Mg 12
Al 13
Si 14
P 15
S 16
Cl 17
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Ar 18
K 19
Ca 20
21
22
23
24
25
26
27
28
29
30
32
38

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50
53
56
82

Classification into metals, metalloids and non-metals

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Metals
Metalloids
Non-metals
The elements in the Modern Periodic table can be classified as metals, metalloids or non-
metals. Most of the elements in the table are metals. In the periodic table, there is a
change from metallic to non-metallic properties across the table, and an increase in
metallic properties down a group. Consequently there is a diagonal nearer the center of
the table ( ) in which there is a borderline between metals and non-metals, and
the metalloids are the borderline cases.

The metals are good conductors of heat and electricity have a shiny lustre, malleable and
ductile, usually have high melting points and high densities.

The non-metals are poor thermal conductors, good heat insulators, and are neither
malleable nor ductile.

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Metalloids are a class of chemical elements that are intermediate in properties between
metals and non-metals. Elements such as arsenic, germanium, and tellurium are
semiconductors and their conductivity increases as their temperature increases.

Periodicity of atomic properties in the Periodic Table

The common atomic properties include

 Atomic radius
 Ionisation energy
 Electron affinity
 Electronegativity
 Electropositivity
 Metallic character
 Standard electrode potential
The factors affecting atomic properties of elements include;

1. Nuclear charge
2. Shielding effect/ screening effect
3. Electronic configuration
4. Atomic radius.
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1. Nuclear charge
This is simply the total number of positive charges in the nucleus of an atom. It is an
equivalent to the number of protons.

2. Shielding effect/ screening effect

This is the repulsion of the outermost electrons by those in the innermost sub energy
levels from nuclear attraction. Electrons in an atom shield each other from the pull of the
nucleus. Shielding effect describes the decrease in attraction between an electron and the
nucleus in any atom with more than one energy level. The greater the number of energy
levels, the greater the shielding effect.

3. Effective nuclear charge( )

This is the net positive charge experienced by an electron in an atom. Effective nuclear
charge is given by the equation;

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Using the formula, it can be interpreted that if the nuclear charge is high and the
screening effect is low, then effective nuclear charge increases. When the screening effect
is high and nuclear charge is low, the effective nuclear charge reduces.

Atomic and Ionic radius

Atomic radius is half the internuclear distance between two atoms in a covalently
bonded diatomic molecule with similar atoms or in a metallic bond.

Similar atoms
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The variation in atomic radius down a group or across a period is determined by the
factors;

1. Nuclear charge
The higher the nuclear charge, the more strongly are the outermost electrons attracted
closer to the nucleus, reducing the atomic radius. The lower the nuclear charge, the
weaker the attraction of the outer most electrons to the nucleus hence the increasing the
atomic radius.

2. Screening effect.
The greater the screening effect, the stronger the repulsion of the outermost electrons
from the nuclear attraction. The electrons are thus far and weakly attracted to the nucleus,
increasing the atomic radius. The lower the screening effect, the lower the repulsion of
the outermost electrons from the nuclear attraction. The electrons are thus nearer and
strongly attracted to the nucleus, reducing the atomic radius.

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Variation in atomic radius and ionic radius in Periods and groups
1. The table below shows variation in atomic and ionic radii across Period 3
Element Na Mg Al Si P S Cl
Atomic radius(nm) 0.156 0.136 0.125 0.117 0.110 0.104 0.099
Ionic radius(nm) 0.095 0.065 0.054 0.212 0.184 0.181
(a) State and explain the trend in atomic radius of the elements
Atomic radius decreases from sodium to chlorine.

This is because from sodium to chlorine, nuclear charge increases because a proton is
added to nucleus from element to element. Screening effect almost remains constant,
because electrons are added to the same energy level. Effective nuclear charge increases,
and outer most electrons get closer and more strongly attracted than repelled by the
nucleus.

(a) Explain why:

(i) the ionic radii of and are smaller than those of the
corresponding atoms.
The ions are formed by losing electrons. When the electrons are lost, the number of
protons becomes greater than the number of remaining electrons. Screening effect is
reduced. Effective nuclear charge increases. The remaining electrons become strongly
attracted by the nucleus than they are repelled.

(ii) the ionic radii of and are larger than those of the
corresponding atoms
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The ions are formed by gaining electrons. When the electrons are gained, the number of
electrons becomes greater than the number of existing protons. Screening effect
increases. Effective nuclear charge reduces. The electrons become more strongly
repelled by the nucleus than they are attracted.

(b) The ions and have the same electronic configuration, yet they
have different ionic radii. Suggest a reason for this.
The ions are formed by losing electrons, reducing the screening effect. The number of
protons however remains unchanged. The effective nuclear charge therefore increases in
the order since proton number increases in the same order. The
ionic radius therefore decreases in the order

2. The table below shows the atomic radii and ionic radii of the elements in Group II of
the Periodic Table.
Element Be Mg Ca Sr Ba

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Atomic radius(nm) 0.089 0.136 0.174 0.191 0.198
Ionic radius(nm) 0.031 0.065 0.099 0.113 0.135

(a) State and explain the trend in atomic radius of the elements
Atomic radius increases from Beryllium to Barium.

This is because from Beryllium to Barium, nuclear charge increases; screening effect
also increases, because an extra energy level completely filled with electrons is added.
Increase in screening effect outweighs increase in nuclear charge. Effective nuclear
charge decreases, and outer most electrons are far and weakly attracted by the nucleus.

(b) Explain why the ionic radius is smaller than the atomic radius of corresponding
neutral atom for each element.
The cations are formed by losing electrons. When the electrons are lost, the number of
remaining electrons becomes lower than the number of existing protons. Screening effect
decreases. Effective nuclear charge increases. The electrons become more strongly
attracted by the nucleus than they are repelled reducing the ionic radius. In the neutral
atom, the screening effect is counterbalanced by nuclear charge.
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Ionisation energy

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CHAPTER THREE
STRUCTURE AND BONDING
CHEMICAL BONDING
Chemical bonding is one of the basic fundamentals of chemistry that explain other
concepts such as chemical reactions. An atom consists of the nucleus containing protons
and neutrons and electrons in certain energy levels rotating around the nucleus. In
chemical bonding, only the valence electrons (electrons located in the outermost energy
levels) of an atom are involved.

Chemical bonds are forces that hold atoms, ions or molecules together to make
compounds. During formation of a chemical bond, atoms combine in order to acquire a
noble gas electronic structure. This can be achieved by either transfer of electrons from

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

one atom to another or by sharing electrons contributed by each atom or by electrostatic
attraction between delocalized electrons and positively charged ions.

Lewis Dot symbols

The American chemist G.N. Lewis devised a system of symbols called Lewis electron
dot symbols that can be used to predict the number of bonds formed by most elements in
their compounds. Each Lewis Dot symbol consists of the chemical symbol of the element
surrounded by dots. The dots represent the valence electrons of an element.

The following steps can be followed to draw Lewis Dot symbols of different elements

1. Identify the number of valence electrons for the element. These are the total number
of electrons in the outermost energy level. They can be known by the electronic
configuration
2. Write the correct chemical symbol of the element
3. Put one dot in all directions; up, down, left and right of the element symbol
4. If some electrons are left, begin doubling the dots
From the Lewis Dot symbol of each element, we can predict the number of bonds an
element can form during bonding.
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Examples

Draw the Lewis Dot symbols for the elements Boron, Carbon, Nitrogen and Oxygen

Element Atomic Electronic Number Lewis Dot Number of bonds

number configuration of structure that can be formed
Valence
electrons

3 1 Three bonds

6 4 Four bonds

7 5 Three bonds

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8 6 Two bonds

Note that the Lewis Dot symbols below cannot be correct because dots have to be placed
in all directions before pairing occurs.

The table below shows the electronic configuration of the first 20 elements of the
Periodic Table. Use the valence electrons of each element to draw its Lewis Dot
structure and predict the number of bonds the element can form
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Symbol Atomic Electronic configuration Lewis Dot Number of

number structure bonds that can
be formed
H 1
He 2
Li 3
Be 4
B 5
C 6
N 7
O 8

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

F 9
Ne 10
Na 11
Mg 12
Al 13
Si 14
P 15
S 16
Cl 17
Ar 18
K 19
Ca 20
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The octet rule and ions

Most elements, except noble gases, combine with other elements to form compounds.
Compounds are the result of formation of chemical bonds between two or more atoms of
different elements.

In the formation of a chemical bond, atoms lose, gain or share valence electrons to
completely fill their outermost energy levels and attain a noble gas configuration. This
tendency of atoms to have eight electrons in their outermost energy levels is known as the
octet rule.

It states that; an atom is most stable when there are eight electrons in its outermost
energy level.

Only the and electrons are involved in the octet rule. It does not apply to or
electrons.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Atoms of metallic elements have few electrons in their outer most sub energy levels. By
losing those electrons, metals can gain a noble gas configuration and satisfy the octet
rule. Similarly, atoms of nonmetals have close to eight electrons in their outermost sub
energy levels. They tend to readily accept electrons to achieve the noble gas
configuration, satisfying the octet rule.

The octet rule is important in the following ways;

1. It explains the formation of chemical bonds in various compounds depending on

the nature of the elements involved.
2. It is used to predict stability of atoms
Point of thought;
1. Outline the importance of the Octet rule in formation of ions and
stability of compounds.
2. Identify the stable ions of the first 20 elements of the Periodic Table
using the Octet rule.
Stable ions without an Octet

There are a number of elements whose atoms can exist in stable compounds by forming
bonds with less than eight valence electrons. When this occurs, the atom of the element
within the molecule is said to have an incomplete octet. The examples include; hydrogen
ion, beryllium ion, boron ion and aluminium ion. The boron ion and aluminium ion can
form stable ions in covalent compounds like boron trifluoride and aluminium chloride.
The phosphorus atom in phosphorus pentachloride has 10 electrons and Sulphur in
Sulphur hexafluoride has 12.
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Ionic bond formation

An ionic bond is also called an electrovalent bond.

It is formed by complete transfer of one or more electrons from one atom to another to
form oppositely charged ions.
The electron or electrons are transferred from a metallic element to a nonmetallic
element.
The element that loses electrons is electropositive since it forms a positive ion. The

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

element gaining electrons is electronegative since it forms a negative ion.
The cation and anion formed are held together by strong electrostatic forces of
attraction.
Examples;

(i) Formation of sodium chloride

𝑵𝒂 𝑪𝒍 𝑵𝒂 𝑪𝒍

The sodium atom has electronic The chlorine atom has electronic configuration,
configuration, . The 3s . The 3p subenergy level has
subenergy level has one electron and is five electrons and is unstable. The electron
unstable. This electron is transferred to the transferred from sodium occupies this sub energy
chlorine atom by sodium to form noble gas level to form noble gas
configuration, . A Sodium ion is configuration, . A chloride ion
formed. is formed.

The sodium ion and chloride ion get hold together by strong electrostatic forces of
attraction.
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(ii) Formation of magnesium oxide

2 2

𝑴𝒈 𝑶 𝑴𝒈 𝑶

The magnesium atom has electronic The oxygen atom has electronic configuration,
configuration, . The two 3s . The 2p sub energy level has four
electrons are transferred to the oxygen atom electrons and is unstable. The two electrons
by magnesium to form noble gas transferred from magnesium occupy this sub
configuration, . A magnesium energy level form noble gas
ion is formed. configuration, . An oxide ion is
formed.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The magnesium ion and oxide ion get hold together by strong electrostatic forces of
attraction.

Giant ionic structures

In giant ionic structures, metallic elements combine with non-metallic elements.
The ionic bonds formed in these compounds are strong electrostatic attractions between
the ions of opposite charges (cations and anions).
Each ion is surrounded by the greatest number of oppositely charged ions called the
coordination number.
Examples of giant ionic solids include sodium chloride, caesium chloride and zinc
blende.
Check under matter (specifically under the solid state of matter for details about
giant ionic structures)
Structures of some ionic compounds
Compound Structure
Sodium oxide
Magnesium oxide
Calcium chloride
Sodium hydride
Magnesium sulphate
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The properties of ionic compounds

Property Explanation
1. High melting and boiling There are strong electrostatic forces of attraction between
points. the oppositely charged ions that require a high amount of
energy to break.
2. They are strong electrolytes in In the ionizing solvent, the forces of attraction between the
molten state or aqueous state ions are greatly reduced and the oppositely charged ions
become free to move in molten or aqueous state under the
influence of an electric field.
3. They readily dissolve polar The ion-solvent interactions are stronger than ion-ion
solvents like water but interactions of the compound for polar solvents. Ion-ion
insoluble in non-polar solvents interaction is stronger than ion-solvent interaction and
like methylbenzene solvent-solvent interaction for non-polar solvents.
4. Exist as crystalline solids at There are strong electrostatic forces of attraction between
room temperature the oppositely charged ions that require a high amount of
energy to break at room temperature, keeping the
molecules so closely packed together.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Explain why sodium chloride is soluble in water but insoluble in benzene.
On dissolving in water, the electrostatic forces of attraction between the sodium ions and
chloride ions in the crystal lattice are greatly reduced. The ions become free to move in
solution. Since water is a polar molecule, the sodium ions get attracted to the negative
end of water molecules and the chloride ions get attracted to the positive end of the water
molecules. The formation of ion-solvent interactions releases enough energy to break the
sodium-chlorine bonds. The ion-solvent interactions are stronger than ion-ion
interactions in sodium chloride.

Benzene is non-polar. Ion-ion interaction is stronger than ion-solvent interaction and

solvent-solvent interaction in benzene.
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Covalent character in ionic compounds

The partial covalent character of an ionic bond is explained in terms of polarising power
and polarisability.
1. Polarising power
Polarising power is the power of a cation to distort the electron cloud of an anion.
The greater the polarising power of the cation, the greater the tendency of the cation to
form a covalent bond.

Polarising power of a cation depends on;

(i) Charge of the cation
Cations with high charges have high polarising power. The larger the positive charge on
the ion, the greater the attraction of the valence electrons. The ion therefore has a
higher polarising power than the due to its higher charge.

(ii) Cationic radius

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The smaller the ionic radius, the higher the polarising power of the cation. The ion
therefore has a higher polarising power than the due to its smaller ionic radius.

(iii) Charge density or charge-radius ratio.

Charge density is the ratio of ionic charge to ionic radius.

Ion
Ionic radius(nm) 0.095 0.065 0.050
Charge density

The higher the charge density, the higher the polarising power of the cation. From the
table above, charge density and hence polarising power increases in the order
.The covalent character of the chlorides formed by the elements
increases from sodium chloride to magnesium chloride to aluminium chloride due to the
increase in polarising power.

In general, compounds in which a cation has a high charge and small ionic radius tend
to have a high charge density and high polarising power. This makes such compounds
tend to a covalent character and exhibit properties contrary to ionic compounds

Aluminium chloride, beryllium chloride, aluminium hydride, beryllium hydride,

beryllium oxide and beryllium hydroxide are partly covalent for reasons explained above.
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1. Polarisability
Polarisability is the ease by which the electron cloud of the anion can be distorted.
The greater the polarisability of the anion, the greater the tendency of the anion to form a
covalent bond.
Polarisability of an anion depends on the size of the anion
The smaller the anion, the lower it is polarizable and the larger the anion, the easier it is
polarized.
If we consider the halide ions, polarisability increases in the order

Examples to show effect of polarising power of cations and polarisability of anions

(i) The table below shows the melting points of the chlorides formed by the three
Period 3 elements.
Chloride
Melting point of the choride (oC) 801 712 180

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

State and explain the trend in melting points of the chlorides of the three metals.
Melting points of the chlorides decrease from sodium chloride to aluminium chloride.

Sodium chloride and magnesium chloride have giant ionic structures held by strong
ionic bonds which require a high amount of energy to break. The decrease in melting
point from sodium chloride to magnesium chloride is because magnesium ion has a
smaller ionic radius, higher charge density and higher polarising power than sodium
ion making magnesium chloride less ionic than sodium chloride. Aluminium chloride has
the lowest melting point because among the cations, the aluminium ion has the smallest
ionic radius, highest charge density and highest polarising power. Aluminium chloride
is therefore predominantly covalent. Covalent bonds require a low amount of energy to
break

(ii) Aluminium chloride dissolves in methylbenzene but sodium chloride does not.
The aluminium ion in aluminium chloride has a higher charge and a smaller ionic
radius than the sodium ion in sodium chloride. The aluminium ion therefore has a higher
charge density and higher polarising power than the sodium ion. The chloride ion being
greatly polarized by the aluminium ion makes aluminium chloride mainly covalent
hence soluble in non-polar methylbenzene. However, sodium chloride is purely ionic and
insoluble in non-polar solvents.
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(iii) The melting point of lead(II) chloride is 500℃ whereas that of tin(II) chloride
is 247℃. Explain this observation.

Lead(II) ion has a larger ionic radius than tin(II) ion. Therefore the tin(II) ion has a
higher charge density and polarising power than the lead(II) ion. This makes tin(II)
chloride mainly covalent whereas lead(II) chloride is mainly ionic. Covalent bonds need
a lower amount of energy to break than ionic bonds.
(iv) Lead(II) chloride is insoluble in ethanol whereas lead(IV) chloride readily
dissolves in ethanol.
The lead(II) ion in lead(II) chloride has a smaller charge and a larger ionic radius than
the lead(IV) ion in lead(IV) chloride. Therefore the lead(II) ion has a lower charge
density and lower polarising power than the lead(IV) ion. This makes lead(II) chloride
mainly ionic hence insoluble in nonpolar solvents whereas lead(IV) chloride is mainly
covalent hence soluble in non-polar solvents.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(v) the melting point of calcium oxide is higher than that of calcium chloride
The oxide ion in calcium oxide has a smaller ionic radius than the chloride ion in
calcium chloride. Therefore the oxide ion less easily polarized by the calcium ion
whereas the chloride ion is more easily polarized by the calcium ion. This makes
calcium oxide more ionic than calcium chloride. The ionic bonds in calcium oxide
require a higher amount of energy to break.

(vi) The table below shows the melting points of magnesium halides.
Formula of halide
Melting point(OC) 1263 714 711 634
Explain the general trend in melting points of the halides.
The melting points of the halides decrease from magnesium fluoride to magnesium
iodide. This is because the anionic radius increases from the fluoride ion to the iodide
ion. The degree of polarization of the anions also therefore increases from the fluoride
ion to the iodide ion, increasing the covalent character of the halides. Thus a
decreasing amount of energy is required to break the magnesium-halogen bonds that
become increasingly more covalent.
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Questions
1. Explain why
(a) calcium iodide is ionic whereas aluminium iodide is covalent
(b) Sodium chloride melts at 800 oC whereas aluminium chloride sublimes at 180 oC
(c) Beryllium chloride is more soluble in ethanol than in water whereas barium
chloride is more soluble in water than in ethanol
(d) The solubility of lithium chloride in ethanol is higher than the solubility of
potassium chloride in ethanol.
(e) aluminium fluoride sublimes at whereas aluminium chloride sublimes at

(f) aluminium chloride is soluble in methylbenzene and has a low melting point yet
aluminium fluoride is soluble in water and has a higher melting point.
(g) tin(II) chloride is a solid whereas tin(IV) chloride is a liquid at room temperature
(h) lead(II) fluoride has a higher melting point than lead(IV) fluoride

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(i) iron(II) chloride is more ionic than iron(III) chloride
2. Explain why
(i) the solubility of lead(II) halides increases in the order;
(ii) melting points of the halides of aluminium decrease in the order;

3. The table below shows the melting points of the chlorides of Group II elements.

Chloride
Melting point (OC) 405 714 782 875 962
Explain why;
(i) the melting point of beryllium chloride is very low
(ii) melting point increases from magnesium chloride to Barium chloride

Covalent bond formation

A covalent bond is formed when electrons are shared in pairs between two bonded
atoms.
In a single covalent bond between two atoms, one electron is contributed by each atom
and is shared as a pair of electrons.
The shared pair of electrons is called a covalent bond.
The shared pair of electrons occupies the same orbital with opposing spins and each of
the electrons must be unpaired from the orbital in which it is got.
In double covalent bonds, two pairs of electrons are shared and in a triple covalent bond,
three pairs of electrons are shared.
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Covalent bonds may be formed between atoms of the same element or atoms of
different elements
Usually the bonding atoms contribute an equal number of electrons towards formation of
a normal covalent bond.
Examples

(i) Formation of chlorine molecule

𝑪𝒍 𝑪𝒍 or

The chlorine atom has electronic configuration, . The

chlorine molecule is formed by each of the chlorine atom sharing one of its

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

valence electrons with another atom. The two atoms approach each other
closely for their atomic orbitals to overlap.

(ii) Formation of hydrogen chloride molecule

or
𝑯 𝑪𝒍

The hydrogen atom has electronic configuration and the chlorine atom has
electronic configuration, . Hydrogen contributes its only electron and
chlorine contributes one of its valence electrons. The electron pair is shared to make
hydrogen have a full s sub energy level and chlorine to have a full octet.

(iii) Formation of ethene

In an ethene molecule, each carbon atom shares one pair of electrons with a hydrogen
atom and two pairs of electrons with the other carbon atom. When atoms share two pairs
of electrons, a double bond is formed between them. Each carbon atom forms single
bonds to two hydrogen atoms and a double bond to the other carbon atom.
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𝑯 𝑯

or
𝑪 𝑪

𝑯 𝑯

In a simple way, covalent bonds are usually represented by a line to indicate a pair of
shared electrons, double lines to indicate two shared pairs and triple lines to indicate a
three shared pairs.
Other covalent molecules include; .

Types of covalent bonding

There are three types of covalent bonds which include; normal covalent bond, polar
covalent bond and a dative covalent bond.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

1. The normal covalent bond
In a normal covalent bond, two atoms with very similar electronegativities or almost
similar electronegativities are bonded together and the combined atoms contribute an
equal number of electrons to be shared.
One electron is contributed by each atom for a single covalent bond.
The two electrons that are shared between the atoms must be unpaired and the must also
have opposite spins from the orbitals from which they are got.
The normal covalent bond results from overlapping of the atomic orbital or charge cloud
of one electron with another.
The two atomic orbitals produce one molecular orbital on overlapping as shown below.

𝑯 𝑯 𝑯 𝑯

Overlapping of atomic orbitals of hydrogen Resulting molecular orbital of hydrogen

2. Polar covalent bond

When a covalent bond is formed between two atoms whose electronegativity values are
greatly different, the bond becomes polar. For example in hydrogen fluoride molecule,
fluorine is more electronegative than hydrogen. The fluorine atom therefore pulls the
bonding electrons more towards its self. This makes fluorine gain a partial negative
charge and hydrogen a partial positive charge, making the hydrogen fluorine bond polar.
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The bonding electron density is greater towards the fluorine atom with a small negative
charge than towards hydrogen with a small positive charge

Other polar covalent bonds as a result of difference in electronegativity of the bonding

atoms include; , , , , , etc.

For two equal but opposite separated electrical charges, there exists an electric dipole
moment. An electric dipole moment is a product of one of the charges, or and
the distance between the atomic nuclei. Any individual polar covalent bond must have a

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

corresponding dipole moment.
However, there are molecules in which the individual bonds in it are polar but the
molecule as a whole is non-polar. This will be seen later under polarity of molecules.

3. Dative covalent bond

A dative covalent bond is a covalent bond formed when the shared pair of electrons is
contributed by only one of the bonded atoms.
A dative covalent bond is also called a coordinate covalent bond.
The atom that contributes the pair of the electrons is the donor atom and the other atom
is called the acceptor atom. For an atom to act as a donor atom, it must have atleast one
pair of unshared electrons, called a lone pair.
For an atom to act as an acceptor atom, it must have atleast one vacant orbital. An
acceptor can be a transition metal atom or an atom in a molecule.
An arrow ( ) is always drawn from the donor atom to the acceptor atom to show a
dative bond.
Examples

(i) Formation of hydroxonium ion.

[ ]

This ion is formed by coordination of water to a hydrogen ion. The oxygen atom in the
water molecule has two lone pairs of electrons. The hydrogen ion has electronic
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configuration .The hydrogen ion therefore accepts one of the lone pairs of electrons
from oxygen to have a full 1s sub energy level. This results into formation of the
hydroxonium ion.

(ii) Formation of Ammonium ion

[ ]

This ion is formed by coordination of ammonia to a hydrogen ion. The nitrogen atom in
the ammonia molecule has a lone pair of electrons. The hydrogen ion has electronic
configuration .The hydrogen ion therefore accepts the lone pair of electrons from
nitrogen to have a full 1s subenergy level. This results into formation of the ammonium
ion.

(iii) Formation of dimerised aluminium chloride , dimerised iron(III)

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

chloride and dimerised beryllium chloride .

(iv) Reaction between ammonia and anhydrous aluminium chloride

or

The nitrogen atom in the ammonia molecule has a lone pair of electrons. The aluminium
atom has only three valence electrons. When aluminium covalently bonds with three
chlorine atoms in aluminium chloride, it has six electrons in its outermost energy level,
requiring two electrons to complete its octet. Since nitrogen is more electronegative than
hydrogen in ammonia, it has a partial negative charge. Also aluminium is less
electronegative than chlorine in aluminium chloride, hence has a partial positive charge.
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There is therefore an attraction between nitrogen atom and aluminium atom. The lone
pair of electrons on the nitrogen atom is donated to the aluminium atom to form a dative
bond.
Ammonia can also form coordinate bonds with boron trifluoride or boron trichloride

or

or

(v) Formation of transition metal complexes

In transition metal complexes, the donor atoms in ligands donate lone pairs of electrons
to the central metal atoms. These electrons occupy the empty d-orbitals of the transition
metal atoms. The ion formed is called a complex ion. An example is the

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

tetraamminecopper(II) ion.

[ ]

A distinction between the different types of covalent bond

Normal covalent bond Polar covalent bond Dative or coordinate

covalent bond
Can be formed between two The atoms involved must be A dative bond is formed
similar atoms of the same different between two different atoms
element
Can occur between atoms of The bond occurs between atoms with different
the same electronegativity or electronegativities
almost similar
electronegativities
Each atom contributes an equal number of electrons to be The bonding electrons are
shared contributed by only one of
the involved atoms
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Covalent bond strength

The strength of a bond is represented by its bond dissociation energy.
Bond dissociation energy is defined as the heat absorbed when one mole of a covalent
bond is broken down into its constituent gaseous atoms.
Bond dissociation energy is an endothermic process hence denoted by a positive value.

Strength of a covalent bond depends on the following factors;

(i) Bond length
The shorter the bond length, the stronger the covalent bond and the longer the bond
length, the weaker the covalent bond. This is because when bond length increases, the
region of space between atoms in which electrons are shared becomes proportionally
smaller as atomic radius increases.
(i) Atomic radius
The larger the atomic radii of bonding atoms, the greater the bond length and the lower

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

the bond dissociation energy. The lower the bond dissociation energy the lower the bond
strength. The smaller the atomic radii, the smaller the bond length and the higher the
bond dissociation energy. The higher the bond dissociation energy the higher the bond
strength.
(ii) Electronegativity difference of bonding atoms
The greater the electronegativity difference between the atoms covalently bonded
together, the greater the bond polarity and the higher the bond dissociation energy. Bond
strength increases with increase in polarity of bonds
(iii) Number of bonding electron pairs
Triple bonds involve three electron pairs and are shorter and stronger than double bonds
which involve two electron pairs which are also shorter and stronger than single bonds
that involve one electron pair between similar atoms. The energy required to break the
bonds therefore decreases as for the case of carbon-carbon bonds shown below
Bond Bond dissociation energy( )

Examples

1. The respective bond energies of the covalent bonds of group IV elements are
given below.
Bond C C Si Si Ge Ge
-1
Bond dissociation energy(kJmol ) 346 175 168
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State the trend in bond energy. Give a reason for your answer.
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The bond energy decreases from carbon-carbon bond to silicon- silicon bond to
germanium-germanium bond. This is because the atomic radius increases from carbon
to germanium, bond length increases and bond strength decreases.

2. The table below gives bond energies of hydrogen halides.

Hydride HF HCl HBr HI
-1
Bond energy(kJmol ) 556 431 336 299
Explain the observed trend in bond energy
The bond energy decreases from hydrogen fluoride to hydrogen iodide. This is because
the atomic radius increases from fluorine to iodine, bond length increases and bond
strength decreases.

Question
The table below gives bond energies of Carbon-halogen bonds.
Bond C F C Cl C Br C I

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

-1
Bond energy(kJmol ) 452 351 293 234
Explain the observed trend in bond energy

Giant covalent structures

When many very strong covalent bonds link one atom to another to form an extensive
three dimensional lattice, a giant covalent structure is formed.
Examples of giant covalent solids include diamond, graphite, silicon, silicon(IV) oxide
and fullerene.
Giant covalent solids have high melting points and are non-volatile due to the strong
covalent bonds holding the atoms together.
Check under matter (specifically under the solid state of matter for details about
giant covalent structures)

Properties of covalent compounds

Property Explanation
1. Low melting and boiling There are weak forces of attraction between the molecules thus
points. a low amount of energy is required to break them.

2. They do not conduct They neither form free mobile ions nor have delocalized
electricity except graphite electrons to conduct electricity.
3. Most covalent substances are In polar solvents, the solvent-solvent interaction is much
insoluble in polar solvents like greater than interaction between the covalent molecules in the
water but soluble in non-polar solute or the interaction between the covalent molecules and
solvents like benzene, ethanol the polar molecules in the solution. Covalent compounds tend
or propanone to dissolve in non-polar solvents because van der Waals’
forces are the binding forces in both cases.
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Note that some covalent compounds containing polar bonds as

or may dissolve in water due to interaction
between the polar bond and the water.
4. Exist as gases or liquids at There are weak van der Waals’ forces of attraction between
room temperature the molecules that require a low amount of energy to break at
room temperature, keeping the molecules far apart.

Point of thought; Compare properties of ionic and covalent compounds.

Intermolecular forces
Intermolecular forces are forces that exist between molecules. There a number of types of
intermolecular forces. They include; van der Waals forces and the hydrogen bond.
They are different from forces holding individual atoms in a molecule. The forces
between atoms in a molecule are called the intramolecular forces.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Intermolecular forces Intramolecular forces
van der Waals forces Covalent bond
Hydrogen bonds Ionic bond
Metallic bond

Intermolecular attraction intramolecular attraction (polar covalent bond)

(hydrogen bond)

Van der Waals’ forces

These forces are neither ionic nor covalent. The van der Waals forces may exist between
polar molecules and these are called dipole-dipole interactions. The van der Waals
forces that exist between non-polar molecules are called London dispersion forces
(temporary dipole-dipole attractions).

(i) Dipole- dipole interactions

Polar molecules like hydrogen chloride and ammonia, interact to form an ordered
arrangement. In this arrangement, partial positive charge in one molecule is adjacent to
partial negative charge in another molecule.
The dipole-dipole attractive forces are increased by one dipole inducing a dipole in
another neighbouring molecule.
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(ii) London dispersion forces (temporary dipole-dipole)

Attractions also exist between non-polar molecules like the molecules of gases
, halogens and noble gases.
This is due to momentary polarization of the molecules.
If two nonpolar molecules are very close to each other, the arrangement of electrons is on
average symmetrical.
However at any given instant, the electron distribution in one molecule may be
unsymmetrical and a dipole may be in that molecule at that particular instant. This dipole
is called a temporary dipole.
The temporary dipole in one molecule can attract the electron cloud of the neighbouring
molecule and this makes both molecules to have dipoles.
The dipoles are in such a way that the molecules attract each other.
Since electrons move at high speed, the dipole may be in the other molecule in the next
instant. The induced dipole by one molecule into another results into an attraction.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The dipoles are temporary, but the net attraction which they produce is permanent. This
attraction is due to London dispersion forces.
The London dispersion form of van der Waals force is usually very weak and only
function when the molecules are very close to each other.
The size of the force however increases as the number of electrons in the molecules
increase.

Van der Waals forces are in general very weak compared to ionic or covalent bonds. This
is shown by the low melting and boiling points of substances held together by van der
Waals‟ forces

Examples to explain the effect of van der Waals’ forces

1. Explain why graphite is soft and slippery.

Each carbon atom in graphite is covalently bonded to three other carbon atoms to form
two dimensional layers of hexagonal rings of carbon atoms. The hexagonal layers held
together by weak Van-der-Waals’ forces of attraction which allow the layers to slide over
each other.
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Strong covalent bond

Layer one
Weak van der Waals forces
Carbon atoms
Layer two

2. The table below shows the melting points of the some elements in Period 3 of the
Periodic Table.
Element P S Cl Ar
Melting point(OC) 44.2 115.2 -101.5 -189.4

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Explain the trend in the melting points the elements
Phosphorus, Sulphur, chorine and argon have simple molecular structures with weak
Van-der-Waal’s forces of attraction whose magnitude increases in strength with
increase in molecular weight. Sulphur is octatomic (S8) with a higher molecular weight
hence stronger Van der Waal’s forces of attraction than Phosphorus which is
tetratomic(P4). Chlorine is diatomic (Cl2), with a higher molecular weight and stronger
Van-der-Waal’s forces than argon which is monoatomic. The energy required to break
the Van-der-Waal’s forces therefore decreases from phosphorus to argon.

3. Silicon, phosphorus, Sulphur and chlorine are period 3 elements that form
oxides whose melting points decrease in the order .
Explain the trend in melting points of the oxides
Silicon(IV) oxide has a giant covalent structure in which each silicon atom is bonded to
four oxygen atoms making very many strong covalent bonds that require a high amount
of energy to break. Phosphorus pentoxide, sulphur trioxide and Chlorine(VII) oxide have
simple molecular structures whose molecules are held by weak van der waal’s forces of
attraction whose strength decreases with decrease in polarity of the molecules as a
result of increase in electronegativities of the atoms bonded to oxygen

4. Briefly explain why carbon dioxide is a gas whereas silicon(IV) oxide is a solid at
room temperature.
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Carbon dioxide is non-polar. It has discrete molecules with a simple molecular structure
held by weak van der Waals forces of attraction which are easily overcome at room
temperature keeping the molecules far apart from each other.
However, in silicon(IV) oxide, each silicon atom is covalently bonded to four oxygen
atoms to form a tetrahedral structure which is continuous to form a giant molecular
structure with very many strong covalent bonds that are not easily broken at room
temperature, keeping its molecules very close to each other.

5. The table below shows the boiling points of the hydrides of group IV elements.

Hydride CH4 SiH4 GeH4 SnH4 PbH4

0
Boiling point( C) -161.5 -111.9 -88 -52 -13

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Explain the trend in variation of the melting points of the hydrides.
(Note that all these hydrides are gases)
Boiling point increases from methane to plumbane.
This is because molecules of the hydrides are held by weak van der Waals’ forces of
attraction whose strength increases with increase in molecular weight and molecular
size.
6. Explain why fluorine and chlorine exist as gases whereas bromine and iodine
exist as liquid and solid respectively at room temperature
From fluorine to iodine, atomic radius increases, molecular size and molecular mass
increases, hence magnitude of Van der Waals’ forces of attraction holding the molecules
increase in the order; . The Van der Waals’ forces in bromine and
iodine are strong enough to hold the molecules closer to each other existing as liquid and
solid respectively. Fluorine and chlorine have weaker Van der Waals’ forces due to their
small size and low molecular masses. Their molecules are therefore far apart.

7. The table below shows the boiling points some alkylhalides

Element
Boiling point(OC)
Explain the trend in boiling points of the chloroalkanes.
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Boiling point increases from chloromethane to chloroethane to chloropropane to

chlorobutane.
This is because molecules of the chloroalkanes are held by weak van der Waals’ forces of
attraction whose strength increases with increase in molecular weight and molecular
size.
8. The table below shows the boiling points some alkylhalides

Element
Boiling point(OC)

Explain the trend in boiling points of the alkylhalides

Boiling point increases from fluoromethane to chloromethane to bromomethane to

iodomethane.
This is because the atomic radius of the halogen atoms increases in the order;
, molecular size and molecular mass of the alkylhalides increases,

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

hence magnitude of Van der Waals’ forces of attraction holding the molecules increases.

9. 2, 2-dimethyl propane boils at a lower temperature than n-pentane yet both are
of the same molecular weight.

2, 2-dimethyl propane is a branched isomer giving it a spherical shape which reduces its
size and weaker Vander Waal’s forces of attraction will exist between the molecules.
n-pentane is a straight chain molecule which gives the molecule an extended structure
resulting into relatively stronger Vander Waal’s forces.

The hydrogen bond

A hydrogen bond is a dipole- dipole attraction which occurs between a hydrogen atom
attached to a strongly electronegative atom and a second strongly electronegative atom
with a lone pair of electrons.
The electronegative atoms are commonly fluorine, oxygen or nitrogen.
Fluorine has the highest electronegativity. For this reason, hydrogen fluoride forms the
strongest hydrogen bonds which persist even in vapour state.
The greatest number of hydrogen bonds known are those which unite two oxygen atoms.
The hydrogen bond is weaker than a normal covalent bond.
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Types of hydrogen bonding

(i) Intermolecular hydrogen bonding
This is the type of hydrogen bond that occurs between two or more similar or different
molecules.
Intermolecular hydrogen bonds occur in the following examples;
(a) Hydrogen fluoride , water and ammonia molecules
Hydrogen fluoride
If two polar hydrogen fluoride molecules are close enough, there is an attraction between
the positive end of one molecule and the negative end of the other molecule. Since the
attraction between the hydrogen atom in one molecule and the fluorine atom in the other
molecule is stronger than the repulsion between the two hydrogen atoms and between the
two fluorine atoms, the two molecules are bonded together by a hydrogen bond.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Intermolecular hydrogen bond

This explains why hydrogen fluoride is a liquid whereas other group VII hydrides are
gases at room temperature; hydrogen fluoride has a higher boiling point than any other
hydride of group VII.

Water molecules

Water molecules also associate through intermolecular hydrogen bonding. Each water
molecule forms four hydrogen bonds with other water molecules. This explains why
water has higher boiling point and is a liquid whereas hydrogen sulphide has a lower
melting point and is a gas although both Sulphur and oxygen are group VI elements.

Intermolecular hydrogen bonds

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Ammonia

Both ammonia and phosphine are trigonal pyramidal but ammonia has a
higher boiling point than phosphine . This is because nitrogen has a
smaller atomic radius and is more electronegative than phosphorus. This makes the
nitrogen- hydrogen bond strongly polar whereas the phosphorus- hydrogen bond is non-
polar. Ammonia molecules are therefore held together by strong hydrogen bonds which
require a high amount of energy to break than the weak van der Waals‟ forces in
phosphine.

Comparison between hydrogen fluoride, water and ammonia

Molecule Boiling point

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Although fluorine is more electronegative than oxygen, meaning the hydrogen- fluorine
bond is more polar than hydrogen-oxygen bond and hydrogen fluoride would have
stronger hydrogen bonds than water, this is not shown by the boiling points of the two
compounds. Water has a higher boiling point than hydrogen fluoride because each
water molecule forms four hydrogen bonds whereas each hydrogen fluoride molecule
forms two hydrogen bonds. The higher the number of hydrogen bonds a compound
forms, the higher the boiling point. Since nitrogen is the least electronegative element,
the nitrogen- hydrogen bond is less polar than oxygen- hydrogen bond or hydrogen-
fluorine bond. Ammonia therefore forms weaker hydrogen bonds than those in water
or hydrogen fluoride.

(b) Alcohols
Alcohols associate in their liquid form due to intermolecular hydrogen bonding. The
boiling points of alcohols are higher than boiling points of corresponding alkanes or alkyl
halides with similar molar mass because of association through hydrogen bonding.
For example the boiling point of methanol is whereas that of methane is
.

Alcohols are also more soluble in water than alkanes or alkyl halides of similar molecular
mass because of the ability to form hydrogen bonds with water.
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Alcohols with more hydroxyl groups have higher boiling points than alcohols with one
hydroxyl group. Propane-1,2,3-triol, ethane-1,2-diol and ethanol have boiling points
, and respectively.
Viscosity of alcohols also increases as number of hydroxyl groups increases due to
increased hydrogen bonding.
(c) Carboxylic acids
When methanoic acid or ethanoic acid is dissolved in benzene or
other organic solvents and the relative molecular mass of the acid determined by
cryoscopic method, the value obtained is normally twice the actual value. This is
because in liquid state form or in solution in benzene, the acids associate through
intermolecular hydrogen bonds to form dimers. The same scenario happens when

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

measurements in the vapour phase of the acids are done.

Association(dimerization of methanoic acid) Association(dimerization of ethanoic acid)

Intermolecular hydrogen
bond

In aqueous solution however, molecules of carboxylic acids do not dimerise but form
intermolecular hydrogen bonds with water. This explains their solubility in water.

(d) Amines
Amines also associate in their liquid form due to intermolecular hydrogen bonding. The
boiling points of amines are higher than boiling points of corresponding alkanes with
similar molar mass because of association through hydrogen bonding.

Amines are also soluble in water because of the ability to form hydrogen bonds with
water.
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Amines have lower boiling points than corresponding alcohols or carboxylic acids
because nitrogen is less electronegative than oxygen. The nitrogen-hydrogen bonds are
less polar than oxygen- hydrogen bonds so the hydrogen bonds formed in amines are
weaker than in alcohols.

Primary amines have higher boiling points than secondary amines which also have higher
boiling points than tertiary amines of the same molecular mass. This is because the
nitrogen atom in primary amines has two hydrogen atoms hence can form more
intermolecular hydrogen bonds than the nitrogen atom in secondary amines which has
one hydrogen atom hence can form one intermolecular hydrogen bond. The nitrogen
atom in tertiary amines has no hydrogen atom that can form hydrogen bonds.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(e) Phenols
Phenols associate in their liquid form due to intermolecular hydrogen bonding. The
boiling points of phenols are higher than boiling points of corresponding alkanes or alkyl
halides because of association through hydrogen bonding.

Phenols are more soluble in water than corresponding alkanes or alkyl halides because of
the ability to form hydrogen bonds with water just like alcohols.

(ii) Intramolecular hydrogen bonding

This is the type of hydrogen bonding that occurs within the same molecule.
An example is the intramolecular hydrogen bond formed in 2-nitrophenol,
2-chlorophenol, 2-hydroxybenzaldehyde and 2-hydroxybenzoic acid |

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2-nitrophenol 2-hydroxybenzaldehyde 2-hydroxybenzoic acid

Intramolecular
hydrogen bonds

The intramolecular hydrogen bonding prevents intermolecular hydrogen bonding

between two or more molecules. Intramolecular hydrogen bonding is not possible for 3-
and 4- substituted isomer (para and meta isomers) because of the substituent groups are
far apart. However the para and meta isomers can form intermolecular hydrogen bonds.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The intramolecular hydrogen bonding in ortho- substituted compounds explains their
difference in physical properties from their para- and meta-substituents. For example 2-
nitrophenol boils at whereas 3-nitrophenol and 4-nitrophenol boil at and
respectively.

Examples to explain the effect of hydrogen bonding

1. Explain why hydrogen fluoride is a liquid whereas other hydrides are gases at
room temperature.
Fluorine atom has the smallest atomic radius and highest electronegativity among the
halogens making the hydrogen-fluorine bond highly polar. The molecules of hydrogen
fluoride are held by strong intermolecular hydrogen bonds which keep the molecules
closer to each other. Molecules of hydrogen chloride, hydrogen bromide and hydrogen
iodide are held by weak Van der Waals’ forces that keep the molecules far apart.

2. The table below shows both boiling points of group VII hydrides.
Hydride HF HCl HBr HI
O
Boiling point( C) +19.9 -85.0 -66.7 -35.4
Explain the variation in boiling points, including any anomalies involved.
Boiling points increases from hydrogen chloride to hydrogen iodide. However, hydrogen
fluoride has an abnormally high value of boiling point.
The increase in melting point from hydrogen chloride to hydrogen iodide is because the
three hydrides have simple molecular structures held by weak Van der Waals’ forces
whose magnitude increases with the increasing molecular weight leading to an increase
in amount of energy required to break the forces.
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Hydrogen fluoride has an abnormally high melting point because the fluorine atom
has the smallest atomic radius and the highest electronegativity, making the hydrogen-
fluorine highly polar. The hydrogen fluoride molecules are therefore held by strong
intermolecular hydrogen bonds which require a high amount of energy to break.

3. Explain why;
(i) 2-chlorophenol is less soluble in water than 4-chlorophenol.
Intramolecular
hydrogen bond

Intermolecular hydrogen bond

Molecules of 2-chlorophenol form intramolecular hydrogen bonds because the choro

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

group is nearer the hydroxyl group. This suppresses the hydroxylic character of the
compound or prevents formation of intermolecular hydrogen bonds between
2-chlorophenol and water molecules reducing its solubility. However, molecules of
4-chlorophenol cannot form intramolecular hydrogen bonds because the chloro group is
far from the hydroxyl group. Molecules 4-chlorophenol therefore form intermolecular
hydrogen bonds with water. This increases its solubility.

(ii) The boiling point of 2-nitrophenol is whereas that of 3-nitrophenol is

.

Intramolecular
hydrogen bond

Intermolecular hydrogen bond

Molecules of 2-nitrophenol form intramolecular hydrogen bonds because the nitro
group is nearer the hydroxyl group. This suppresses the hydroxylic character of the
compound or prevents formation of intermolecular hydrogen bonds between
2-nitrophenol molecules hence only weak van der Waals’ forces hold the molecules.
However, molecules of 3-chlorophenol cannot form intramolecular hydrogen bonds
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because the nitro group is far from the hydroxyl group. Molecules of 3-nitrophenol
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therefore form intermolecular hydrogen bonds which are stronger hence not easily
broken.
4. Explain why ice is less dense than water

Intermolecular
hydrogen
bonds

In ice, each oxygen atom in a water molecule is surrounded tetrahedrally by four other

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

oxygen atoms through extensive intermolecular hydrogen bonds. This gives ice an open
structure. The water molecules in ice are spaced and further apart than they are in
liquid water. Therefore ice occupies a bigger volume than that of liquid water of the
same mass. Since density is inversely proportional to volume, ice has a lower density
than water. However when ice melts, the hydrogen bonds break down and the molecules
pack closely together so that liquid water has a lower volume hence a higher density
than ice.

Questions
1. Explain why
(a) The melting of silicon is much higher than that of phosphorus yet both silicon and
phosphorus are covalent substances.
(b) hydrogen and helium gases show a small deviation from ideal behaviour
(c) For gases methane, ammonia, oxygen and carbon dioxide, the deviation from ideal
behaviour increases in the order .
(d) The boiling point of the given arylhalides increases in the order

(e) The boiling point of chlorobenzene is higher than benzene which is also higher
than cyclohexane
(f) Both carbon and silicon are group IV elements. However, the melting point of
carbon dioxide is whereas that of silicon dioxide is .
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2. The table below shows the boiling points some alkanes

Element
Boiling point(OC)
Explain the trend in boiling points of the alkanes.
3. The table below shows the boiling points of halogens
Element F2 Cl2 Br2 I2
O
Boiling point( C) -187.9 -34.0 58.2 +184.5
Explain the trend in boiling points of the halogens

4. Explain the following observations;

(a) hydrogen fluoride has a higher boiling point than hydrogen chloride.
(b) melting point of 4 – nitrophenol is much higher than that of 2 – nitrophenol
(c) 4-nitrophenol is more soluble in water than 2-nitrophenol

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(d) 2-hydroxybenzaldehyde has a lower boiling point than 3-hydroxybenzaldehyde
although the relative molecular masses of the two compounds are the same.
(e) boiling points of the given homologous series decreases in the order;
of the same molecular
mass.
(f) methyl amine ( ) boils at -6.3oC while methanol
( ) boils at 46oC.
(g) 2-methylpropan-2-ol boils at a lower temperature than butan-1-ol yet they all have
the same molecular weight.
(h) ethane boils at lower temperature than butane.
(i) water( ) is a liquid at room temperature whereas hydrogen
sulphide ( ) is a gas at room temperature

Metallic bonding
A metallic bond is the electrostatic force of attraction between positive metal ions and
delocalized electrons.
A metallic solid consists of a lattice of metal ions with the outer most electrons forming a
“sea” of delocalized electrons. The delocalized electrons freely move throughout the
structure and can conduct electricity. Electrostatic attractions exist between the
delocalized electrons and the metal ions.
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Properties of metals
The metallic bond is the bond that is responsible for the properties of metals.

1. High melting and boiling points.

This is because of a high amount of energy is required to break the strong metallic bonds.
Melting point increases as the number of electrons contributed per atom of a metal
towards metallic bonding increases. Transition elements have higher melting points than

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

main group elements because their atoms contribute both 4s and 3d electrons towards
bonding.

Qn. Explain why group II elements form metals with higher melting and boiling
points than group I elements

Both group I and group II elements form metallic bonds whose strength depend on the
number of electrons contributed per atom to the formation of the metallic bonds. Group
II elements contribute two electrons per atom forming stronger metallic bonds that
require a higher amount of energy to break than Group I elements which only
contribute one electron per atom towards forming weaker metallic bonds that require a
lower amount of energy to break.

Qn. Explain why the melting point of chromium is higher than that of calcium

Calcium has a larger atomic radius and only contributes the two 4s electrons per atom
towards metallic bonding hence forming weaker metallic bonds that require a lower
amount of energy to break than chromium which has a smaller atomic radius and
contributes both the one 4s electron and the five 3d electrons forming stronger metallic
bonds that require a higher amount of energy to break.
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2. Electrical conductivity
Metals are good conductors of electricity and heat due to presence of free mobile
electrons throughout the lattice. If a potential difference is applied between the ends of a
metal, the delocalized electron cloud will towards the positive potential.
However, electrical conductivity of a metal decreases with increase in temperature
because resistance increases. This is because increase in temperature increases thermal
vibration within the metal. The regularity within the metallic lattice is upset and therefore
the electrons cannot easily move in the lattice.

3. Thermal conductivity
They conduct heat due to exchange of kinetic energy between free mobile electrons in the
lattice. When heat is supplied to one end of a piece of a metal, the kinetic energy of the
electrons is increased. This increase in kinetic energy is transmitted through the system of

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

delocalized electrons to other parts of the metal.

4. Malleability and ductility

Metals are malleable (can be hammered-beaten into sheets) and ductile ( can be drawn
out under tension-pulled out into wires). This is due to the ability of layers of atoms to
roll over each other into new positions without breaking the metallic bond.

5. Insoluble in polar and non-polar solvents.

The metal-metal attractions are much stronger than the solvent-solvent attractions or the
metal-solvent attractions. The solvent molecules cannot penetrate the metal lattice.

Strength of a metallic bond

The strength of a metallic bond is determined by three factors;

1. Charge of the cation

The higher the cationic charge, the stronger the metallic bond because there will be a
stronger attraction of the delocalized electrons.

2. Number of delocalised electrons per atom

The higher the number of electrons contributed per atom towards metallic bonding, the
stronger the metallic bond. This is because there will be a greater attraction between the
nucleus and the delocalised electrons.

3. Ionic radius
The smaller the ionic radius of the cation, the stronger the metallic bond because there
will be a stronger attraction of the delocalised electrons.
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VALENCE BOND THEORY

The Valence Bond Theory (VBT) is one of the theories that were developed to explain
chemical bonding, along with the molecular orbital theory.
According to the theory, a covalent bond is formed between two atoms by the overlap of
atomic orbitals of each atom containing an unpaired electron.
The atomic orbitals of two atoms overlap to form chemical bonds but they do not lose
their identity.

The shape of a molecule depends upon the shapes of the combining atomic orbitals. Only
outer atomic orbitals for a valence energy level are involved in bonding. The number of
covalent bonds formed is equal to half the number of combining atomic orbitals.

Sigma and pi bonds

The nomenclature and used for atomic orbitals is replaced by and for molecular
orbitals.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Sigma bond
A sigma bond is formed by head to head or collinear overlap of two atomic orbitals
along their internuclear axis.
Only one sigma bond can exist between any two atoms. It is a strong bond because
orbitals can overlap to a greater extent.

pi bond

A pi bond is formed by sideways or collateral overlap of two atomic orbitals.

One or two bonds can exist between any two atoms. A bond shortens the bond
length (internuclear distance). Two bonds (as in a triple bond) shorten the bond length
to a greater extent than one bond (as in a double bond). It is a weak bond because of
poor overlapping of orbitals.
It exists only when a bond is already present between two atoms.
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Hybridisation of atomic orbitals

and orbitals of comparable energy can combine within an atom to form hybrid
orbitals. The hybrid orbitals have different shapes from and orbitals and they form
stronger bonds due to great overlap during bonding.

Below are some important points about hybridization:

1. Usually atomic orbitals containing one electron each are considered in

hybridisation
2. In most cases, one or more electrons are promoted to the next higher energy levels
so that the number of unpaired electrons becomes equal to the oxidation state of the
central atom in the molecule.
3. Lone pairs are also involved in hybridization if the geometry of the molecule can be

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

explained by involving them.
4. An orbital can accommodate a maximum of two electrons with opposite spins.
5. Hybrid orbitals have greater potential for overlapping than the ground state orbitals
from which they are constructed.
6. The experimentally determined bond angles of molecules are very close to the
directions of the hybrid orbitals.
Hybrid orbitals

(a) -hybridisation
This occurs when one and one -orbital of the same atom combine to form a set of two
equivalent -hybrid orbitals which are to each other.

The beryllium atom with electronic configuration has both the and
subenergy levels completely filled with electrons.

From the configuration in the ground state of Beryllium, it may not form compounds
since it has no unpaired electrons. However beryllium is known to form compounds in
which it is divalent.
For beryllium to form compounds, one of the electrons is promoted to the
subenergy level to form an excited beryllium atom, .
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The two and electrons combine to form two collinear hybrid orbitals.
In formation of beryllium chloride for example, the two hybrid orbitals overlap with
the two orbitals of two chlorine atoms to form to form two sigma bonds.
Two collinear hybrid orbitals Formation of two -bonds in beryllium
chloride

(b) -hybridisation

This occurs when one and two -orbitals of the same atom combine to form a set of
three equivalent -hybrid orbitals which are trigonal planar with a bond angle .
The boron atom with electronic configuration has the subenergy level
having one unpaired electron.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

From the configuration in the ground state of Boron, two of the three two orbitals are
unoccupied.
For boron to form compounds, one of the electrons is promoted to one of the empty
orbitals to form an excited boron atom, . The excited boron atom therefore has two p
electrons.
Hybridization occurs between the remaining orbital and the two orbitals to form three
equivalent hybrid orbitals.
The axes of these orbitals lie in the same plane and at to each other.
This resulting hybridization therefore implies that the compounds of boron are
trigonal planar.
Three hybrid orbitals in the same
plane at
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DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(c) -hybridisation
This occurs when one and three -orbitals of the same atom combine to form a set of
four equivalent -hybrid orbitals which point towards the corners of a regular
tetrahedron with a bond angle of to each other.

The carbon atom with electronic configuration has the subenergy level
having one unpaired electron.

From the configuration in the ground state of carbon, two of the three two orbitals have
one unpaired electron each.
For carbon to form compounds, one of the electrons is promoted to the empty
orbital to form an excited carbon atom, . The excited carbon atom therefore has three p
electrons.
Hybridization occurs between the orbital and the three orbitals to form four
equivalent hybrid orbitals.
These are directed outwards from the carbon atom at an angle of with each other.
This resulting hybridization therefore implies that the molecules of methane or
tetrachloromethane are in a shape of a regular tetrahedron with the carbon atom at the
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centre and the hydrogen or chlorine atoms at the four corners.

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Four hybrid orbitals directed

outwards from the carbon atom at an
angle of

Geometry for different types of hybridisation

Type of Spatial Bond angle Examples
hybridization arrangement

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Linear
Trigonal planar
Tetrahedral

The formation of single, double and triple bonds

The formation of single, double and triple bonds in organic compounds is due to
hybridization.
(i) the carbon-carbon single bond
The carbon-carbon single bonds are all -bonds formed by
hybridization.
(ii) the carbon-carbon double bond
The carbon-carbon double bond for example in ethene consists of one -bond and one
bond formed by hybridization.

From the configuration in the ground state of carbon, two of the three two orbitals have
one unpaired electron each.
One of the electrons is promoted to the empty orbital to form an excited carbon
atom, .
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Hybridization occurs between the and the orbitals to form three equivalent
hybrid orbitals. Two of the hybrid orbitals form -bonds with the orbitals of
hydrogen. The remaining hybrid orbital forms a -bond between the carbon atoms
The unhybridised orbital forms a bond between the carbon atoms.
The two carbon atoms and four hydrogen atoms are all in the same plane and the bond
angle is . This gives ethene a trigonal planar shape.

(iii) the carbon-carbon triple bond

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The carbon-carbon triple bond for example in ethyne consists of one -bond and two
bonds formed by hybridization.

From the configuration in the ground state of carbon, two of the three two orbitals have
one unpaired electron each.
One of the electrons is promoted to the empty orbital to form an excited carbon
atom, .
Hybridization occurs between the and the orbitals to form two equivalent
hybrid orbitals. One of these two hybrid orbitals forms a -bond with the orbital of
hydrogen. The remaining hybrid orbital forms a -bond between the carbon atoms.
The two unhybridised and orbitals form two bonds between the carbon
atoms.
This gives ethyne a linear shape.
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The double bond formation in benzene

Benzene has the structure as shown below;

or

Between each pair of adjacent carbon atoms is a sigma bond formed by overlapping
hybrid orbitals.
Because orbitals are planar, all the six carbon atoms and six hydrogen atoms lie in
the same plane and the bond angles are .
There are unhybridised orbitals for each of the carbon atoms with an axis at right
angles to the plane of the carbon atoms.
These six orbitals overlap with each other all around the ring to form delocalised
bonds.
The electrons in these orbitals are free to move between all the carbon atoms in the
ring and they are described as delocalised electrons.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

NOTE: Benzene, just like ethene is formed by hybridisation but the difference is
what happens with the unhybridised orbitals.

DRAWING LEWIS STRUCTURES OF MOLECULES AND

POLYTATOMIC IONS
Lewis structures
A Lewis structure is a simplified representation of the arrangement of the outermost
electrons of each atom in a molecule and the lone pairs of electrons that may exist in the
molecule or polyatomic ions.
The electrons are shown as dots or as lines (for bonding electrons between two atoms).
For example when two chlorine atoms combine to form a chlorine molecule, the
following Lewis structure can be drawn;

The Lewis structure of a chlorine molecule shows 3 unshared electron pairs for each atom
(lone pairs) and one shared pair of electrons (bonding pair).
A line is sometimes used to indicate a shared pair of electrons.
The single shared pair of electrons is called a single bond.
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Drawing Lewis structures of some simple molecules

Molecule Description Lewis structure
It is known from the Lewis
Dot symbol of Nitrogen that
Ammonia it has one lone pair and can
form three bonds. Hydrogen
can form one bond and has
no lone pair
It is known from the Lewis
Dot symbol of Oxygen that it
Water has two lone pairs and can
form two bonds. Hydrogen
can form one bond and has
no lone pair
It is known from the Lewis
Dot symbol of Sulphur that it
can form two bonds and has

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

two lone pairs Each oxygen
Sulphur dioxide atom also has two lone pairs
and can form two bonds. But
for oxygen to form the two
bonds, one lone pair of
Sulphur must be used.
It is known from the Lewis
Dot symbol of Carbon that it
has no lone pair and can
Carbon tetrachloride form four bonds. Each
Chlorine atom has three
lone pairs and can form one
bond.

Steps for writing Lewis structures for more complex molecules/

polyatomic ions
1. Write the skeleton structure of the molecule or ion. The central atom is usually the
least electronegative element in the compound and then place a bonding pair of
electrons between each pair of adjacent atoms or draw a line to indicate a single
bond. In the water molecule for example, there is a bonding pair of electrons between
each oxygen atom and each hydrogen atom.
2. Determine the total number of Valence electrons for the atoms in the molecule or ion.
For a neutral molecule, this is the sum of valence electrons on each atom. This can be
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got from the Lewis Dot symbol of the atom or its electronic configuration. For a
negatively charged ion, add one electron for each negative charge.
For a positively charged ion, subtract one electron for each positive charge.
3. Subtract two valence electrons for each bond formed in the skeleton structure.
4. Beginning with the terminal atoms, add enough electrons of the remaining electrons
as valence electrons to satisfy the octets of the atoms (two for hydrogen). These
electrons are the lone pairs.
5. The remaining electrons are then placed on the central atom (some central atoms can
accommodate more than eight electrons)
6. If the central atom has fewer electrons than an octet, use lone pairs from terminal
atoms to form multiple (double or triple) bonds to the central atom to achieve an
octet. This will not change the number of electrons on the terminal atoms
Examples

In this table, we are using each of the steps 1-7 for different molecules or polyatomic

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

ions to draw their Lewis structures.

[ ]

Since there is a positive

charge, the total electrons
remain
3
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[ ]

6 Not applicable

Nitrogen cannot get an octet for

reasons explained later.

1
[ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

* +

Since there is a positive charge, the total electrons

remain
Since there are 2 negative charges, the total
electrons becomes
3

4
[ ]
5
* +

All the remaining 18 electrons have been used

but carbon doesn’t have a full octet yet. Rule 6
must be satisfied.
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6 Not applicable
* +

More resonance structures can be made for this

ion as we shall see later.

Exceptions of the Octet rule

We already have an idea about the octet rule and we have applied it in many bonding
situations in this topic. We have equally used it in drawing Lewis structures.

However, there are three exceptions of the Octet rule, which include;

(a) Incomplete octet

(b) Expanded octet
(c) Odd number electron

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(a) Incomplete octet
Molecules with atoms containing an incomplete octet of electrons generally contain the
lighter s-block and p-block elements especially beryllium with just four electrons around
the central atom and boron, typically with six electrons. Examples include;

 Beryllium chloride
 Boron trichloride
(b) Expanded octet
This is the most exception of the Octet rule. In applies to a molecule or an ion with at
least one atom that possesses more than an octet of electrons.
This applies commonly to compounds in period 3 and beyond. Examples from the p-
block elements include;
 Sulphur hexafluoride
 Sulphate ion
 Phosphate ion
 Phosphorus pentafluoride
Try to come up with probable Lewis structures of the above molecules/ ions
(c) Odd number electron
There are molecules such as nitrogen monoxide that have an odd number of electrons.
This is seen in one of the examples above.
Molecules of most s-block and p-block elements contain an even number of electrons.
Their bonding can therefore easily be described using the rules stated above.
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However, molecules or ions containing d-block elements commonly contain an odd

number of electrons. Their bonding cannot adequately be explained using the rules seen
above.
There also a few molecules however for the p-block elements that have an odd number of
electrons. These include;
Molecule Total number of electrons
Nitrogen monoxide
Nitrogen dioxide
Chlorine dioxide

Questions

Write the Lewis structures for the following species

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

1. 9.
2. 10.
3. 11.
4. 12.
5. 13.
6. 14.
7. 15.
8. 16.

Formal charges
A formal charge compares the number of electrons around a neutral atom and the number
of electrons around an atom in a molecule.
A formal charge is assigned to an atom in a molecule on assumption that the electrons in
all chemical bonds are shared equally between atoms regardless of relative
electronegativity.

( ) ( )
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Examples

1. Calculate the formal charges of the atoms in ammonia.

( )

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. Calculate the formal charges of the atoms in the carbonate ion

* +

( )

( )

( )
Note;
(a) When formal charges on each of the atoms in a molecule are added, they must give
the total charge on the molecule.
(b) The structure with the most formal charges of zero on its atoms is the most stable
Lewis structure.
(c) In the case where there must be either positive or negative formal charges on
various atoms, the most stable structures have negative formal charges on the more
electronegative atoms and positive charges on the less electronegative atoms.
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Resonance
This is the situation in which two or more Lewis structures can be written. Resonance is
used when a single Lewis structure cannot fully describe the bonding in a molecule or
ion. Resonance structures arise when there are more than one way to draw a Lewis
structure that satisfies the Octet rule. They are drawn by placing double bonds between
different atoms and lone pairs on different atoms. Molecules with multiple resonance
structures are more stable than those with fewer resonance structures. Some resonance
structures contribute more to the stability of a molecule than others. This can be
determined using the concept of formal charges. The most stable resonance structure is
one with the least formal charge.

An illustration of how resonance structures arise

The carbonate ion

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

* + * + * +

The nitrate ion

* + * + * +

VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR)

THEORY
Beryllium chloride is a linear molecule without a dipole moment whereas tin(II)
chloride is a bent molecule with a dipole moment. Boron trichloride is
trigonal planar whereas ammonia is trigonal pyramidal.
A theory was put forward to explain the differences in shapes of molecules and ions. This
theory is known as the Valence Shell Electron Pair Repulsion Theory.
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The theory points out that the arrangement of electron pairs around a central atom in a
molecule depends of the number of electron pairs.
Between any electron pair and any other electron pair, there is a force of electrostatic
repulsion.
The electron pairs can be bonding or shared pairs which constitute the covalent bonds or
unshared (lone pairs).
Any lone pairs of electrons on the central atom repel the bonding pairs of electrons and
this affects the geometry (bond angle and shape) of the molecule.

For the purpose of determining electron geometry, the VSEPR theory considers the
electron pairs in a double bond or a triple bond are treated as one pair
Since the lone pairs are closer the to the central atom, they cause greater repulsion than
bonding pairs and the repulsions are in the order;

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

.

Predicting the shapes of molecules and ions

Note; In some of the three dimensional structures, the lone pairs of electrons are not
shown. These will be shown in further examples.

Number
of Total Number Number
valence electron of of lone Shape of molecule 3-dimensional Examples
electrons pairs bonding pairs presentation
pairs

4 2 2 0 Linear

, ,
[ ]
Bent or
6 3 2 1 V-shaped

6 3 3 0 Trigonal planar
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8 4 4 0 Tetrahedral

8 4 3 1 Trigonal

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pyramidal

Bent or
8 4 2 2 V-shaped

Trigonal
10 5 5 0 bipyramidal

10 5 4 1 Irregular
tetrahedral

10 5 3 2 T-shaped

10 5 2 3 Linear
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12 6 6 0 Octahedral

12 6 5 1 Square pyramidal

12 6 4 2 Square planar

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(a) Steps followed to draw the structure of molecules and cations
1. Determine the number of valence electrons on the central atom from its electronic
configuration or the number of its group in the Periodic Table.
 If the structure is for a cation, subtract an electron for each positive charge on the
number of valence electrons.
 If the central atom is a transition element, calculate the oxidation state and use it as
number of valence electrons.
Molecule or ion Electronic Number of valence
configuration of electrons for central
central atom atom

2. Add one electron to the valence electrons in (1) above for each atom/ligand bonded to
the central atom as shown below.
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Molecule or ion Number of valence Total number of

electrons on central valence electrons
atom

3. Divide the total number of valence electrons by two to get the total number of
electron pairs. This is because electrons bond in pairs
Molecule or ion Total number of Total number of
valence electrons electron pairs

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

4. From the total number of electron pairs, subtract the number of bonding pairs to get
the number of lone pairs. The number of bonding pairs corresponds to the number of
bonded atoms to the central atom.
Molecule or ion Total number of Number of Number of
electron pairs bonding pairs lone pairs

5. Then draw the structure of the molecule using the summary in the table above,
showing prediction of shapes of molecules. The lone pairs are shown as two dots
around the central atom for each electron pair. Put the VSEPR theory into
consideration as you draw the molecule/ion.
Molecule or ion Number of Number of Structure Shape
bonding pairs lone pairs
Trigonal
̈ pyramidal
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[ ] Tetrahedral

Octahedral

..
O.. Bent

NOTE;

(i) It is strictly that number of bonding pairs and lone pairs that guide us on the

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

geometry of the molecule.
(ii) Bond angles and bond lengths should be put into consideration when
drawing the structures
(iii) The lines that represent the bonds should strictly not leave a lot of space
between the atoms.

(b) Steps followed to draw the structure of oxy-anions and oxy-

molecules
These are molecules or anions containing oxygen atoms. They are treated in a
special way since they contain –OH bonds , =O bonds and bonds.

1. Determine the number of valence electrons on the central atom from its electronic
configuration or the number of its group in the Periodic Table.
 If the central atom is a transition element, calculate the oxidation state and use it as
number of valence electrons.
 The number of valence electrons is used to deduce the expected number of bonds to be
formed by the central atom.
Molecule or ion Electronic Number of valence
configuration of electrons on central
central atom atom
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Oxidation state of Mn
is

6. Deduce the nature of bonds in the ion or molecule. Begin with bonds, followed
by bonds and then bonds.
(i) For every negative charge in the anion, there is one bond.
(ii) For every hydrogen atom, there is one bond.
(iii) All the remaining oxygen atoms are double bonded after (i) and (ii) or if (i)
and (ii) do not apply to the molecule.
Molecule or ion Expected number Nature of bonds
of bonds formed by
central atom
bonds

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

bonds
bond
bonds
bond
bond
bond
bonds
bonds
bond
bond
bond
bonds
bonds
7. Since for each single bond, one electron of the valence electrons of the central atom is
used, and two for a double bond, the unbounded electrons are the lone pairs. The lone
pairs are obtained by subtracting the number of bonds formed from the number of
valence electrons.
Number of valence Number of
Number of electrons involved in non-bonding
Molecule or valence Nature of bonds bonds electrons
ion electrons of (lone pairs)
central atom
bonds
bonds
bond (1 lone pair)
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bonds
bond
bond
bond (1 lone pair)
bonds
bonds
bond
bond
bond
bonds
bonds

8. Draw the structure of the molecule/ion using the nature of bonds and lone pairs.
Where there are no lone pairs in the molecule/ ion, the bonds are symmetrically
placed around the molecule.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Molecule or Nature of bonds Number of Structure Shape
ion lone pairs

bonds Trigonal
planar

̈
bonds Trigonal
bond pyramidal

bonds Tetrahedral
bond

̈
bond Bent
bond

bonds Tetrahedral
bonds
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bond
bond Trigonal
bond planar

bonds Tetrahedral
bonds

(a) Molecules or ions with a linear shape

Linear molecules have two bonding pairs and no lone pairs. The molecules are linear
with a bond angle of because the bonding pairs greatly repel themselves.
The molecules in gaseous beryllium chloride are linear because the two bonded pairs

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

around the beryllium atom repel each other as fully as possible giving the molecule a
bond angle of .
For example in ,
 It is treated as an oxy-molecule.
 The carbon (central) atom has valence electrons from its electronic
configuration.
 Carbon is therefore expected to form bonds with the oxygen atoms.
 Each oxygen atom forms a double bond to the carbon atom and no lone pair
remains.
 The two bonding pairs greatly repel themselves greatly to form a linear molecule,
bond angle .
Some ions also form a linear structure. These have two bonding pairs and three lone
pairs.
For example in ,
 The iodine (central) atom has valence electrons from its electronic configuration.
 Since the structure is for an anion with negative charge one, the total electrons
are .
 of these electrons are used for bonding with the chlorine atoms.
 This leaves 6 electrons not used for bonding and form the three lone pairs.
 The geometry of two bonding pairs and three lone pairs corresponds to a linear
molecule, bond angle .
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In or , there are three lone pairs and one bond pair surrounding the central
oxygen atom. They are also linear species.
Molecule Structure Shape

Linear
[ ̈ ]

(b) Molecules or ions with a bent shape

Bent molecules or ions are also called V-shaped molecules or ions. They either have;

(i) two bonding pairs and one lone pair or

(ii) two bonding pairs and two lone pairs

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

For example in ,
 The sulphur (central) atom has valence electrons from its electronic
configuration.
 Since it is bonded to two hydrogen atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives four electron pairs.
 Of the four electron pairs, there are two bonding pairs since Sulphur is bonded to
two hydrogen atoms and two lone pairs.
 The repulsion between the two lone pairs of electrons is greater than the repulsion
between lone pairs and bonding pairs of electrons which is also greater the
repulsion between the bonding pairs of electrons.
 This reduces the bond angle to making the molecule V-shaped.
For example in ,
 The lead atom has valence electrons from its electronic configuration.
 Since it is bonded to two chlorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives three electron pairs.
 Of the three electron pairs, there are two bonding pairs since lead is bonded to two
chlorine atoms and one lone pair.
 The two bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater.
 This reduces the bond angle to a value smaller than making the molecule
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Some ions also form a bent structure.

For example in ,
 It is an oxy-anion
 The chlorine atom has valence electrons from its electronic configuration.
 Chlorine is therefore expected to form seven bonds.
 The negative charge in the anion means there is one bond.
 The remaining oxygen atom is doubly bonded to chlorine
 This implies that 3 of the 7 electrons are used for bonding and the remaining 4
form two lone pairs.
 The repulsion between the two lone pairs of electrons is greater than the repulsion
between lone pairs and bonding pairs of electrons which is also greater the
repulsion between the bonding pairs of electrons.
 This reduces the bond angle making the molecule V-shaped.
Molecule Structure Shape

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

.. ..
S

̈
V-shaped

..
Cl..

(c) Molecules or ions with a trigonal planar shape

Trigonal planar molecules have three bonding pairs of electrons and no lone pairs. The
three bonding pairs lie in the same plane and the molecules have a bond angle of
because the bonding pairs greatly repel each other equally.

For example in ,

 The boron atom has valence electrons from its electronic configuration.
 Since it is bonded to three fluorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives three electron pairs.
 All the three electron pairs are used in bonding to form three bonding pairs since
boron is bonded to three fluorine atoms and there is no lone pair.
 The three bonding pairs of electrons repel each other equally.
 This makes the bond angle making the molecule trigonal planar.
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For example in ,

 The carbon atom has valence electrons from its electronic configuration.
 Two of these are used to bond to each hydrogen atom and two to form a double
bond with oxygen .No lone pair remains.
 This gives the molecule three bonding pairs and no lone pair.
 The three bonding pairs of electrons repel each other equally.
 This makes the bond angle making the molecule trigonal planar.
Molecule Structure Shape

Trigonal planar

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C

(d) Molecules or ions with a tetrahedral shape

Tetrahedral molecules or ions have four bonding pairs of electrons and no lone pairs.
They have a bond angle of because the bonding experience mutual repulsion.

For example in ,
 The silicon atom has valence electrons from its electronic configuration.
 Since it is bonded to four chlorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives four electron pairs.
 All the four electron pairs are bonding pairs since silicon is bonded to four chlorine
atoms and no lone pairs.
 The four bonding pairs of electrons mutually repel each other, resulting into a bond
angle of making the molecule tetrahedral.
Some ions also form a tetrahedral structure.
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For example in ,

 It is an oxy-anion
 The phosphorus atom has valence electrons from its electronic configuration.
 Phosphorus is therefore expected to form five bonds.
 The three negative charges in the anion means there are three bonds.
 The remaining oxygen atom is doubly bonded to phosphorus
 This gives a total of five bonds, and all the electrons are used for bonding. There is
no lone pair.
 The four bonding pairs of electrons mutually repel each other, resulting into a bond
angle of making the molecule tetrahedral.
Some complexes also form a tetrahedral structure.

For example in ,

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Molecule Structure Shape

Tetrahedral

[ ]

(e) Molecules or ions with a trigonal pyramidal shape

Trigonal pyramidal molecules or ions have three bonding pairs of electrons and one
lone pair. They have a bond angle smaller than , which is observed in the
tetrahedral molecules. This is due to increased repulsion caused by the lone pair.
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For example in ,

 The phosphorus atom has valence electrons from its electronic configuration.
 Since it is bonded to three hydrogen atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives four electron pairs.
 Of the four electron pairs, there are three bonding pairs since phosphorus is bonded
to three hydrogen atoms and one lone pair.
 The three bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater.
 This reduces the bond angle to making the molecule trigonal pyramidal.
For example in ,

 It is an oxy-molecule/ oxy-acid
 The chlorine atom has valence electrons from its electronic configuration.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

 Phosphorus is therefore expected to form seven bonds.
 For the hydrogen atom present, there is one bond.
 The two other oxygen atoms form two bonds.
 This gives a total of five bonds, and two electrons are not used for bonding. There is
one lone pair therefore.
 The three bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater.
 This reduces the bond angle making the molecule trigonal pyramidal.
Some ions also form a trigonal pyramidal structure.

For example in ,

 It is an oxy-anion
 The Sulphur atom has valence electrons from its electronic configuration.
 Phosphorus is therefore expected to form six bonds.
 The two negative charges in the anion mean there are two bonds.
 The remaining oxygen atom is doubly bonded to Sulphur, .
 This gives a total of four bonds, and two electrons are not used for bonding. There
is one lone pair therefore.
 The three bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater.
 This reduces the bond angle making the molecule trigonal pyramidal.
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Molecule Structure Shape

̈ Trigonal pyramidal

(f) Molecules or ions with a trigonal bipyramidal shape

Trigonal bipyramidal molecules have five bonding pairs of electrons and no lone pairs.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

For example in ,

 The phosphorus atom has valence electrons from its electronic configuration.
 Since it is bonded to five fluorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives five electron pairs.
 All the five electron pairs are used in bonding as bonding pairs.
The complex also has a trigonal bipyramidal shape,

Molecule Structure Shape

Trigonal bipyramidal |

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(g) Molecules or ions with an irregular tetrahedral shape

Irregular or distorted tetrahedral molecules have four bonding pairs of electrons and one
lone pair.

For example in ,

 The Sulphur atom has valence electrons from its electronic configuration.
 Since it is bonded to four fluorine atoms, the total number of valence electrons in
the molecule is .
 The total number of valence electrons divided by two gives five electron pairs.
 Four of the five electron pairs are used as bonding pairs to bond with the four
fluorine atoms.
 One electron pair remains as a lone pair.
 The four bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Molecule Structure Shape

̈ Irregular tetrahedral

(h) Molecules or ions with an octahedral shape

Octahedral molecules have six bonding pairs of electrons.

For example in ,

 The sulphur atom has valence electrons from its electronic configuration.
 Since it is bonded to six chlorine atoms, the total number of valence electrons in the
molecule is .
 The total number of valence electrons divided by two gives six electron pairs.
 All the six electron pairs are used in bonding as bonding pairs.
The complex also has an octahedral shape,

Molecule Structure Shape

Octahedral
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Octahedral

[ ]

(i) Molecules with a square pyramidal shape

Square pyramidal molecules have five bonding pairs of electrons and one lone pair.

For example in ,

 The bromine atom has valence electrons from its electronic configuration.
 Since it is bonded to five fluorine atoms, the total number of valence electrons in
the molecule is .

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

 The total number of valence electrons divided by two gives six electron pairs.
 Five of the six electron pairs are used in bonding as bonding pairs.
 One electron pair remains as a lone pair.
 The five bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater.
Molecule Structure Shape

̈
Square pyramidal

(j) Molecules or ions with a square planar shape

Square planar molecules have four bonding pairs of electrons and two lone pairs.

For example in ,

 The iodine (central) atom has valence electrons from its electronic configuration.
 Since the structure is for an anion with negative charge one, the total electrons
are .
 of these electrons are used for bonding with the chlorine atoms.
 This leaves 4 electrons not used for bonding and form the two lone pairs.
 The lone pair-lone pair repulsion is greater than lone pair-bond pair repulsion
which is also greater than bond pair- bond pair repulsion.
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Molecule Structure Shape

* + Square planar

Qn. Draw the structure and name the shapes of the following molecules or ions
Molecule Structure Shape

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The effect of lone pairs on Molecular Geometry
The effect of lone pairs on molecular geometry is explained basing on the VSEPR theory.

1. Explain the structures of the following species;

(i) beryllium chloride
(ii) nitrate ion
(iii)
(iv) Chlorate(V) ion
(v) Hydrogen sulphide
Molecule / ion Structure Explanation
Beryllium chloride molecule has two bonding pairs
of electrons and no lone pair. The two bonding pairs
repel each other greatly to form a linear molecule
with a bond angle of .
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The nitrite ion possesses three bonding pairs of

electrons and no lone pair. The three bonding pairs
lie in the same plane and repel each other equally
to form a trigonal planar shape with a bond angle of
.
̈ Nitrosyl chloride molecule has two bonding pairs of
electrons and one lone pair. The two bonding pairs
of electrons repel each other but the lone pair-bond
pair repulsion is greater.
This reduces the bond angle making the molecule
V-shaped.
The chlorate(V) ion possesses three bonding pairs of
̈ electrons and one lone pair. The three bonding pairs
of electrons repel each other but the lone pair-bond
pair repulsion is greater. This reduces the bond
angle making the molecule trigonal pyramidal.
The hydrogen sulphide molecule has two bonding

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pairs and two lone pairs.
The repulsion between the two lone pairs of
.. ..
S electrons is greater than the repulsion between lone
pairs and bonding pairs of electrons which is also
greater the repulsion between the bonding pairs of
electrons alone. This reduces the bond angle to
making the molecule V-shaped.

2. Explain why;
(i) Beryllium bromide has a bond angle of but tin(II) bromide has a bond
angle less than
̈

Beryllium bromide molecule has two bonding pairs of electrons and no lone pair. The
two bonding pairs repel each other greatly to form a linear molecule with a bond angle
of . Tin(II) bromide molecule has two bonding pairs of electrons and one lone
pair. The two bonding pairs of electrons repel each other but the lone pair-bond pair
repulsion is greater. This reduces the bond angle making the molecule V-shaped.
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(ii) The sulphate ion is tetrahedral but the sulphite ion is trigonal pyramidal

The sulphate ion has four bonding pairs and no lone pairs. The four bonding pairs of
electrons mutually repel each other, resulting into a bond angle of making the
molecule tetrahedral. The sulphite ion possesses three bonding pairs of electrons and
one lone pair. The three bonding pairs of electrons repel each other but the lone pair-
bond pair repulsion is greater. This reduces the bond angle making the molecule
trigonal pyramidal.

(iii) Sulphur dioxide has a bond angle of while Sulphur dichloride has bond
angle of although both are V-shaped molecules.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

.. ..
S
̈

The Sulphur dioxide molecule has two bonding pairs and one lone pair. The two
bonding pairs of electrons repel each other but the lone pair-bond pair repulsion is
greater. This makes the bond angle .The Sulphur dichloride molecule also
possesses two bonding pairs of electrons but has two lone pairs. Since the Sulphur
dichloride molecule has more lone pairs than the Sulphur dioxide molecule, there exists
lone pair-lone pair repulsion, and the lone pair-bond pair repulsion is also greater than
in Sulphur dioxide. This reduces the bond angle in Sulphur dichloride.

The effect of electronegativity on size of bond angles

For two molecules or ions in which the central atoms are different but the bonded atoms
are the same, the increase in electro negativity increases the attraction for the
bonding electrons by the central atoms in their molecules. This makes the bonding
pairs of electrons closer to the more electronegative atom than to the less
electronegative element. This implies that the bonding pairs of electrons are closer to
the central atom leading to an increased repulsion between them, which increases the
bond angle.

For two molecules or ions in which the central atoms are similar but the bonded atoms
are the different, the increase in electro negativity of the bonded atoms increases the
attraction for the bonding electrons by the bonded atoms in their molecules. This
makes the bonding pairs of electrons closer to the more electronegative atom than to
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the less electronegative element. This implies that the bonding pairs of electrons far
apart leading to a decreased repulsion between them, which reduces the bond angle.

Examples
Explain why;
(i) the bond angle in ammonia is while that in phosphine is .

̈ ̈

107O 94O
Both ammonia and phosphine molecules adopt a trigonal pyramidal shape. However, the
nitrogen atom is more electronegative than the phosphorus atom. The bonding pairs of
electrons are closer to the nitrogen atom in ammonia than they are to the phosphorus
atom in phosphine. This causes an increased repulsion between the bonded pairs of
electrons in ammonia than it is in phosphine, therefore ammonia has a bigger bond
angle than phosphine.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(ii) the bond angle in hydrogen sulphide is while that in water is .
.. .. .. ..
S O

Both hydrogen sulphide and water molecules adopt a V- shaped structure. However, the
oxygen atom is more electronegative than the sulphur atom. The bonding pairs of
electrons are closer to the oxygen atom in water than they are to the sulphur atom in
hydrogen sulphide. This causes an increased repulsion between the bonded pairs of
electrons in water than it is in hydrogen sulphide, therefore the water molecule has a
bigger bond angle than hydrogen sulphide.

(iii) the bond angle in phosphorus trifluoride is while that of phosphorus

trichloride is .
̈ ̈

96O 107O

Both phosphorus trifluoride and phosphorus trichloride molecules adopt a trigonal

pyramidal shape. However, the fluorine atom is more electronegative than the chlorine
atom. The fluorine atoms therefore withdraw away the bonded pairs of electrons from
the phosphorus atom more than the chlorine atoms do. This makes the bonded pairs to
be far apart in phosphorus trifluoride than they are in phosphorus trichloride,
reducing the repulsion between them. Therefore phosphorus trifluoride has a smaller
bond angle than phosphorus trichloride.
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Polarity of molecules
Polarity is a condition of a molecule to have positive and negative charges. Polarity of
molecules is related to the electronegativity difference of the bonding atoms and bond
symmetry.

Factors that determine the polarity of molecules

(i) electronegativity difference of atoms in the molecule
(ii) bond symmetry or spatial arrangement of various bonds in the molecule
Polar covalent bonds are formed as a result of difference in electronegativity of the
bonding atoms. These include; , , , ,
, etc.
For two equal but opposite separated electrical charges, there exists an electric dipole
moment. An electric dipole moment is a product of one of the charges, or and
the distance between the atomic nuclei. Any individual polar covalent bond must have a
corresponding dipole moment.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

However, there are molecules in which the individual bonds in it are polar but the
molecule as a whole is non-polar. An example is tetrachloromethane which has a zero
dipole moment, although the individual carbon-chlorine bonds in it have dipole moments.
This is due to the symetrical distribution of the chlorine atoms around the carbon atom
such that the effects of the four dipoles cancel each other. Another example is the carbon
dioxide molecule.

All molecules in which the atoms are symmetrically distributed around the central atom
are non polar. This is only possible if all the symmetrically distributed atoms around
the central atom are the same. These include;

(i) linear molecules

(ii) trigonal planar molecules
(iii) square planar molecules
(iv) tetrahedral molecules
(v) trigonal bipyramidal molecules
(vi) octahedral molecules

Explain why;
(a) Carbon tetrachloride is non-polar yet the carbon-chlorine bond is polar.
Chlorine is more electronegative than carbon. The chlorine atom therefore tends to
attract the bonding electrons towards itself hence acquires a partial negative charge
(δ −) and the carbon atom gains a partial positive charge (δ+). This makes the
carbon- chlorine bond polar.
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However, the whole molecule is non-polar because it has a tetrahedral structure in

which the chlorine atoms are symmetrically distributed about the carbon atom. This
creates equal and opposite dipole moments in all directions that cancel out making the
resultant dipole moment zero.

Note; For the same reason, a stream of tetrachloromethane is not deflected by a

charged rod while that of chloroform is deflected.

(b) The carbon- oxygen bond is polar but carbon dioxide is non-polar.
Oxygen is more electronegative than carbon. The oxygen atom therefore tends to attract

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

the bonding electrons towards itself hence acquires a partial negative charge
(δ −) and the carbon atom gains a partial positive charge (δ+). This makes the
carbon- oxygen bond polar.
However, the whole molecule is non-polar because it has a linear structure in which the
oxygen atoms are symmetrically distributed about the carbon atom. This creates equal
and opposite dipole moments in all directions that cancel out making the resultant
dipole moment zero.

Molecules in which the bonded atoms are not symetrically distributed around the central
atom like chloromethane, dichloromethane, trichloromethane, water and ammonia have
an overall dipole moment over the molecule. Therefore both the individual bonds and the
whole molecule are polar.

Differences between polar and non-polar molecules

Polar molecules Non-polar molecules

Asymmetrical Symmetrical
One end of the molecule is positive Does not have distribution of charges at
whereas the other has a positive charge opposite ends
Can interact through hydrogen bonds There are van der Waals forces between
non polar molecules
Have a dipole moment Have no dipole moment
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Miscellaneous Questions
1. Use dot and cross diagrams to show how the following atoms can combine

(a) Lithium and fluorine

(b) Hydrogen and fluorine
(c) Magnesium and fluorine
(d) Lithium and oxygen
(e) Sodium and fluorine
(f) Aluminium and fluorine
(g) Calcium and oxygen

2. (a) What is meant by the term hydrogen bonding?

(b) Explain how hydrogen bonding arises in;

(i) hydrogen fluoride
(ii) ice

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(iii) Methylamine
(iv) Ethanoic acid
(c) Which practical evidence is there for existence of hydrogen bonds in ice and
ethanoic acid?

3. Explain the following observations;

(i) Both graphite and copper conduct electricity
(ii) Solid copper(II) sulphate is a non-conductor but aqueous copper(II) sulphate
conducts electricity.
(iii) Nitrogen is a gas at room temperature but phosphorus can exist in several solid
forms at room temperature.
(iv) Diamond is hard and an electrical insulator whereas graphite is soft and a good
electrical conductor
(v) Both diethyl ether and butan-1-ol have the same molecular mass but diethyl
ether boils at whereas butan-1-ol boils at .
(vi) Magnesium has a higher melting point that sodium
(vii) Sodium is softer than copper
(viii) Both sodium and copper are good electrical conductors.
(ix) Chlorine is a gas whereas iodine is a solid at room temperature.
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4. Explain why;
(i) trichloromethane is deflected by a charged rod but tetrachloromethane is
not.
(ii) Boron trichloride is non-polar whereas nitrogen trichloride is polar
(iii) A stream of chloroform is deflected by a charged rod but a stream of
tetrachloromethane is not.
(iv) the bond angle in ammonium ion is whereas that in ammonia is
.
5. (a) State the type of hybridization expected in simple compounds of;
(i) Boron
(ii) Beryllium
(iii) carbon
(b) state the effect of the type of hybridization stated in (a) above on the geometry
of the following;

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(i) boron trifluoride
(ii) beryllium chloride
(iii) carbon tetrafluoride

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CHAPTER FOUR
THERMOCHEMISTRY
(CHEMICAL ENERGETICS)
Thermochemistry is the study of energy changes that accompany chemical reactions. It
is also called chemical energetics or chemical thermodynamics.
Thermochemistry investigates;
 the position of equilibrium in the reaction
 the feasibility of the reaction
 and how far the reaction can go.

CHEMICAL ENERGY

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Energy is the capacity to do work. There are many forms of energy among which
chemical energy is one.
Chemical substances also have capacity to do work, thus possess chemical energy.
The chemical energy must be converted to another form of energy for chemical
substances to do work. The form of energy to which chemical energy is converted is the
heat energy.
Heat is a form of kinetic energy associated with motion of atoms and molecules. It is the
transfer of energy from regions of high temperature to regions of low temperature.
The heat evolved by a chemical substance can be used as a measure of the chemical
energy liberated. The change in chemical energy of a chemical substance is measured
only if the substance is treated in a certain way, for example when it is burnt in oxygen.

During a chemical reaction, bonds between atoms of the reactants are broken and new
bonds are formed in the products formed. Energy is absorbed to break the bonds
between atoms and energy is given out when new bonds are formed.

Heat content of a substance

Every substance has some stored chemical energy. The heat content differs from one
substance to another because the molecules of different substances differ in the number
and type of atoms and the number and type of bonds between their atoms.
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Enthalpy,
Enthalpy is the total energy content of a substance.
It is denoted by the symbol, .

Enthalpy change,
Enthalpy change is the heat content of a substance measured at standard temperature
and pressure during a chemical reaction.
Enthalpy change is called heat of reaction and is denoted as

Standard enthalpy change,

This is the heat change when molar quantities of reactants shown in the balanced
equation for the reaction in their standard states react completely at 1 atmosphere and
298K.
Standard state of the substance is the phase in which a pure substance exists at 1
atmosphere and 298K.

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The units for standard enthalpy of reaction are

TYPES OF HEAT OF REACTIONS

All chemical reactions are accompanied by evolution or absorption of heat. This results
into two types of reactions namely;
(i) exothermic reaction
(ii) endothermic reaction

Exothermic reaction Endothermic reaction

 Proceed with evolution of heat to the  Proceed with absorption of heat from the
environment environment
 Denoted by a negative sign  Denoted by a positive sign
 The products are at a lower energy level  The products are at a higher energy level
than the reactants than the reactants
For example; For example;

The equation can be interpreted as; The equation can be interpreted as

1 mole of hydrogen gas reacts with 1 mole of 1 mole of carbon reacts with 1 mole of steam
gaseous iodine to form 2 moles of hydrogen to form 1mole of carbon monoxide gas and 1
iodide gas with evolution of mole of hydrogen gas with absorption of
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The sign of the enthalpy change for a reaction is an indicator of its feasibility. The more negative
(exothermic) the value of , the more is the reaction likely to be feasible.

Energy level diagrams for exothermic and endothermic reactions

An energy level diagram is a graph of potential energy of a reaction against reaction path or
reaction coordinate.
For the exothermic reaction shown above; For the endothermic reaction shown above;
Activated
complex
Activated
Potential complex
Potential
energy
energy
( )
( )

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Reaction coordinate Reaction coordinate
is the activation energy for the reaction.
It can also be called activation energy for forward reaction.
is activation energy for backward reaction
is the enthalpy of reaction
Activation energy is the minimum energy which is required to be possessed by reactants in order
to react and form products.
Activated complex is the intermediate unstable compound formed immediately once the
reactants have absorbed the activation energy available.
This unstable compound undergoes bond re-organization by releasing some of the energy to form
the final stable product. The activated complex can also be called a transition state.
The enthalpy of reaction can be got from the expression ;
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Questions
1. For the reaction
(a) Draw a well labeled energy level diagram for the reaction.
(b) The activation energies for the forward and reverse reactions are known to be
respectively and . Calculate the heat of reaction.
2. (a) Define the term activation energy
(b) and react to form and according to the following equation

(i) Draw a fully labeled potential energy versus reaction coordinate diagram for
the reaction of and .
(ii) Calculate the activation energy of the backward reaction. (the activation for
forward reaction is

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

3. Dinitrogen tetraoxide dissociates at 40 oC and 1 atm according to the following
equation.

Draw a well labelled energy level diagram for the reaction above

Applications of exothermic reactions in everyday life

(i) In hot packs which are used to treat sports injuries and warming the body in case
of coldness. The instant hot packs have separate compartments of water and
anhydrous calcium chloride separated by a thin film placed in a plastic bag. When
the bag is squeezed, the thin film breaks and the anhydrous calcium chloride
dissolves in the water exothermically to release heat.
→

There are other salts that dissolve exothermically and can be used in a hot pack for
example anhydrous magnesium sulphate and anhydrous copper(II) sulphate
(ii) Combustion of fuels to release energy during cooking of food
(iii) In cellular respiration, where energy is obtained from carbohydrates and used by
living organisms. During the process carbohydrates react with oxygen to form
carbon dioxide, water and energy.
(iv) Condensation during formation of rain from water vapour
(v) Freezing of water into ice
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Applications of endothermic reactions in everyday life

(i) In instant cold packs which are used to treat sports injuries. The instant cold
packs have separate compartments of water and solid ammonium nitrate separated
by a thin film placed in a plastic bag. When the bag is squeezed, the thin film
breaks and the solid ammonium nitrate dissolves in water endothermically to
provide instant coldness. Heat is absorbed from the surrounding such as the
injured area of the athlete‟s body.
→

There are other salts that dissolve endothermically and can be used in a cold pack for
example ammonium chloride, potassium nitrate and sodium thiosulphate.
(ii) Photosynthesis. Energy is absorbed to convert carbon dioxide and water to sugars
in presence of chlorophyll.
(iii) Evaporation of liquid water

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(iv) Melting of ice

Factors affecting enthalpy of reaction

1. Temperature at which the reaction is carried out
2. Pressure of gaseous reactants or products
3. Amount of reactants used
4. Physical state of reactants and products
Latent heat is involved in changes of state so that the state of the reagents and
products affect the enthalpy of a reaction
Combination of hydrogen and oxygen to form liquid water at 25 and atmospheric
pressure evolves

When 2g of hydrogen are burnt just above 100 , less heat is given out.

The observed difference is due to heat of vapourisation of 1 mole of water.

5. Allotropic modifications
There is an enthalpy change involved in conversion one allotrope to another. A particular
allotrope of an element used in a reaction affects the enthalpy of reaction. For example;
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CALORIMETRY
Calorimetry is a technique used to measure amounts of heat transferred to or from a
substance. A calorimeter is a container that is insulated against heat loss that is used to
measure the amount of heat involved in a chemical or physical process.
The common calorimeters used in laboratory experiments include the coffee cup
calorimeter and the bomb calorimeter.
The coffee cup calorimeter is used when measuring the heats of neutralisation, solution,
precipitation. It is constructed from a polystyrene cup with a lid. A thermometer is
usually inserted in it to measure heat changes.
The bomb calorimeter is mainly used to determine heat of combustion of a solid
substance.

Heat capacity of a calorimeter

The heat capacity of a calorimeter is the quantity of heat absorbed by the calorimeter

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for each rise in temperature. Its unit is

The heat capacity of a calorimeter must be determined experimentally.

Experiment to determine heat capacity of a simple calorimeter/

plastic cup calorimeter
Using a measuring cylinder, measure of water into the calorimeter and record its
temperature, using a thermometer.
Measure another of water into a beaker and heat it to . Keep the
temperature steady to for to minutes.
Then pour the hot water quickly into the calorimeter containing cold water and stir the
mixture. Record the temperature, .
Treatment of results

[ ] [( )] ( )
[ ] ( ) [( )]
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( ) [( )]

[ ]
( )

TYPES OF ENTHALPY CHANGES

Enthalpy of formation
Enthalpy of formation of a compound is the heat evolved or absorbed when one mole
of a compound is formed from the constituent elements in their standard states.
When enthalpy of formation is determined under standard conditions, it is called
standard enthalpy of formation.

Standard enthalpy of formation

The standard enthalpy of formation of a compound, , is the heat evolved or

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absorbed when one mole of the compound is formed from its elements in their normal
states at 298K and 1 atmosphere.

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CHAPTER FIVE
PHYSICAL EQUILIBRIA
Equilibrium represents the state of a process in which the properties like temperature,
pressure, concentration of the system do not show any change with passage of time.

A physical equilibrium is an equilibrium that exists between different phases or physical

properties. It represents the existence of the same substance in different physical states.
This equilibrium does not involve any chemical change. It involves only physical
changes like phase changes or solubility.

SYSTEMS, PHASES, COMPONENTS AND PHASE

DIAGRAMS
System

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A system is that part of the universe, the set of substances and energy associated with
them, that is being studied.
For example if reactions are occurring in a conical flask, everything inside the flask is a
system.

Phase
A phase is a homogeneous part of a system which is physically distinct from other parts
of the system by a definite boundary.
Each of the three homogeneous states (solid, liquid and gas) in which a substance can
exist is called a phase.
 For example a mixture of gases is one phase
 A solution is one phase
 A saturated solution in the presence of an excess of the solute is a two-phase
system
Except under special conditions, only two phases can exist in equilibrium.

Component
A pure substance in a system that defines part of the composition of that system
A mixture of water and ethanol has two components but one phase
A mixture of ice and water has two phases but one component
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Phase diagram
When a substance can exist in different phases, for example water which can exist as a
liquid, gas (water vapour) or solid (ice), the conditions under which each phase exists,
and the various equilibria that can exist between the three phases can be represented by a
phase diagram.
A phase diagram is a graph on which pressure is plotted against temperature showing
equilibria between different phases of a substance and the temperatures and pressures
at which each phase exists.
 An area/ region of a phase diagram represents one phase
 A line or curve represents the temperatures and pressures under which two phases
can exist in equilibrium
 A triple point represents the temperature and pressure under which three phases
can coexist in equilibrium.

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COMPONENT SYSTEMS
There are two types of components systems namely;
(i) One-component system
Only one pure chemical substance is involved in the equilibrium
(ii) Two-component system
Two chemically independent components are involved in the equilibrium

One component systems

Examples of one component systems include;
 The water system
 The sulphur system
 The carbon dioxide system

The water system

Water can exist as liquid, as a solid(ice) or as a vapour. It is called steam when its
temperature is above .
Below is a phase diagram for the water system.
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Phase diagram for water

B
Pressure C
Liquid

Solid Vapour
O
A

Temperature
At low temperature and low pressure, water exists as ice. At low temperature and high

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pressure, it exists as vapour. At high temperatures and high pressures, it exists as a
liquid.
Curves/lines
shows the variation of vapour pressure of ice with temperature
OA The line summarises the conditions under which solid ice and water
vapour can be in equilibrium.
This curve is called the sublimation curve of ice.
shows the variation of vapour pressure of liquid water with
temperature
OC The line summarises the conditions of temperature and pressure under
which liquid water and water vapour are in equilibrium.
This curve is called the vapourisation curve of liquid water.
shows the effect of pressure on the melting point of ice or freezing
OB point of water.
The line shows equilibrium between ice and liquid water.
It is called the freezing curve/ fusion curve.
Note: Line OB slopes upwards to the left because the melting point of ice decreases as
the pressure increases.
This decrease in melting point with increase in pressure is related to Le Chatelier‟s
principle. (Check next Chapter)

Points
O Triple point of water
C Critical point of water
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The triple point refers to the particular temperature and the particular pressure at
which ice, water vapour and liquid water co-exist at equilibrium.
The critical point represents the particular temperature and particular pressure above
which water vapour cannot condense to liquid water no matter how much pressure is
applied.
The critical temperature is the temperature above which vapour cannot be
converted into liquid water no matter how much pressure is exerted.
Beyond the critical temperature, liquid water and water vapour are undistinguishable
Effect of temperature and pressure on the phases
Y
Pressure J Z
F H P G

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

B
A C
M Q
X K

Temperature
1. The diagram above is a phase diagram for the water system
(a) Name the ;
(i) regions A, B and C
(ii) points Q and Z
(iii) curves QY, QX and QW
(b) State why line QY slants to the left
2. Explain the changes that take place when ;
(i) temperature of the system is increased from F to G at a constant
pressure
(ii) pressure of the system is reduced from J to K at constant temperature.

(i) At F, water exists in the solid phase (ice).

Increase in the temperature of ice moves the system from F to H without change
in phase.
At H, ice begins to melt and the temperature remains constant until all the ice has
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melted.
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After all the ice has melted, further increase in temperature will move the system
from H to P in the liquid phase.
At point P, liquid water begins to vapourise and the temperature remains constant
until all the water has vapourised.
Further increase in temperature moves the system from P to G in the vapour
phase.

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Examples of solutions that deviate negatively from Raoult’s law

They include;
 Water and nitric acid  Trichloromethane(chloroform) and
 Water and hydrofluoric acid ethoxyethane
 Water and hydrochloric acid  Trichloromethane and benzene
 Water and hydrobromic acid  Trichloromethane and propanone
 Water and hydroiodic acid  Propanone(acetone)and
 Water and chloric(VI) acid aminobenzene(aniline or
 Water and sulphuric acid phenylamine)
 Methanol and ethanoic acid  Propanone and ethanol
 Water and methanoic acid  Phenol and phenylamine

N.B. Please refer to bonding and structure to identify forces of attraction between
the individual molecules and when each of the two liquids above are mixed.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

In general, for solutions that deviate negatively from Raoult‟s law;
 Forces of attraction between different molecules(A and B) are stronger than
forces of attraction between similar molecules (A and A) or (B and B)
 Heat is evolved on mixing the components of the solution
 Volume of the solution is less than the sum of the volumes of the two liquids
mixed
 The solution has a lower vapour formation tendency compared to the ideal
solution.
 The solution can’t be separated to its pure components by fractional distillation
because at a certain point during distillation the solution form an azeotropic
mixture whose liquid and vapour composition are at equilibrium and boils at
constant temperature.

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Characteristic vapour pressure-composition diagram for negative

deviation from Raoult’s law

Liquid phase

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Vapour
pressure Vapour phase
Azeotrope

Instead of percentage composition, mole fraction may be used

Component A is more volatile than B (A has a higher saturated vapour than B)

Maximum boiling point-composition diagram

(Negative deviation from Raoult’s law)

When two liquids in solution associate through intermolecular bonding, their escaping
tendencies into vapour reduce, hence a reduction in vapour pressure than what is
expected basing on Raoult‟s law. For such solutions, a minimum is seen in the vapour
pressure-composition diagram. The minimum vapour pressure implies that the boiling
point at that composition will be maximum.
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Considering the mixture of A and B above, the boiling-point composition diagram can
be drawn a shown below.

Azeotropic mixture Vapour phase

Boiling point of Azeotropic

mixture
Boiling point of pure B

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Temperature 𝐶 Boiling point of pure A
Liquid phase

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Positive deviation from Raoult’s law

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Calculations involving steam distillation

Examples
1. An organic compound X is steam distilled at normal atmospheric pressure and
the distillate was found to contain 75% by composition of X at a given
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temperature. If at the same temperature, the vapour pressure of water is

640mmHg. Calculate the relative molecular mass of X.

2. A mixture of nitrobenzene and distilled water boiled at at one atmosphere.

Calculate the percentage composition of the distillate. The saturated vapor
pressure of water at is .

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

⁄

The distillate contains water

and nitrobenzene.
3. The vapour pressure of water at is . A liquid Y is insoluble in
water and has a relative molecular mass of 160. A mixture of Y and water steam
distills at under standard atmospheric pressure. Calculate the mass of
water collected in the distillate if the mass of Y in the distillate is 40g.

⁄
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4. Chlorobenzene forms an immiscible mixture with water. It’s mixture with steam
distills at an atmospheric pressure of . A sample of distillate
contains chlorobenzene for every of water. Calculate the vapour
pressure of water and chlorobenzene at .

But

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Questions on steam distillation

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COLLIGATIVE PROPERTIES
All solutions containing non-volatile solutes have certain properties in common. All these
properties vary with the compositions of the solutions in a similar way.
Each of these properties can be measures over a range of concentrations of the solutions
and the results obtained depend on the total number of solute particles present in a fixed
amount of solvent and hold for dilute solutions.
The properties are called colligative properties.
Colligative properties are therefore defined as physical properties of a dilute solution
which depend on the number of non-volatile dissolved particles in the solution but do
not depend on the chemical nature of the solute particles.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The greater the number of particles in solution, the greater the extent to which the
colligative property is affected.
The colligative properties include:
1. Lowering of the vapour pressure of a solvent
2. Elevation of boiling point
3. Freezing point depression
4. Osmotic pressure of solution
Colligative properties are important and useful for the determination of molecular
masses for non-volatile solutes
Limitations of colligative properties
A correct value of relative molecular mass obtained by use of any colligative property is
only obtained if;
(i) Solute does not associate or dissociate in solution.
When solute particles associate in solution, the number of particles in solution decreases,
lowering the colligative property and increasing the relative molecular mass.
Molecular mass obtained by a colligative property for a solute that associates in solution
is always twice the actual value

When solute particles dissociate in solution, the number of particles in solution increases,
and the colligative property also increases, reducing the relative molecular mass.
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Molecular mass obtained by a colligative property for a solute that dissociates in solution
is lower than the actual value.

(ii) The solution is dilute

(iii) There is no chemical reaction between the solute and the solvent.
(iv) The solute is non-volatile

Vapour pressure lowering

Vapour pressure of a liquid is the pressure exerted by the vapour when it is in
equilibrium with the liquid at a given temperature.

The vapour pressure of a solvent in solution is less than the vapour pressure of the pure
solvent at the same temperature.
This is because the non-volatile solute particles occupy some of the surface of the
solution. This reduces the escaping tendency of the solvent particles into the vapour

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

phase. The solution there has a lower vapour pressure than that that would be exerted
by a pure solvent.
Question; Explain why an aqueous solution of glucose has a lower vapour pressure
than water at a given temperature
Glucose is non-volatile solute . When dissolved in water, glucose particles occupy some
of the surface of the solution. This reduces the escaping tendency of the solvent
particles into the vapour phase. The solution there has a lower vapour pressure than
that that would be exerted by a pure water.

For a solvent in solution, the vapour pressure lowering ( ) is given by;

,

Derivation of expression for relative vapour pressure lowering

For a solution made up of a volatile solvent and a non-volatile solute, the total vapour
pressure of the solution is equal to the partial vapour pressure of the solvent
because the solute does not contribute to the vapour pressure.
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But , where

Where represents number of moles.

From the above expression, is called relative lowering of vapour

pressure and the whole expression represents the Raoult’s law of vapour pressure
lowering.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Raoult’s law of vapour pressure lowering therefore states that the relative lowering of
vapour pressure of a solution containing a non-volatile solute is equal to the mole
fraction of the solute in the solution at a given temperature.
For dilute solutions, is small compared to this implies that;

Where; and are masses of the solute and solvent respectively

and are the molar masses of water and the liquid respectively.
Note: The lowering of vapour pressure of a solvent by a non-volatile solute at a given
temperature is directly proportional to the concentration of the solute and inversely
proportional to the relative molecular mass of the solute.

Assumptions/ limitations of vapour pressure lowering

(i) Solute does not associate or dissociate in solution.
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(ii) The solution is dilute

(iii)There is no chemical reaction between the solute and the solvent.
(iv) The solute is non-volatile
Calculations involving lowering of vapour pressure
Examples
1. The vapour pressure of pure ethoxyethane at a certain temperature is
. Calculate the vapour pressure of a solution of camphor,
in ethoxyethane at the same temperature.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. (a) Define the term relative lowering of vapour pressure of a solvent.
(b) (i) At , an aqueous solution of carbamide of
concentration has a vapor pressure of . Determine
the vapour pressure of water at this temperature.
(ii) State the assumptions you have made in b(i).
(a) Relative lowering of vapour pressure is the difference of vapour pressure of a pure
solvent and the vapour pressure of the solvent above its solution with a non-volatile
solvent divided by the vapour pressure of the pure solvent.
(b) (i)
⁄

⁄
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(i) Carbamide does not associate or dissociate in solution.

The solution is dilute
There is no chemical reaction between the carbamide and water.
Carbamide is non-volatile
Density of solution is

3. The vapour pressure of pure benzene at a certain temperature is 640mmHg. A

non-volatile, nonelectrolyte solid weighing 2.175g is added to 39g of benzene, the
vapor pressure of a solution of the solid in benzene is 600mmHg. Calculate the
molar mass of solid substance.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

⁄

3. The vapour pressure of carbon disulphide at a certain temperature is

. At the same temperature, a solution of 5g of sulphur in of
carbon disulphide has a vapour pressure of . If the density of
carbon disulphide at this temperature is .
(a) Calculate the relative molecular mass of sulphur
(b) Deduce the molecular formula of sulphur in carbon disulphide.
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(a)
⁄

The relative molecular mass of sulphur is

⁄ 256
(b) Molecular formula of sulphur in carbon
disulphide is
4. The vapour pressure of water is at a certain temperature. Calculate
the lowering in vapour pressure that occurs when 12g of urea, are
dissolved in one litre of water at the same temperature.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

⁄

5. A solution contains 4.45g of solute X in 1kg of carbon disulphide. Another

solution contains 6.42g of sulphur in the same mass of carbon disulphide. If the
two solutions have the same vapour pressure at the same temperature, calculate:
(a) the relative lowering of vapour pressure
(b) Structural formula of the dissolved sulphur
(Relative molecular mass of X=178)
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(a) For a solution of X in ; For a solution of Sulphur in ;

⁄ ⁄

(b) Since the two solutions have the same

vapour pressure, and the same solvent(same
vapour pressure of pure solvent) is used, then
both the lowering of vapour pressure

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

and the relative lowering of vapour pressure is
Molecular formula is
the same.
Structural formula is;

Questions
1. (a) State Raoult’s law of relative lowering of vapour pressure.
(b) (i) Calculate the vapour pressure of a solution containing 18g of glucose
in 50g of water at . (Vapour pressure of water at is
150mmHg.)
(ii) State any assumptions made in (b)(i).
2. A solvent Y of molecular mass 62 has a vapor pressure of at .
23.3g of a non volatile solute of molecular mass 270 was added to 100g of Y at
.
(i) Calculate the vapor pressure of solution
(ii) State and explain the effect of increasing the concentration of the solute on
the boiling point of Y.
3. The vapor pressure of water at is . At this temperature, a solution of
of carbamide in of water has a vapour pressure of . Find the
relative molecular formula of the carbamide.
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4. The vapour pressure of a 3% solution of a non-volatile solute X in ethoxyethane is

at a certain temperature. The vapour pressure of pure ethoxyethane at the
same temperature is .
(i) Calculate the relative molecular mass of X
(ii) State any other assumptions made in (i) apart from X being non-volatile
5. of a certain solute were dissolved in in ethoxethane at and vapour
pressure of the solution was measured to be . At this temperature vapour
pressure of ethoxyethane was found to be . Calculate relative molecular
mass of the solute.
6. When of sucrose were dissolved in of water at , the vapour pressure
decreased by . Calculate the molar mass of sucrose ( Vapour pressure of water
at is )
7. The vapour pressure of pure water at is . The vapour pressure of a
solution of 4g of a sugar in 100g of water at the same temperature is .

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Calculate the relative molecular mass of the sugar.
8. 19 g of solute K, were dissolved in 90g of water and vapour pressure of the solution
was lowered by 42 mmHg. Calculate molar mass of solute K if vapour pressure of
pure water is 92 mmHg.
9. The vapour pressure of a solution containing of a substance in 1000g of
water was reduced by of water at (The vapor pressure of water at
is .
(a) Calculate the relative molecular mass of substance .
(b) State four assumptions made in (a)
(c) Explain why the vapor pressure of the solution containing a nonvolatile solute is
less than the vapor pressure of a pure solvent.

Graphical representation of vapour pressure lowering

From the expression;

⁄

( )
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Comparing with the equation a graph of the lowering of vapour pressure( )

plotted against mass of solute for a given mass of water can be plotted.
A graph of lowering of vapour
pressure( )
against mass of solute is a straight
line through the origin.
𝑝 The slope of the graph gives the
𝑷𝒂 value ( )

( )

𝒎𝒂𝒔𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆
𝒈

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The data you are usually given requires you to calculate first before graph plotting.
is the vapour pressure at . Each value is subtracted from the
value to get values at the different values.
Also from the expression;

⁄ ( )

( )
Since

Comparing with the equation a graph of the lowering of vapour pressure( )

plotted against mass of solute of a solute in a given solvent
can be plotted.
The density if given in must be multiplied by 1000 to convert it to
since units of concentration are usually expressed per litre
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A graph of lowering of vapour

pressure( )
against
of solute in a solvent is a straight
line through the origin.
𝑝 The slope of the graph gives the

𝑷𝒂 value
( )

𝟑
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒎𝒐𝒍𝒅𝒎
The data you are usually given may require you to calculate first before graph
plotting. is the vapour pressure at . Each value is

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

subtracted from the value to get values at the different
values.
Questions
1. (a) (i) Define the term vapour pressure
(ii) State Raoult‟s law of vapour pressure lowering
(b) The vapour pressure of aqueous solutions of glucose containing 9.0g of water at
27 varies with the mass of glucose dissolved as shown in the table below.
Mass of glucose in 9.0g of water 0.00 0.45 0.90 1.80 3.60 4.50 7.20
Vapour pressure of 31.82 31.66 31.50 31.32 30.55 30.23 29.27
solution(mmHg)
(i) Plot a graph of lowering in vapour pressure(ΔP) against mass of glucose
dissolved in 9.0g of water.
(ii) Use your graph in b(i) above to determine the molar mass of glucose.
(c) State the effect of water on the molecular state of glucose. Give a reason for your
answer using the molar mass calculated in b(i) above.
2. The lowering in vapour pressure of a volatile solvent is a colligative property.
(a) (i) Define the term colligative property
(ii) State two other examples of colligative properties
(b) The vapour pressure of different solutions of solute Y dissolved in solvent X at
40 are shown in the table below.
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Concentration of Y 0.00 0.10 0.20 0.30 0.40 0.50

Vapour pressure of 16.000 15.971 15.942 15.914 15.880 15.860
solution
(i) Plot a graph of lowering in vapour pressure(ΔP) against concentration of Y.
(ii) Use your graph in b(i) above to determine the relative molecular mass of
solvent X if its density is .
(iii) State two assumptions made in b(ii) above.

Elevation of boiling point (Ebullioscopy)

Boiling point of a liquid is the constant temperature at which its saturated vapour
pressure becomes equal to the external pressure on the liquid.
A pure liquid will only boil when its saturated vapour pressure is equal to the external
pressure. The external pressure is usually the atmospheric

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

pressure
The vapour pressure of a liquid decreases when a non-volatile solute is dissolved in it
The decreased vapour pressure implies that the solution will have to be heated to a higher
temperature than the boiling point of the pure liquid so that its equilibrium vapour
pressure becomes equal to the atmospheric pressure for boiling to take place.
Pure water boils at an aqueous solution of sodium chloride boils at at
. Explain
Sodium chloride is non-volatile solute. When dissolved in water, sodium chloride
particles occupy some of the surface of the solution. This reduces the escaping
tendency of the solvent particles into the vapour phase. The solution there has a lower
vapour pressure than that that would be exerted by pure water. The solution should
therefore be heated at a higher temperature than the boiling point of pure water so that
its equilibrium vapour pressure becomes equal to the atmospheric pressure for boiling
to take place.

In simple terms, the boiling point of a solution containing a non-volatile solute

is always higher than the boiling point of pure solvent( ). This
increase in boiling point is called the elevation in boiling point .
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Vapour pressure-temperature diagrams and boiling points

C

760 B
F
Vapour pressure A
(mmHg)
D E

𝑻𝟎𝒃 𝑻𝒃
Temperature ( 𝑪)

Curve ABC represents the variation of vapour pressure of pure solvent with
temperature
Curve DEF represents the variation of vapour pressure of solution with temperature

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Curve DEF is below curve ABC at all temperatures because the vapour pressure of the
solution is always lower than that of pure solvent
is the boiling point of pure solvent
is the boiling point of the solution.
The elevation in boiling point, . The greater the concentration of the
solute particles in solution, the greater the boiling point elevation.
Therefore a curve of a more concentrated solution will still be below curve DEF at all
temperatures.
The boiling point constant of the solvent or molal boiling point constant
(Ebullioscopic constant, )
This is the elevation in boiling point caused when one mole of a non-ionizing and non-
volatile solute is dissolved in 1000g of a solvent.
The units of the ebullioscopic constant are or
Boiling point elevation is directly proportional to magnitude of vapour pressure lowering

The vapour pressure lowering is proportional to the molality, m (not molarity) of the
solute particles.

Therefore boiling point elevation is directly proportional to molality of the solute.

where is molality of the solute in solution and is the boiling point constant of the
solvent or molal boiling point constant or ebullioscopic constant.
The molal concentration (or molality; symbol m) is the amount of substance per unit mass
of solvent, commonly given in units of .
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( )

Experimental determination of molecular mass using boiling point elevation method

Using Cottrell’s apparatus to find relative molecular mass of benzoic acid in
propanone

Beckmann thermometer

To condenser
Inner tube Side arm

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Cottrell pump Wide tube
Solvent/Solution
Platinum wire

A known mass of pure propanone, is placed in a wide tube fitted with a side arm
leading to a reflux condenser.
The boiling tube is closed by a stopper through which is passed a second inner tube, open
at the lower end and fitted with a Beckmann thermometer.
In the liquid is immersed a Cottrell pump, C to prevent super heating
The propanone is then heated until the Beckmann thermometer shows a constant
temperature and the boiling point is measured.
A known mass of benzoic acid, in pellet form is then added through the side arm to
the solvent
The resulting solution is also heated until the Beckmann thermometer shows a constant
temperature and the boiling point of the solution is also measured.
Treatment of results

Let the boiling point elevation constant of propanone be

( )
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( )

( )

The relative molecular mass of the benzoic acid is ( )

Assumptions/ limitations of the boiling point elevation method for determining
relative molecular mass
(i) Solute does not associate or dissociate in solution.
(ii) The solution is dilute
(iii) There is no chemical reaction between the solute and the solvent.
(iv) The solute is non-volatile

Explain why the molecular mass of ethanoic acid obtained by ebullioscopic method
is 120g using benzene as a solvent.
Molecular mass of

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The molecular mass of ethanoic acid obtained by boiling point elevation method is twice
the actual value. This is because ethanoic acid associates through intermolecular
hydrogen bonds to form dimers in benzene. The number of ethanoic acid molecules in
benzene solution is half the original number in the pure solute. This lowers the boiling
point elevation but increasing the relative molecular mass to twice the actual value.
Intermolecular hydrogen bond

The relative molecular mass of sodium chloride obtained by boiling point elevation
method is 29.25. Explain.
Actual relative molecular mass of sodium chloride
The obtained relative molecular mass is half the actual value.
Sodium chloride being a strong electrolyte, completely ionises in water to form sodium
ions and chloride ions

Therefore 1 mole of sodium chloride will form a total of 2 moles of ions in solution.
Since boiling point elevation is a colligative property, directly proportional to the
number of solute particles in solution, the ionisation of sodium chloride increases the
boiling point elevation but reduces the relative molecular mass to half the actual value.
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Calculations involving boiling point elevation

Examples
1. (a) A solution containing 60g of and 50g of water was boiled. Calculate
the boiling point of the solution.

(b) State any assumption(s) you have made in your calculation.

(a)
( )

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(b) does not associate or dissociate in solution.
The solution is dilute
There is no chemical reaction between and water.
is non-volatile

2. A aqueous solution of urea ( ) has a boiling point of .

Calculate the boiling point of pure water.

( )

( )
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3. 2.00g of phosphorus raise the boiling point of 37.4g carbon disulphide by

(a) Calculate the molar mass of phosphorus in carbon disulphide

(b) (i) Hence determine the molecular formula of phosphorus in carbon

disulphide.
(ii) State any two assumptions made in the calculation in (a) above
(iii) Comment on the result in b(i) above.
(a)
( )

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(b) (i) Molecular formula of Phosphorus in carbon
disulphide is
(ii) The solution is dilute
There is no chemical reaction between phosphorus and carbon disulphide.
Phosphorus is non-volatile
(iii) Phosphorus exists as a tetratomic molecules in carbon disulphide

4. 0.900g of a solute was dissolved in of benzene at 25 . The solution

formed boiled at 0.25 higher than the boiling point of benzene. Calculate
relative molecular mass of the solute.

( )

( )
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3. (a) The boiling point of pure water is 100 but when 1.97g of potassium chloride
is dissolved in 125g of water, the solution boiled at 100.11 at a pressure of
760mmHg. Explain this observation.
(b) From the information given in (a) above, calculate the boiling point constant
of water.
(a) Potassium chloride is non-volatile solute. When dissolved in water, potassium chloride
particles occupy part of the surface of the solution. This reduces the escaping tendency of the
water molecules into the vapour phase. The solution there has a lower vapour pressure than
that that would be exerted by pure water. The solution should therefore be heated at a higher
temperature than the boiling point of pure water so that its equilibrium vapour pressure
becomes equal to the atmospheric pressure for boiling to take place.
(b)
( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

4. (a) Define the term boiling point elevation constant of a substance.

(b) The boiling point of benzene under certain pressure condition is .
Calculate the boiling point elevation constant of benzene, if a solution
containing 5g of 2,4,6-trinitrophenol, in 100g of benzene,
boils at .
(b)
( )

( )
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5. Calculate the mass of sucrose, , that would have to be dissolved in

1000g of water to raise its boiling point to 101.7 .

( )

Questions
1. Calculate the boiling point of a solution formed by mixing 8g of glucose, ,
and 120g of water.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. Calculate the boiling point of a solution containing 0.360g of glucose dissolved in
100g of water. The boiling point of pure water is
.
3. The boiling point of ethanol is 78 . Calculate the boiling point of a solution
containing 2.7g of ethanamide in 75g of ethanol (Boiling point
elevation for 1000g of ethanol is )
4. The boiling point of ethanol is 78 and its molal boiling point constant is
. A solution containing 0.56g of camphor in 16g of ethanol has a
boiling point of 78.278 . Calculate the relative molecular mass of camphor.
5. 0.900g of a solute was dissolved in of benzene at 25 . The solution formed
boiled at 0.25 higher than the boiling point of benzene. Calculate relative molecular
mass of the solute.

6. The boiling point of an aqueous solution containing 3g of a non-volatile solute in

200g of water is 100.45 . Calculate the molar mass of the
solute.
7. A solution containing 1.00g of a non-volatile solute in 10.0g of benzene boils at
1.22 higher than pure benzene. Calculate the molecular mass of the
solute.
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8. (a) State what is meant by the term ebullioscopic constant.

(b) 0.40g of camphor when dissolved in 33.5g of trichloromethane produces a
solution boiling at 0.30 above the boiling point of pure solvent. Calculate the
ebullioscopic constant of trichloromethane. ( ).
9. (a) Define the term boiling point elevation constant of a substance.
(b) An aqueous solution of glucose containing 12g of the solute dissolved in 100g of
water was found to boil at while pure water boils at . Calculate
the boiling point elevation constant of water.
10. Calculate the mass of sucrose, , that would have to be dissolved in 1000g
of water to raise the boiling point by 1.0 .
11. (a)Explain the terms;
(i) Boiling point of a liquid
(ii) Boiling point elevation constant of a liquid
(iii) Relative molecular mass

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(iv) Colligative property
(b) Describe an experiment to determine the relative molecular mass of naphthalene in
chloroform by the elevation of boiling point method.
(c) State, with reasons why the method in (b)(i) above is not suitable for determining
relative molecular mass of;
(i) polyvinylchloride
(ii) ethanoic acid
(d) (i) A solution of 2.8g of cadmium(II) iodide in 20g of water boiled at at
standard pressure. Calculate the relative molecular mass of the solute and
comment on your answer.
(ii) A solution contains 1 mole of sugar per kg of water. Another solution contains
1 mole of urea per kg of water. State and explain which of the two solutions
will have a higher elevation in boiling point.

Graphical representation of Boiling point elevation

The elevation in boiling point is proportional to the lowering in vapour pressure

Since the lowering in vapour pressure is directly proportional to the concentration of

solute and inversely proportional to relative molecular mass of the solute;
, where is concentration in grams of solute per litre of solvent
This implies that
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where the constant is the boiling point constant

A graph of boiling point elevation against concentration can be plotted
A graph of elevation of boiling
point ( ) against
𝑇 of solute
in a solvent is a straight line
𝑪
through the origin.
The slope of the graph gives the
value

𝟑
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒈𝒅𝒎
If of the solvent is known, the relative molecular mass of the solute can be calculated.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The data you are usually given may require you to calculate first before graph
plotting.
Freezing point depression (Cryoscopy)
Freezing point of a liquid is the constant temperature at which the liquid coexists with
its solid form at the same saturated vapour pressure.
The vapour pressure of a solvent decreases when a solute is dissolved in it and therefore
the solid-liquid equilibrium will only exist at a temperature lower than that of the pure
solvent.

Explain why freezing point of a solution containing a non-volatile solute is always

lower than freezing point of the pure solvent
When a non-volatile solute is dissolved in a solvent, the solute particles occupy part of
the surface of the solution. This reduces the escaping tendency of the solvent molecules
into the vapour phase. The solution there has a lower vapour pressure than that that
would be exerted by pure solvent. Therefore the temperature at which the solution is at
equilibrium with the solid solvent is lower than that for the pure solvent.

In simple terms, the freezing point of a solution containing a non-volatile

solute is always lower than the freezing point of pure solvent( ). This decrease
in boiling point is called the freezing point depression( ).
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Vapour pressure-temperature diagrams and freezing point

B D

760

Vapour pressure A
(mmHg) C
E
F

𝑻𝒇 𝑻𝟎𝒇
Temperature ( 𝑪)

Curve AB represents the variation of vapour pressure of pure solvent with temperature

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Curve CD represents the variation of vapour pressure of solution with temperature
Curve FCA represents the variation of vapour pressure of pure solid solvent with
temperature. It is called the sublimation curve of the solid solvent.
The point A, at which curves FCA and AB meet is the freezing point of pure solvent.
Point C is the freezing point of the solution.
Curve CD is below curve AB at all temperatures because the vapour pressure of the
solution is always lower than that of pure solvent
is the freezing point of pure solvent
is the free point of the solution.
The depression in freezing point, . The greater the concentration of the
solute particles in solution, the greater the depression in freezing point
Therefore a curve of a more concentrated solution will still be below curve CD at all
temperatures.
The freezing point constant of the solvent or molal freezing point depression
constant (Cryoscopic constant, )
This is the amount by which the freezing point of 1000g of a solvent is lowered when
one mole of a non-ionizing and non-volatile solute is dissolved in it.
The units of the cryoscopic constant are or
Freezing point depression is directly proportional to magnitude of vapour pressure
lowering

The vapour pressure lowering is proportional to the molality, m (not molarity) of the
solute particles.
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Therefore freezing point depression is directly proportional to molality of the solute.

where is molality of the solute in solution and is the freezing point constant of
the solvent or molal freezing point constant or cryoscopic constant.

Experimental determination of molecular mass using freezing point depression

method using Beckmann’s freezing point apparatus
Beckmann thermometer
Stirrers
Side arm
Air jacket
Glass tube Ice-salt freezing mixture

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Wider tube Freezing tube
Solvent/ Solution

A known mass of pure solvent, g is placed into a glass tube that is fitted with a
Beckmann thermometer, stirrer and has a side arm.
The freezing tube is placed in a wider tube that acts as an air jacket to ensure uniform
cooling.
The whole apparatus is put in a vessel containing an ice-salt freezing mixture that is kept
stirred
The solvent is allowed to cool while stirring until a constant temperature, is
obtained when it begins to freeze and recorded from the Beckmann thermometer.
The solvent is warmed until it melts.
A known mass of solute, g, in pellet form is added to the solvent through a side arm.
The solution is cooled while stirring and the steady temperature, at which it freezes,
is recorded.
Treatment of results

Let the freezing point depression constant of the solvent be

( )
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( )

( )

( )

The relative molecular mass of the solute is ( )

Assumptions/ limitations of the freezing point depression method for determining
relative molecular mass
(i) Solute does not associate or dissociate in solution.
(ii) The solution is dilute
(iii) There is no chemical reaction between the solute and the solvent.
(iv) The solute is non-volatile

Explain why 0.1 mole of sodium chloride depresses the freezing point of 1 of

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

water twice as much as 0.1 mole of glucose does.
Sodium chloride completely ionises in water to form sodium ions and chloride ions

Glucose is non-ionising solute

Therefore 0.1 moles of sodium chloride will form a total of 0.2 moles of ions in
solution. Glucose remains in its molecular state in solution and will still exist as 0.1
moles in solution. Since freezing point depression is a colligative property, directly
proportional to the number of solute particles in solution, the amount by which freezing
point of water is depressed by sodium chloride doubles that of glucose.

Calculations involving freezing point depression

Examples
1. Liquid camphor freezes at 175 . A solution of 1.54g of naphthalene, , in
18g of camphor freezes at 148.3 . Calculate the freezing point constant of
camphor.

( )
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( )

2. (a) Explain what is meant by the term cryoscopic constant

(b) Calculate the melting point of a solution made by dissolving 0.36g of
naphthalene, , in 6.0g of camphor. The melting point of camphor is
177 and for camphor is 40 for 1 mole in 1000g.
(b)
( )

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

3. Calculate the mass of water in which 10g of glucose, should be
dissolved to obtain a solution that freezes at .

( )

( )

4. A solution containing 1.2g of ethanoic acid in 80g of water freezes at .

Calculate the relative molecular mass of ethanoic acid.
( )
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( )

( )

5. (a) Explain what is meant by the term colligative property.

(b) 0.72g of a compound X was dissolved in 80g of water and the resultant
solution had a freezing point of . When 2.9g of the same compound
was dissolved in 111g of benzene the freezing point was depressed by .

Calculate the apparent molecular mass of X in ;

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(i) water
(ii) benzene
(c) Explain why the molecular mass of X differs in the solvents.

(b)(i)
( )

( )

(ii)
( )

( )

(c) The apparent molecular mass is X in benzene is twice that of benzene in water because two
molecules of X associate in benzene to give a dimer.
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6. (a) An aqueous solution containing 7.2g of a non-cyclic substance Z in 250g of

water freezes at . Calculate the molecular mass of Z.

(b) If Z contains carbon, hydrogen, and the rest being oxygen

(i) Calculate the simplest formula of Z
(ii) Determine the molecular formula of Z
(iii) Write the structures of all possible isomers of Z
(c) Z forms a yellow precipitate with phenyl hydrazine and iodine solution in
presence of sodium hydroxide. Name Z.
(a)
( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

(b) (i)

(iii) (iv)

(c) Z is Butanone
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Questions
1. A solution containing 0.368g of methanoic acid in 50g of benzene freezes at 5.093 .
(a) Calculate the relative molecular mass of methanoic acid.
( )
(b) Comment on the value in (a)
2. The melting point of camphor is 177.5 while that of a solution containing 1g of
naphthalene in 10g of camphor is 147 . Calculate the cryoscopic constant of
camphor. (Molar mass of naphthalene is 128)
3. The freezing point of a solution of 22.0g of carbon tetrachloride dissolved in 800g of
benzene is 4.59 . If the freezing point of benzene is 5.50 Calculate the molal
freezing point depression constant of benzene.
4. Calculate the freezing point of a solution containing 3.33g of ethane-1,2-diol in 14g of
water.
5. Calculate the freezing point of a solution containing 60g of glucose, in 200g

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

of water.
6. A solution containing 25.6g of sulphur dissolved in 1000g of naphthalene gave a
freezing point lowering of . Determine the molecular formula of sulphur in
naphthalene.

7. An organic compound W contains 22.8% nitrogen, 28% oxygen , 8.5% hydrogen and
the rest being carbon.
(a) Calculate the empirical formula of W
(b) 0.5g of W dissolved in 80g of water forming a solution that freezes at .
Calculate the molecular formula of W.

(c) When W was refluxed with potassium hydroxide, ethanoic acid and ammonia was
produced.
(i) Identify W
(ii) Write equations to show how W is obtained from a carbonyl compound.
8. (a) A compound Y contains 80% carbon, 6.7% hydrogen, and the rest being oxygen.
Calculate the empirical formula of Y.
(b) 0.48g of Y was dissolved in 50.0g of benzene and caused a freezing point
depression of 0.44 . Determine the molecular formula of Y.
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(c) Compound Y forms a yellow precipitate with 2,4-dinitrophenylhydrazine and

reacts with a mixture of iodine and sodium hydroxide to form a yellow precipitate.
Write;
(i) the structural formula of Y
(ii) equation and outline mechanism for the reaction between Y and 2,4-
dinitrophenylhydrazine.
9. of an organic compound Y on complete combustion gave 0.88g of carbon
dioxide gas and 0.18g of water. 0.53g of Y in 22g of ethanoic acid lowered the
freezing point of ethanoic acid by 0.78K.
(a) (i) Calculate the empirical formula of Y.
(ii) Determine the molecular mass of Y and write the possible structural
formula of Y.
(b) Y burns with a yellow sooty flame, gives a yellow precipitate with 2,4-
dinitrophenylhydrazine but does not form silvery deposits with ammoniacal silver

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

nitrate solution.
(i) Identify Y
(ii) Write an equation and suggest a possible mechanism between Y and 2,4-
dinitrophenylhydrazine in acidic media.
(c) Write equations indicating conditions to show how you would obtain
phenylethyne from Y.
10. (a) Define the term freezing point depression constant of a solvent.
(b) In an experiment, a 5 per cent solution of glucose, in water found give
the same freezing point depression as a 3.3 percent aqueous solution of .
(i) Determine the molecular formula of .
(ii) The compound in b (i) above forms a crystalline white precipitate with
saturated sodium hydrogen sulphite solution but no observable change with
ammoniacal silver nitrate solution. It also reacts with ethanoic acid in the
presence of concentrated sulphuric acid to give a product with a sweet
fruity smell. Write the structural formula and name of .
11. (a) Describe an experiment to determine the relative molecular mass of naphthalene in
benzene. (Include a well labelled diagram to illustrate your answer)
(b) The freezing point of pure benzene is . A solution containing 0.321g of
naphthalene, in 25g of benzene freezes at . A solution containing
0.305g of benzoic acid in 25g of the same solvent freezes at
(i) Calculate the molar freezing point depression constant for benzene.
(ii) Hence calculate the relative molecular mass of benzoic acid in benzene.
Also revisit questions 15, 18 and 19 under empirical and molecular formulae in matter
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Graphical representation of freezing point depression

The depression in freezing point is proportional to the lowering in vapour pressure

Since the lowering in vapour pressure is directly proportional to the concentration of

solute and inversely proportional to relative molecular mass of the solute;
, where is concentration in grams of solute per litre of solvent
This implies that

where the constant is the freezing point constant

A graph of boiling point elevation against concentration can be plotted
A graph of depression in freezing
point ( ) against

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

𝑇 of solute
in a solvent is a straight line
𝑪
through the origin.
The slope of the graph gives the
value

𝟑
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒈𝒅𝒎
If of the solvent is known, the relative molecular mass of the solute can be calculated.
The data you are usually given may require you to calculate first before graph
plotting.
From the expression;

A graph of freezing point of solution, when plotted against concentration will

be a straight line with a negative slope. The from which molar mass of the
solute can be obtained if is known. The graph has an intercept on the axis.
The intercept gives the freezing point of pure solvent, .
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Questions
1. The table below shows the freezing points of various concentrations of a non-volatile
solute Q in water at 760mmHg.
Concentration of Q 0 30 60 90 120 150
Freezing point 0 -0.16 -0.32 -0.49 -0.65 -0.81
(a) Plot a graph of freezing point depression against concentration of Q
(b) Determine the :
(i) slope of the graph you have drawn in (a).
(ii) relative molecular mass of Q.
2. (a) State what is meant by the following terms
(i) Colligative property
(ii) Freezing point constant of a substance
(b) (i) Describe an experiment to determine the molecular mass of naphthalene using

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

camphor as a solvent. (Diagram not required)
(ii) State three limitations of the method in (b)(i) above.
(c) The freezing points of solutions of various concentrations of a solute X in solvent
Y at 1.0 atm are given below.
Concentration 20 40 60 80 100 120 140
Freezing point -0.11 -0.22 -0.32 -0.43 -0.54 -0.65 -0.76
(i) Plot a graph of freezing point against concentration
(ii) Use your graph to determine the freezing point of Y
(iii) Determine the relative molecular mass of X.
(d) Ethanoic acid has a freezing point of 16.63 . On addition of 2.5g of an organic
solute to 40g of the acid, the freezing point was lowered by 15.48 . Calculate the
molecular mass of the solute. ( )

Osmotic pressure,
Osmosis is the movement of solvent molecules from a dilute solution to a more
concentrated solution through a semi-permeable membrane.
If two solutions of different concentrations are separated by a semi-permeable membrane,
the solvent molecules from the dilute solution will pass through the semi-permeable
membrane to the concentrated solution so that the two solutions have equal
concentrations. The osmosis can be stopped by applying pressure on the concentrated
solution. This pressure is called osmotic pressure, .
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Osmotic pressure is the minimum pressure required to prevent the movement of solvent
molecules from a dilute solution to a more concentrated solution when the solution is
separated from pure solvent by a semi-permeable membrane.
Experiment to determine osmotic pressure of a solution
(Using the Berkeley and Hartley’s method)

Pressure applied
Piston Water reservoir
Pressure gauge
Capillary tube Solvent Tap

Gun metal casing

Solution Semi permeable membrane

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

A solution whose osmotic pressure is to be determined is put in a gun metal casing
The solution is separated from the solvent in a cylindrical porous tube by a semi-
permeable membrane.
External pressure is applied by pushing down the piston until the level of the solvent in
the capillary tube is just stationary.
This applied pressure is the osmotic pressure of the solution and is read off directly from
the pressure gauge.

Suitability of osmotic pressure in determining molecular mass of non-volatile large

molecules e.g. proteins or polymers or plastics
Osmotic pressure is a better method to determine relative molecular mass of large
molecules than ebullioscopic and cryoscopic methods because;
Polymers have high relative molecular masses and in dilute solutions, the give few
dissolved particles. Relative molecular mass is inversely proportional to either freezing
point depression or boiling point elevation. The freezing point depression or boiling point
depressions caused by the few dissolved polymer particles in dilute solutions are very
small and cannot be measured by ordinary thermometers. However, dilute solutions of
polymers have reasonable and accurately measurable osmotic pressures at room
temperature.
In addition, the ebullioscopic method is not suitable because polymers tend to fragment
and decompose at high temperatures.
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In general, the advantages of the osmotic pressure are;

1. Osmotic pressure of a solution containing few particles is appreciable and can be
measured accurately than its elevation in boiling point or depression in freezing point
2. Osmotic pressure can be measured at room temperature hence more suitable for
substances that are not stable at higher temperatures.

Determination of relative molecular mass by osmotic pressure measurement

If the osmotic pressure of a solution containing of a solute in of solution is
measured at a temperature, , the number of moles of solute, can be determined from
the expression;

Since where is the molar mass of the solute.

Then;

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The molar gas constant, , is commonly used as when the units of
pressure, volume and temperature are and Kelvin respectively.
Recall that;

( )

Calculations involving osmotic pressures and molar masses

Examples
1. Calculate the osmotic pressure of a solution containing 4.0g of a non-volatile
solute per litre of solution at . The relative molecular mass of the solute is
40.
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2. A solution containing of a polymer was found to have an osmotic pressure

of atmospheres at . Calculate the molecular mass of the
polymer.

For osmotic pressure ONLY; 1.5% means

1.5g in a volume of 100

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The molecular mass of the polymer is
1,018,332.1g
3. The osmotic pressure of an aqueous solution of a non-electrolyte containing
of solution is at . Calculate the freezing
point of solution.
( )

The molar mass of the polymer is 189.58g

Assuming density of solution is . The volume of water used is 1000 and its mass
is 1000g.

( )
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4. The osmotic pressure of a solution containing 1.4g of a polymer per 100 of

a solution is at .
(a) Calculate the relative molecular mass of
(b) Determine the number of monomers in

(a)

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The relative molecular mass of the
polymer is 28,891.1g
(b)
Note that number of monomers should never be a decimal but a whole number.

Questions
1. (a) Define the term osmotic pressure.
(b) At ,a solution of a polymer has an osmotic pressure of
atmospheres. Calculate the formula mass of the polymer.
(c) Explain why in the determination of molecular mass of polymers, osmotic
pressure is used instead of ebullioscopic and cryoscopic methods.
2. A solution containing of polyphenylethene in of benzene is found to
have an osmotic pressure of at . Calculate the average relative molecular
mass of polyphenylethene.
3. The osmotic pressure of an aqueous solution of a non-electrolyte containing
per of solution is at . Calculate the freezing point of
solution.
( )
4. (a) Define the term Osmotic pressure.
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(b) A polysaccharide has the formula . A solution containing

of the sugar has an osmotic pressure of at .
Find the value of n.
(c) State any two assumptions made in (b) above.
5. A solution containing 20g of a polymer X in one litre of solvent exerts an osmotic
pressure at .
(i) Calculate the molecular formula of X
(ii) The molecular formula of the monomer of X is . Determine the
number of monomer units in X
(iii) Explain why the freezing point depression method is not suitable for
determining the molecular formula of X.
6. A solution of 42.0g of mannitol in 1 of water has an osmotic pressure of
at . Calculate the relative molecular mass of mannitol.
7. A aqueous solution of compound A has an osmotic pressure of at

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

. Calculate the relative molecular mass of A.
8. A 3.42% solution of substance X has the same osmotic pressure as a 5.96% solution
of substance Y. Calculate the relative molecular mass of Y. (Relative molecular mass
of X is 342)
9. (a) Define the terms;
(i) osmosis
(ii) Osmotic pressure
(b) State conditions under which osmotic pressure laws are valid.
(c) (i) Describe a method that can be used to determine the osmotic pressure of a
sucrose solution.
(ii) The osmotic pressure of a solution containing 1.4% of a polymer is
at . Determine the relative formula mass of the
polymer.
(iii) Briefly explain why osmotic pressure method is the preferred method to
determine the relative formula mass of polymers. |

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Determining relative molecular mass from osmotic-pressure- concentration graphs

From
but

( )
but ( )

A graph of osmotic pressure, against concentration can be plotted.

A graph of osmotic pressure,

against of
𝑶𝒔𝒎𝒐𝒕𝒊𝒄 solute in a solvent is a straight line

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

𝒑𝒓𝒆𝒔𝒔𝒖𝒓𝒆 𝝅 through the origin.
𝟐
𝑵𝒎 The slope of the graph gives the
value

𝟑
𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒈𝒅𝒎
The expression is used to calculate the relative molecular mass of the solute
where and T given in the question.
Note that if the values of osmotic pressure given are in atm or mmHg, they should be
converted as discussed earlier to while computing the slope and then use as
stated with T converted to Kelvin.
Questions
1. The osmotic pressures of various concentrations of solute X in methylbenzene at
are given in the table below.
Concentration of the solution( ) 1.0 2.0 3.0 4.0 5.0 6.0
Osmotic pressure( ) 23 37 53 75 92 109
(a) Plot a graph of osmotic pressure against concentration
(b) Use your graph to determine the relative molecular mass of X.
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2. (a) Define the terms

(i) Colligative property
(ii) Osmotic pressure
(b) (i) Describe an experiment to determine the molecular mass of mannitol by
osmotic pressure method.
(ii) State three limitations on this method
(c) The table below shows the osmotic pressure of a solution of mannitol of various
concentrations at .
Concentration of the solution( ) 1.5 3.0 4.5 6.0 7.5 9.0 10.5
Osmotic pressure of the solution(atm) 0.20 0.40 0.60 0.81 1.05 1.20 1.40

(i) Plot a graph of osmotic pressure against concentration of the solution

(ii) Explain the shape of the graph
(iii) Use the graph to determine the relative molecular mass of mannitol.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Miscellaneous questions
1. (a) Define the term colligative property.
(b) State four colligative properties of a solution.
(c) (i) Define the term mole fraction.
(ii) Calculate the mole fraction of potassium chloride in an aqueous solution
containing 10 of potassium chloride per 100 of water. ( )
2. (a) Define the terms;
(i) Colligative property
(ii) Boiling point constant
(b) Describe an experiment that you would carry out to determine the relative
molecular mass of a compound using the boiling point elevation method. Use a
diagram to illustrate your answer.
(c) Explain the effect of association of the solute on the value of the relative
molecular mass determined by boiling point method.
(d) (i) State the laws of osmotic pressure.
(ii) State the conditions under which these laws are valid.
(e) The osmotic pressure of a 1.24% solution of polyvinylchloride is
at 25 . Calculate the;
(i) relative molecular mass of polyvinylchloride
(ii) number of monomer units in polyvinylchloride.
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3. Explain the following observations;

(a) When propanone is mixed with tetrachloromethane, a warm miscible mixture was
formed whose volume was lower than the sum of the volumes of the individual
components.
(b) The boiling points of water and bromobenzene are and respectively.
However a mixture of water and bromobenzene boils below at atmospheric
pressure.
(c) A 0.01M solution of sodium chloride has the same freezing point depression as a
0.02M aqueous solution of glucose
(d) An aqueous solution of ethanol boils at whereas an aqueous solution of
sodium chloride boils at at .
(e) When steam at is blown into an aqueous solution of a solid at , it raises
the temperature of the solution above .
(f) Boiling point elevation method is not suitable for measuring relative molecular mass

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

of a plastic.
(g) The osmotic pressure method cannot be used to measure the relative molecular mass
of sulphuric acid in solution

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CHAPTER SIX
CHEMICAL EQUILIBRIA
THE CONCEPT OF CHEMICAL EQUILIBRIUM
Chemical reactions, just like physical changes can reach a state of equilibrium. Although
some reactions take place in one direction, like the when magnesium burns in air to form
magnesium oxide, other reactions take place in both forward and backward directions at
comparable rates for example the thermal dissociation of calcium carbonate.

The products of thermal dissociation of calcium carbonate are calcium oxide, a base and
carbon dioxide, an acidic gas which can react to form calcium carbonate again.
Apart from thermal dissociation of calcium carbonate, many other reactions do not go to

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

completion and then stop, since the products of the reaction themselves react to form
original reactants. Such reactions are called reversible reactions. Therefore, for
equilibrium to be established there is both a forward and backward reaction.

The characteristics of a chemical equilibrium

(i) The reaction in which it occurs should be reversible
(ii) The reaction should occur in a closed system
(iii) Temperature should be constant
(iv) Rate of forward reaction should be equal to the rate of backward reaction

Reversible and irreversible reactions

A reversible reaction is a reaction takes place in both forward and backward directions
such that both the reactants and products are present in the equilibrium hence does not
go to completion.

For example;

(i) the reaction between hydrogen gas and gaseous iodine to form hydrogen iodide

(ii) the esterification reaction for formation of ethylethanoate from ethanoic acid
and ethanol

(iii) reaction between heated iron and steam to form iron(II) diiron(III) oxide and
hydrogen
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An irreversible reaction is a reaction takes place only in the forward direction, such
that only the products are formed during the reaction hence the reaction can never be
at equilibrium.

(i) For example, the combustion of ethene to form carbon dioxide and water
+
(ii) Burning magnesium in air to form magnesium oxide

(iii) Alkaline hydrolysis of an ethylethanoate to form ethanoate ions and ethanol

̅ ̅

Dynamic equilibrium
A dynamic equilibrium is the equilibrium established when the rate of forward reaction
is equal to the rate of backward reaction, such that the concentration of reactants and

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

products remains constant.

For the reaction between known amounts of hydrogen and iodine in a sealed glass tube
heated to a higher constant temperature and then allowed to cool, the equilibrium mixture
formed contains hydrogen, iodine and hydrogen iodide.

This implies that both forward and backward reactions are still taking place and the rate
of formation of hydrogen iodide is equal to rate of dissociation of hydrogen iodide and
the concentrations of each species remains constant and the system is said to be in
dynamic equilibrium.
This can be proven by injecting iodine containing a small quantity of radioactive iodine-
131 into the equilibrium mixture. Radioactive iodine appears in the hydrogen iodide. This
confirms that both forward reaction and backward reaction are still occuring.

Types of chemical equilibria

There are two types equilibrium systems namely;

(i) Homogeneous equilibrium systems

(i) Heterogeneous equilibrium systems
A homogeneous equilibrium system is one in which all the reactants and products of a
reaction are in the same phase.
They can all gases, all liquids or all in solution.
For example;
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(i) the reaction between ethanol and ethanoic acid to form ethyl ethanoate
/diethyl ether (esterification)

(ii) the reaction between hydrogen gas and gaseous iodine to form hydrogen
iodide

(iii) Dissociation of dinitrogen tetroxide to form nitrogen dioxide.

A heterogeneous equilibrium system is one in which two or more phases are involved.

For example;
(i) Dissociation of calcium carbonate to form calcium oxide and carbon
dioxide.

(ii) Reaction between iron and steam to form triiron tetraoxide and hydrogen

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(iii) Reaction between bismuth chloride and water to form bismuth oxychloride
and hydrochloric acid

Note; if only ions are involved in an equilibrium, an ionic equilibrium (check next
chapter) is established.

THE LAW OF MASS ACTION OR EQUILIBRIUM LAW

For a homogeneous equilibrium, represented as;

[ ] [ ]
[ ] [ ]
Where [ ] represents molar concentration at equilibrium and
is the concentration equilibrium constant
The equilibrium law/ law of mass action therefore states that if a reversible reaction is
allowed to reach equilibrium at a particular temperature, the product of the molar
concentrations of the products raised to appropriate powers divided by the product of
the molar concentrations of the reactants raised to appropriate powers is a constant

or
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The law of mass action states that the in a reversible reaction, there is a fixed
relationship at a given temperature between the molar concentrations of the products
and those of the reactants in the equilibrium mixture.

The concentration equilibrium constant,

Equilibrium constant is the ratio of the product of molar concentration of products
raised to their appropriate powers to the product of molar concentration or reactants
raised to their appropriate powers in a stoichiometric equation of a reversible reaction
at constant temperature.

The pressure equilibrium constant,

For reactions involving gases, it is often more convenient to measure and express the gas
concentrations in partial pressures in atmospheres. If this is done, the equilibrium
constant is known as
For example;

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Using the law of mass action to write equilibrium constant
expressions ( or ) and units
When writing expressions for equilibrium constants, the following should be noted;

1. Check whether only the concentrations /moles in a given volume are given or total
pressure at equilibrium
2. If only concentration/ moles are given, then an expression for should be written.
3. If total pressure at equilibrium is given, then expression for should be written.
4. Solids do not appear in the equilibrium constant expression since their concentration
is assumed to be constant.
5. For a expression, only gaseous reactants and products appear.
6. If water is one of the reactants, and its concentration is not given, or remains
unchanged, it is assumed to be present in a large excess hence does not appear in the
equilibrium constant expression. If water is in gaseous state, then include it in the
expression.
7. When only the expression is required, do not write the equation also as part of the
answer
8. In the case of , strictly square brackets must be used.
9. Sometimes the question may specify for you whether to write a or expression.
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In each of the cases below, write the equation for the equilibrium, the equilibrium
constant expression in terms of either and or both , depending on what is
indicated in brackets and state the units.

1. Reaction between ethanol and ethanoic acid in presence of an acid catalyst ( )

2. The reaction between hydrogen gas and gaseous iodine.(both and )
3. Dissociation of dinitrogen tetroxide to form nitrogen dioxide.(both and )
4. Reaction between iodine solution and potassium iodide.( )
5. Thermal dissociation of calcium carbonate.(both and )
6. Reaction between iron and steam to form triiron tetraoxide and hydrogen .
(both and )
7. Hydrolysis of bismuth(III) chloride.( )
8. Reaction between hydrogen and nitrogen.(both and )
9. Hydrolysis of ethylethanoate using dilute hydrochloric acid.( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

10. Reaction of phosphorus trichloride and chlorine.(both and )
11. Reaction between nitrogen and oxygen.(both and )
12. Conversion of Sulphur dioxide to Sulphur trioxide.(both and )
13. Reaction between carbon monoxide and hydrogen to form gaseous methanol.(both
and )
14. Dissociation of hydrogen iodide.(both and )
15. Dissociation of phosphorus(V) chloride to phosphorus(III) chloride and
chlorine.(both and )
16. Dissociation of Sulphur trioxide.(both and )
17. Reaction between carbon disulphide and hydrogen to form methane and hydrogen
sulphide. .(both and )
18. Reaction between ammonia and oxygen to form nitrogen monoxide and water. (both
and )
19. Redox reaction between iron metal and chromium(III) ions. ( )
20. Hydrogenation of nitrogen dioxide to form ammonia and water.(both and )
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The relationship between and

is related to by the expression;

where is the pressure equilibrium constant

is the concentration equilibrium constant
is the molar gas constant
is the absolute temperature(K)
is the difference between total moles of gaseous products and total
moles of gaseous reactants
Derivation;

Consider a reversible reaction;

[ ] [ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ] [ ]
If the reactants and products are gaseous,

If the gases are ideal, then according to the ideal gas equation

is therefore proportional to
From equation , [ ]
[ ]
[ ]
[ ]
Substituting for , and in equation (ii) gives;
[ ] [ ]
[ ] [ ]
[ ] [ ]
( )
[ ] [ ]

[ ] [ ]
Since [ ] [ ]
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Where is the total number of moles of gaseous products total number of moles of gaseous
reactants in a balanced equation.

EXPERIMENTS ON CHEMICAL EQUILIBRIUM

(a) Experiment to determine the equilibrium constant for the hydrolysis of
ethylethanoate using hydrochloric acid.
A known amount of ethylethanoate (a moles) is mixed with a known amount of water (b
moles)
A known volume of concentrated hydrochloric acid is added to catalyze the reaction.
The mixture is kept in a sealed glass tube at a constant temperature for a week.
The tube is broken in cold water and the solution titrated with a standard solution of
sodium hydroxide using phenolphthalein indicator

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The amount of ethanoic acid present at equilibrium is obtained (x moles)
Treatment of results
Let V be the volume of the solution in dm3
If there are x moles of ethanoic acid at equilibrium, there are also x moles of ethanol at
equilibrium since mole ratio of
Moles of ester hydrolysed and moles of water used are both equal to x, since mole ratio
is also 1:1

Initial moles 0 0
Moles reacted/formed
Moles at equilibrium
concentration

[ ][ ]
[ ][ ]

⁄ ⁄

(( )( ))
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(b) Experiment to determine the equilibrium constant for the esterification reaction
between ethanoic acid and ethanol
A known amount of ethanoic acid (a moles) is mixed with a known amount of ethanol
(b moles) and put in a sealed glass tube.
The sealed tube and its contents is left in a water bath at to for 7 hours
The tube is broken in cold water and the solution titrated with a standard solution of
sodium hydroxide using phenolphthalein indicator

The amount of ethanoic acid present at equilibrium is obtained (x moles)

Treatment of results

Let V be the volume of the solution in dm3

moles of ethanoic acid at equilibrium=x
moles of ethanoic acid converted to ester and water =(a-x)
since mole ratio of

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(a-x) moles of form (a-x) moles of and (a-x) moles
of at equilibrium.
Since mole ratio of
Moles of ethanol that react=(a-x)
Moles of ethanol at equilibrium=b-(a-x) =(b-a+x)

Initial moles 0 0
Moles reacted/ formed
Moles at equilibrium
Concentration

[ ][ ]
[ ][ ]
( )( )

(( ) ( ))
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(c) Experiment to determine the equilibrium constant for the dissociation of

hydrogen iodide to hydrogen and iodine.
A known amount of hydrogen iodide (n moles) is put in a sealed glass bulb of a fixed
volume (v dm3) and kept in a thermostat at a temperature of ℃ until equilibrium is
established.
At equilibrium, the bulb is removed and rapidly cooled to stop the reaction and fix the
equilibrium such that the equilibrium does not adjust itself to the equilibrium value at a
lower temperature.
The tube is then broken under an aqueous solution of potassium iodide to dissolve the
iodine present at equilibrium.
The resultant mixture is titrated with a standard solution of sodium thiosulphate using
starch indicator

The amount of iodine present at equilibrium is obtained.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Treatment of results

Total volume of the bulb= v dm3

Number of moles of hydrogen iodide heated= c moles
Degree of dissociation of hydrogen iodide= α

Initial moles 0 0
Moles dissociated/formed
Moles at equilibrium

Concentration at equilibrium
[ ][ ]
[ ]

( )

( )
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(d) Experiment to determine the equilibrium constant for the reaction between
hydrogen and iodine to form hydrogen iodide.
A known amount of hydrogen (a moles) and a known amount of iodine (b moles) are
put in a sealed glass bulb of a fixed volume (v dm3), kept in a thermostat at a
temperature of ℃ until equilibrium is established.
At equilibrium, the bulb is removed and rapidly cooled to stop the reaction and fix the
equilibrium such that the equilibrium does not adjust itself to the equilibrium value at a
lower temperature.
The tube is then broken under an aqueous solution of potassium iodide to dissolve the
iodine present at equilibrium.
The resultant mixture is titrated with a standard solution of sodium thiosulphate using
starch indicator

The amount of iodine present at equilibrium is obtained.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Treatment of results

Total volume of the bulb= v dm3

Let number of moles of iodine converted to hydrogen iodide= x moles
Moles of hydrogen iodide formed = 2x moles

Initial moles 0
Moles reacted/formed
Moles at equilibrium
Concentration at equilibrium
[ ]
[ ][ ]
( )

( )( )
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CALCULATIONS INVOLVING CONCENTRATION

EQUILIBRIUM CONSTANT AND PRESSURE EQUILIBRIUM
CONSTANT
(a) Equilibria for esterification.
Examples
1. When 60g of ethanoic acid were heated with 46g of ethanol until equilibrium was
established, 12g of water and 58.7g of ethylethanoate were formed. Calculate;
(a) the equilibrium constant for the reaction
(b) the mass of ethylethanoate that would be formed under the same conditions if
90g of ethanoic acid and 92g of ethanol were heated.

(a)

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Initial moles 0 0
Moles reacted/ formed
Moles at equilibrium

[ ][ ]
[ ][ ]
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(b)

Initial moles 0 0
Moles reacted/
formed
Moles at equilibrium
[ ][ ]
[ ][ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. A 10.0 mixture initially contained 0.0515 moles of ethanol, 0.0525 moles of
ethanoic acid, 0.0314 moles of ester, 0.0167 moles of water and 0.001 moles of
hydrochloric acid. If at equilibrium 0.0255 moles of ethanoic acid were found.
Calculate the equilibrium constant for the reaction.
Hydrochloric acid is simply added to catalyse the reaction

Initial moles
Moles reacted/
formed
Moles at
equilibrium
[ ][ ]
[ ][ ]

3. 1 mole of ethanoic acid was mixed with 5 moles of ethanol in a sealed glass tube
left in a water bath at for some hours. The tube was then broken in cold
water and the resultant solution required 289 of 0.2 M sodium hydroxide for
complete neutralisation. Calculate the equilibrium constant, for the reaction.
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( )

Initial moles 0 0
Moles reacted/ formed

Moles at equilibrium

[ ][ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ][ ]

(b) Equilibria involving hydrogen, iodine and hydrogen iodide.

NOTE: All dissociations will be treated in terms involving degree of dissociation for
calculations.
The degree of dissociation is the fraction or percentage of the original
undissociated molecules which have dissociated.

Examples
1. (a) 3 moles of hydrogen and 1 mole of iodine were heated together in a sealed
tube at 500oC until equilibrium was established. Calculate the number of moles
of hydrogen iodide present in the equilibrium mixture at 500oC. (The equilibrium
constant , for the reaction between hydrogen and iodine is 50)
(b) Describe briefly how the concentration of iodine at equilibrium can be
obtained.

Initial moles 0
Moles reacted/formed
Moles at equilibrium
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[ ]
[ ][ ]

√ Moles of hydrogen iodide at equilibrium

(b) The tube is broken under an aqueous solution of potassium iodide to dissolve the iodine present
at equilibrium.
The resultant mixture is titrated with a standard solution of sodium thiosulphate using starch
indicator. The amount of iodine present at equilibrium is calculated using the equation below.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. (a) State three characteristics of a chemical equilibrium.
(b) 25 moles of hydrogen and 18 moles of iodine vapour were heated in a 1 litre
sealed tube at 465 oC. When equilibrium was attained, the tube was rapidly
cooled and found to contain 30.8 moles of hydrogen iodide.
(i) Give a reason why the tube was rapidly cooled.
(ii) Calculate the value of the equilibrium constant for the reaction taking
place in the flask and the degree of dissociation of hydrogen iodide.

(b) (i) Tube is rapidly cooled to stop the reaction and fix the equilibrium such that the
equilibrium does not adjust itself to the equilibrium value at a lower temperature.

Initial moles 0
Moles reacted/formed
Moles at equilibrium
[ ]
[ ][ ]
[ ]
[ ]
[ ]

Note that for the dissociation of HI is the reciprocal of for reaction between
hydrogen and iodine to form HI
For dissociation of hydrogen iodide,
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Initial moles 0 0
Moles dissociated/formed

Moles at equilibrium

Concentration at equilibrium
[ ][ ]
[ ]
( )

( )
√

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

3. When stoichiometric amounts of hydrogen and iodine were allowed to reach
equilibrium in a 1 litre vessel at 450 oC and , 1.56 moles of
hydrogen iodide were formed at equilibrium. Calculate the equilibrium constant
, .
Note that stoichiometric amounts mean amounts of moles as shown by the balanced equation

Initial moles 0
Moles reacted/formed
Moles at equilibrium

( )

( )

( )
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4. The equilibrium constant for the dissociation of hydrogen iodide is 0.02. 1 mole
of hydrogen and moles of iodine are heated together at 450 oC. Calculate the
mass of hydrogen iodide present in the equilibrium mixture at that temperature.

Initial moles 0
Moles reacted/formed
Moles at equilibrium

[ ]
[ ][ ] ( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

5. 1g of hydrogen and 127g of iodine are allowed to attain equilibrium in an

evacuated container of volume 10 at a temperature of 450 oC. If the
equilibrium constant at the same temperature, is 50. Calculate the;
(i) the value of
(ii) the total pressure in the container
(iii) the partial pressure of hydrogen in the container

(i)

Initial moles 0
Moles reacted/formed
Moles at equilibrium
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(ii)

[ ]
(iii)
[ ][ ]

( )

( )
√

6. 3.20g of hydrogen iodide were heated at 450 oC in a glass bulb of volume 800cm3.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

When equilibrium was attained, the bulb was rapidly cooled to room
temperature and then broken under a solution of potassium iodide. The iodine
formed required 36.0 cm3 of a 0.2M sodium thiosulphate solution in the presence
of starch indicator for complete reaction.
(i) Explain why the bulb broken under potassium iodide solution
(ii) Calculate the equilibrium constant for the reaction at 450 oC

(i) The bulb is broken under an aqueous solution of potassium iodide to dissolve
the iodine present at equilibrium.

(ii)

( )

( )

Initial moles 0 0
Moles dissociated/formed

Moles at equilibrium
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[ ] ( )

[ ] ( )
[ ][ ]
[ ] [ ]
( )
Note: The volume was given in .
Multiplying moles in 800 by 1000
converts the concentration to moles per litre
7. The degree of dissociation of 0.5 moles of hydrogen iodide was found to be 25%
at a certain temperature in a 1.5 vessel. Calculate the equilibrium
constant,

Initial moles 0 0
Moles dissociated/formed

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Moles at equilibrium

( )

( )

( )

(( ) )

(( ) )

(c) Equilibria involving hydrogen, nitrogen and ammonia.

Examples
1. Nitrogen reacts with hydrogen according to the following equation

(a) Write expression for equilibrium constant,

(b) Stoichiometric amounts of nitrogen and hydrogen were reacted in a 2 litre
vessel. At equilibrium, 0.8moles of ammonia was formed. Calculate:
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(i) the amount of hydrogen at equilibrium.

(ii) the value of equilibrium constant, .
[ ]
(a) ]
[ ][

Initial moles
Moles dissociated/formed
Moles at equilibrium
[ ] ( )

[ ] ( )
[ ]
[ ][ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ] ( )

2. 0.8 moles of nitrogen and 0.9 moles of hydrogen were heated in a 1500 closed
vessel. At equilibrium, the mixture contained 20% hydrogen. Find the value of
equilibrium constant, .

Initial moles
Moles dissociated/formed
Moles at equilibrium
[ ] ( )

( ) [ ] ( )

[ ] ( )
[ ]
[ ][ ]
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3. When 3 moles of hydrogen and 1 mole of nitrogen were mixed and allowed to
attain equilibrium at 100 atm and 400oC, the equilibrium mixture contained
25% of ammonia by volume. Calculate;
(i) Number of moles of nitrogen and hydrogen at equilibrium.
(ii) Value of at 400oC

Initial moles
Moles dissociated/formed
Moles at equilibrium

( ) ( )

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )
(ii) ( )
( )

4. Ammonia dissociates according to the following equation

Calculate the equilibrium constant, for the reaction given 3.0 moles of ammonia
were found to be 15% dissociated.

Initial moles
Moles dissociated/formed
( )
Moles at equilibrium

[ ]
[ ]
[ ]
[ ][ ]
[ ]
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5. 1.75 moles of ammonia were heated in a 1 litre vessel and the equilibrium
mixture was found to contain 42.9% hydrogen. Calculate the equilibrium
constant, .

Initial moles
Moles dissociated/formed
( )
Moles at equilibrium

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ] [ ]
[ ]
[ ][ ]
[ ]

(d) Equilibria involving phosphorus, chlorine and phosphorus(V) chloride

Examples
1. Phosphorus(V) chloride dissociates at high temperatures according to the
equation

83.4 g of phosphorus(V) chloride were placed in a vessel of 9.23 .At equilibrium

at a certain temperature, 11.1g of chlorine were formed at a total pressure of
.
(a) Calculate the number of moles of phosphorus(V) chloride and chlorine in the
vessel at equilibrium.
(b) Determine the equilibrium constant, , for the reaction and state its units.
(c) Calculate the value of the equilibrium constant, , for the reaction and state
its units.
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(a)

Initial moles
Moles dissociated/formed
Moles at equilibrium

[ ] ( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ] ( )
[ ]
[ ][ ]
(b) [ ]

(c)
( )

( )

( )

2. 1.0 mole of phosphorus(V) chloride was strongly heated in a one litre closed
bulb until equilibrium was obtained. The glass bulb was then rapidly broken
under potassium iodide solution. The bulb was found to contain 40.70% of
chlorine.
(a) Write equations for the reactions that took place when:
(i) the glass bulb was strongly heated
(ii) the glass bulb was broken under potassium iodide solution.
(b) State the reasons why the bulb;
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(i) was rapidly broken

(ii) was broken under potassium iodide solution
(c) Determine the;
(i) degree of dissociation of phosphorus(V) chloride
(ii) equilibrium constant for the reaction.

(a) (i)
(ii)
(b) (i) Bulb was rapidly broken to stop the reaction and fix the equilibrium such that
the equilibrium does not adjust itself to the equilibrium value at a lower
temperature.
(ii) Bulb is broken under potassium iodide to dissolve and oxidise chlorine
present at equilibrium to chloride ions as the potassium iodide is reduced to
iodine.
(c) (i)

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Initial moles
Moles dissociated/formed
Moles at equilibrium

[ ]
[ ]
[ ][ ]
[ ]

[ ]

3. 2.085g of phosphorus(V) chloride was heated in a 1 litre vessel until equilibrium

was attained. The vessel was then broken under excess potassium iodide
solution. The iodine liberated required 40 of 0.1M sodium thiosulphate
solution. Calculate the equilibrium constant, , for the reaction.
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( )

( )

Initial moles
Moles dissociated/formed
Moles at equilibrium

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ]
[ ]
[ ][ ]
[ ]

[ ]

4. 2.00 g of phosphorus(V) chloride were allowed to reach equilibrium at 200oC in

a capacity vessel. If the equilibrium constant of the above reaction is
at this temperature and in the conditions stated. Calculate the
percentage dissociation of phosphorus pentachloride at equilibrium.

Initial moles
Moles dissociated/formed
Moles at equilibrium
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[ ]
[ ] √
[ ]
[ ][ ]
[ ]

5. 3.6 moles of phosphorus(V) chloride in a vessel of volume 2 litres was found to

be 38% dissociated. Calculate the equilibrium constant, , for the reaction.

Initial moles
Moles dissociated/formed

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Moles at equilibrium

[ ] ( )
[ ] ( )
[ ]
[ ][ ]
[ ]

6. Calculate the percentage of chlorine is the equilibrium mixture formed when 0.4
moles of phosphorus(V) chloride were heated in a one litre
vessel .

Initial moles
Moles dissociated/formed
Moles at equilibrium
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[ ]
[ ] √
[ ]
[ ][ ]
[ ]

( )

(e) Equilibria involving sulphur trioxide, sulphur dioxide and oxygen

Examples
1. At 700ºC, and total pressure of 1.0 atm, the partial pressure at equilibrium for

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

sulphur dioxide and oxygen are 0.27 and 0.41 atm respectively. Calculate the
equilibrium constant, for the reaction.

( )
( )

2. 0.425 moles of sulphur dioxide and 0.294 moles of oxygen were heated in a 1.6
litre vessel and at equilibrium, it was found that 52% of oxygen had reacted.
Calculate the value of equilibrium constant, .

Initial moles
Moles reacted/formed
Moles at equilibrium

[ ] ( )
[ ] ( )
[ ] ( )
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[ ]
[ ] [ ]

3. 1 mole of sulphur trioxide was introduced into a vessel. The vessel was
heated to 1000K until equilibrium was attained. At equilibrium, 0.35 moles of
sulphur trioxide was present.
(i) Write equation for the dissociation of sulphur trioxide.
(ii) Write an expression for the equilibrium constant, .
(iii) Calculate the value of .

(i)
[ ] [ ]
(ii)

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ]
Initial moles
Moles dissociated/formed

Moles at equilibrium

[ ] [ ]
[ ]
[ ] [ ]
[ ]

(f) Examples involving other equilibria systems

1. Dinitrogen tetroxide and nitrogen dioxide exist in the following equilibrium.

When 11.04g of dinitrogen tetroxide were placed in a vessel of volume at a

fixed temperature, 5.52g of nitrogen dioxide were produced at equilibrium under a
pressure of 100kPa. Calculate the:
(a) equilibrium number of moles of each gas
(b) equilibrium constant, .
(c) equilibrium constant,
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(a)

Initial moles
Moles dissociated/formed
Moles at equilibrium
(b) [ ]
[ ]
[ ]
[ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(c) ( )

2. For the following gas equilibrium, at 333K, the

equilibrium constant, is 1.33 atmospheres. Calculate the degree of
dissociation of one mole of dinitrogen tetraoxide at 333K if the total pressure of
the system is 2 atmospheres.

Initial moles
Moles dissociated/formed
Moles at equilibrium
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( ) ( )

( )

( )

3. When heated, carbon dioxide dissociates according to the equation:

If at a certain temperature and a pressure of one atmosphere, 60% of the original

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

carbon dioxide remained undissociated. Calculate the equilibrium constant for
the reaction.

Initial moles
Moles dissociated/formed

Moles at equilibrium

( )

( )

4. Nitrogen monoxide reacts with oxygen according to the reaction:

At equilibrium, the equilibrium constant is at a given temperature in

a container of volume, . The equilibrium mixture was found to contain
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0.0148 moles of oxygen. Calculate the ratio of [ ] to [ ] in the equilibrium

mixture.

Moles at equilibrium ?

[ ]
[ ] ( )
[ ]
[ ] [ ] [ ]
√
[ ]
[ ] [ ]
[ ] [ ] [ ]
[ ] [ ]
[ ]
[ ] [ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

5. For the equilibrium system below:

(a) Write the expression for the equilibrium constant, .

(b) When 1 mole of steam and 1 mole of carbon monoxide are allowed to reach
equilibrium, 33.3% of the equilibrium mixture is hydrogen. Calculate the
value of and state its units.

Initial moles
Moles reacted/formed
Moles at equilibrium

Let the total pressure be P |

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6. Methane reacts with steam according to the equation

When 0.18 moles of methane and 0.22 moles of steam were heated in a 5 litre vessel,
0.1 mole of carbon dioxide was found to be present at equilibrium. Calculate the
value of .

Initial moles
Moles reacted/formed
Moles at equilibrium

[ ] ( )
[ ] ( )
[ ] ( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ] ( )
[ ][ ]
[ ][ ]

7. Sulphoryl dichloride dissociates when heated according to the following

equation:
When 67.5g of Sulphoryl dichloride was heated in a 1 litre vessel at 120ºC and 3.6
atmospheres, it was found that at equilibrium, 45% of it had dissociated.
(i) Write the expression for the equilibrium constant, .
(ii) Calculate the number of moles of each substance present at equilibrium.
(iii) Calculate the equilibrium constant, .

(i)

(ii)

Initial moles
Moles dissociated/formed
Moles at equilibrium
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(iii)
[ ]
[ ]
[ ]
[ ][ ]
[ ]

8. The equilibrium constant, for the reaction below at ℃ is

:

Calculate the:

(i) total pressure of the system at equilibrium.

(ii) degree of dissociation of ammonium hydrogen sulphide

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Initial moles
Moles dissociated/formed
Moles at equilibrium
( )
√

Let the total pressure at equilibrium be P

From

Since
( )

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General questions involving calculations on chemical equilibria

1. When 3.12g of ethanoic acid and 2.07g of ethanol were reacted in a 1 litre closed
vessel at 50ºC. 0.36g of water was found at equilibrium. Calculate the value of
equilibrium constant for the reaction, .
2. When 8.28g of ethanol were heated with 60g of ethanoic acid, 49.74g of the acid
remained at equilibrium. Calculate the;
(i) value of the equilibrium constant, .
(ii) mass of ester present in the equilibrium mixture formed from 13.8g of ethanol
and 12g of ethanoic acid.
3. When equimolar quantities of ethanoic acid and ethanol were heated, one third of
each reactant remained at equilibrium. Calculate the equilibrium constant for the
reaction
4. 1 mole of ethanol was reacted with 2 moles of ethanoic acid at ℃. If the
equilibrium constant for the reaction at the same temperature is 4. Calculate the mass
of ethylethanoate in the equilibrium mixture.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

5. 5moles of ethanol, 6 moles of ethanoic acid, 6 moles of ethylethanoate and 4moles of
water were mixed together in a stoppered bottle at 15℃. At equilibrium, the bottle
was found to contain 4 moles of ethanoic acid.
(a) (i) Write an equation for the reaction between ethanol and ethanoic acid to form
ethylethanoate and water.
(ii) Suggest a mechanism for the reaction
(b) Write an expression for the equilibrium constant, for this reaction
(c) Determine the number of moles of ethanol, ethylethanoate and water present in
the equilibrium mixture hence the value of for this reaction
(d) If 1moleof ethanol, 1mole of ethanoic acid, 3 moles of ethylethanoate and 3 moles
of water are mixed together in a stoppered flask at 15℃. Determine the number of
moles of each compound present in the equilibrium mixture.
6. 3.0g of ethanoic acid and 2.3g of ethanol were equilibrated at 100℃ for an hour and
then quickly cooled in an ice bath. 50 of 1.0 M sodium hydroxide solution were
added. When the mixture was titrated with 1.0M hydrochloric acid, 33.3 of the
acid were required for complete reaction.
(a) Explain why the mixture was cooled in an ice bath.
(b) Calculate the equilibrium constant, for the reaction.
7. 4.6g of ethanol and 12.0g of ethanoic acid were mixed in a stoppered flask with
20 of 1M hydrochloric acid as catalyst at 20℃. The mixture was left for a week to
attain equilibrium, and then titrated with 137 of 1.0M sodium hydroxide. (Of the
total volume of base used, only 20 were used to react with hydrochloric acid)
(a)Work out the concentrations of the equilibrium mixture
(b) Calculate the value of equilibrium constant, .
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8. When 60g of ethanoic acid and 46g of ethanol were made to react to equilibrium at
100ºC, the percentage of esterification was
(i) Write equation for the esterification reaction.
(ii) Calculate the value of the concentration equilibrium constant, .
(iii) Outline the mechanism for the reaction between ethanoic acid and ethanol.
9. When 6.22 of hydrogen were heated with 5.71 of iodine in a sealed tube at
o
356 C, it was found out that 9.60 of hydrogen iodide were present at
equilibrium. Calculate the:
(i) equilibrium constant
(ii) volume of hydrogen iodide in the equilibrium mixture formed by reacting
together 6.41 of hydrogen and 10.40 of iodine at 356 oC.
( Hint: Number of moles of a gas is directly proportional to volume)
10. A mixture of 0.8 mole of hydrogen and 0.6 mole of iodine was allowed to react in a
sealed tube at 450ºC. At equilibrium, 0.2 mole of iodine had reacted.
(i) Write an expression for the equilibrium constant, , for the reaction

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(ii) Calculate the value of , at 450ºC.
11. Hydrogen reacts with iodine according to the equation

(a) Calculate the equilibrium concentration of each of the following when:

(i) 0.2 mole of iodine and 0.3 moles of hydrogen are reacted in a one litre
vessel.
(ii) 0.5 mole of iodine and 0.8 mole of hydrogen are reacted in a 4 litre vessel

(b) Equimolar quantities of hydrogen and iodine were heated in a 1 litre vessel until
equilibrium was attained. The equilibrium mixture was found to contain 20.5%
hydrogen iodide Determine the equilibrium constant, .
12. (a) State the law of mass action
(b) Explain what is meant by the following terms:
(i) equilibrium constant
(ii) dynamic equilibrium
(c) Describe an experiment to determine the equilibrium constant for the reaction
between hydrogen and iodine
(d) 1.54g of hydrogen iodide were heated in a 600cm3 bulb at 530 oC. When equilibrium
was attained, the bulb was rapidly cooled to room temperature and broken under
potassium iodide solution. The iodine formed required 67 cm3 of 0.1M sodium
thiosulphate solution for complete reaction. Calculate ;
(i) Number of moles of hydrogen iodide in 1.54g
(ii) Number of moles of iodine formed
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(iii) Value of at 530 oC

13. 1.0g of hydrogen iodide was heated to a certain temperature in a sealed vessel and the
products rapidly cooled. The iodine which had been liberated required 15.0 of
0.1M sodium thiosulphate for complete reaction. Calculate the percentage by mass of
hydrogen iodide which remained undissociated at that temperature.
14. (a) 3.4 moles of hydrogen iodide at 460ºC are found to be 20% dissociated. Calculate
the:
(i) number of moles of hydrogen iodide, hydrogen and iodine formed at
equilibrium
(ii) equilibrium constant for the dissociation reaction.
(b) A mixture containing 28 moles of hydrogen and 22 moles of iodine was heated in
a sealed tube at 460 ºC until equilibrium was attained and 36 moles of hydrogen
iodide was obtained. Calculate the degree of dissociation of hydrogen iodide at
460ºC
15. (a)The equilibrium constant for the dissociation of hydrogen iodide into hydrogen and

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

iodine is 0.02. Calculate the equilibrium composition of the following if they are
heated.
(i) 0.05 mole of hydrogen iodide.
(ii) 0.2 mole of hydrogen iodide.
(b) When 0.4 mole of hydrogen iodide was heated to equilibrium, it dissociated.
Determine the degree of dissociation of hydrogen iodide, given that the
equilibrium constant is 0.025
16. (a) 1 mole of hydrogen iodide gas at 25 was introduced into a container of volume
20 litres. Calculate the pressure of the gas assuming ideal behaviour.( 1 mole of an
ideal gas occupies 22.4 litres under standard conditions)
(b) The sample of hydrogen iodide, considered above was raised to a temperature of
300 and it partially dissociated into hydrogen and iodine. At equilibrium, 1 mole of
iodine was found to be present.
(i) Write an equation for the dissociation
(ii) Calculate the pressure of the equilibrium mixture at 300 assuming no change in
volume.
(iii) Calculate the equilibrium constant at 300
17. Derive an expression for the equilibrium constant for the reaction;

in terms of and , where and are the original number of moles of hydrogen
and nitrogen respectively, and is the number of moles of nitrogen which react at a total
pressure of Pa.
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18. When 0.2 moles and 0.47 moles of nitrogen and hydrogen respectively were heated to
equilibrium in a 1 litre vessel, 0.18 moles of ammonia were formed. Calculate the
equilibrium constant, .
19. When 1.65 moles of hydrogen and 0.6 moles of nitrogen were heated to 150ºC in a
1.5 litre closed vessel, equilibrium was attained when 0.9 moles of ammonia were
formed. Calculate the value of equilibrium constant, for the reaction.
20. Nitrogen and hydrogen are mixed in a ratio 1:3. At equilibrium at 600OC and 10
atmospheres, the percentage of ammonia in the mixture of gases is 15%
(a) Write equation for the reaction
(b) Write an expression for the equilibrium constant.
(c) Calculate the equilibrium constant at that temperature and state its units.
21. Stoichiometric amounts of hydrogen and nitrogen were reacted at 50 atm. At
equilibrium, 0.8 moles of ammonia were formed. Calculate:
(i) Amount of hydrogen and nitrogen present at equilibrium

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(ii) Value of the equilibrium constant
22. (a) For the reaction,

Calculate the molar percentage of ammonia in the equilibrium mixture formed at

o 7
400 C and at a pressure of 3 × 10 Pa, when gaseous hydrogen and nitrogen are mixed in
a 3:1 ratio and there is 61% conversion of nitrogen to ammonia.
(b) (i) Determine the equilibrium constant, of the reaction.
(ii) Given that the value of at a given temperature is ,
calculate the pressure at which ammonia is 95% dissociated into its elements
at that temperature.
23. (a) Write equation for the reaction leading to formation of ammonia
(b) The value of the pressure equilibrium constant, for the reaction in (a) above is
at 500℃ . Calculate the percentage of a 1:3 mixture of
nitrogen and hydrogen that would be converted to ammonia at 500 atmospheres.
24. (a) Write an equation for the reaction between hydrogen and nitrogen.
(b) At 500 oC, the equilibrium concentration of hydrogen is 0.250 moll-1 and that of
nitrogen is 2.7 moll-1 Calculate the equilibrium concentration of ammonia at the same
temperature given that at 500 oC.
25. When nitrogen was reacted with hydrogen at 690K, the total pressure of the system at
equilibrium was 32 atmospheres and the partial pressures of hydrogen and nitrogen
were 8 and 3 atmospheres respectively. Calculate the:
(i) partial pressure of ammonia in equilibrium mixture.
(ii) equilibrium constant for the reaction
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26. At a certain temperature, the equilibrium constant for the reaction between nitrogen
and hydrogen, , is and the partial pressures of nitrogen and
hydrogen are 30 and 120 atm respectively.
(i) Write the expression for the equilibrium constant, .
(ii) Calculate the partial pressure of ammonia at equilibrium.
27. When 80.4 g of phosphorus(V) chloride were placed in a 9.0 litre vessel and heated
at a certain pressure, 8.4 g of chlorine were formed at equilibrium. Calculate the:
(i) amount of phosphorus(V) chloride and phosphorus(III) chloride at
equilibrium in moles per litre.
(ii) equilibrium constant, , for the reaction and state its units.
28. (a) When 2.6 mole of phosphorus(V) chloride was heated in a 1.5 vessel,
equilibrium was established when 1.04 mole of phosphorus(III) chloride was formed.
Calculate the value of equilibrium constant, .
(b) 3.0 mole of phosphorus pentachloride was heated in a 1 litre vessel and when
equilibrium was attained, it was found to contain 1.14 mole of chlorine gas.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Determine the value of equilibrium constant, .
29. 75.06g of phosphorus(V) chloride were heated to 200ºC in a vessel of volume
1000 at a pressure of 170kPa. Calculate the;
(a) degree of dissociation of phosphorus(V) chloride
(b) value of equilibrium constant, , at 200ºC
30. 0.2 moles of phosphorus pentachloride were heated at 500K in 5 litre flask. At
equilibrium, 60% of phosphorus pentachloride was found to have dissociated and the
total pressure was found to be 300mmHg.
(a) Calculate the equilibrium constant, .
(b) What will be the total pressure if phosphorus pentachloride dissociated only by
35%
31. When 2.4 moles of phosphorus pentachloride were heated in a 1.5 vessel and at
equilibrium, it was found to contain 23.53% phosphorus trichloride.
(a) Write equation for the dissociation of phosphorus pentachloride
(b) Write the expression for the equilibrium constants, , and , for the reaction.
(c) Determine the value of equilibrium constant, .
32. (a) 2.6 mole of phosphorus pentachloride was heated in a 500 closed vessel. At
equilibrium, it was found to contain 1.04 mole of phosphorus trichloride. Determine
the value of equilibrium constant, .
(b) 3.0 mole of phosphorus pentachloride was heated in a 750 vessel until
equilibrium was established. The vessel contained 1.14 moles of chlorine.
Determine the value of equilibrium constant, .
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33. Determine the mass of each of the components of the equilibrium mixture formed
when 0.52 moles of phosphorus(V) chloride is heated at equilibrium.

34. 0.04 moles of sulphur trioxide were allowed to dissociate at 900K in a flask of volume
3.04 litres. At equilibrium, 0.0289 moles of sulphur trioxide were found to be present.
(i) Derive the relationship between and for this reaction. Show clearly how
you arrive at your answer.
(ii) Calculate equilibrium constants and .
35. At 700℃ and total pressure of one atmosphere, the partial pressures at equilibrium for
sulphur dioxide and oxygen are 0.27 and 0.41 atmospheres respectively. Sulphur
dioxide is oxidized to sulphur trioxide according to the following equation:

Calculate the equilibrium constant, , for the reaction

36. When 0.6 and 0.425 moles of sulphur dioxide and oxygen respectively were reacted
in a 1litre vessel to equilibrium, the equilibrium mixture contained 18.75% sulphur

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

dioxide. Calculate the equilibrium constant value, .
37. Dinitrogen tetraoxide dissociates at 40 oC and 1 atm according to the following
equation.

(i) Write an equation for the equilibrium constant , .

(ii) Draw a well labelled energy level diagram for the reaction in (i) above
(iii) The reaction mixture of the reaction was found to contain 60% by volume of
nitrogen dioxide at equilibrium. Calculate the equilibrium constant at 40
o
C for the reaction.
38. (a) At 40℃ and under a pressure of 1 atmosphere, dinitrogen tetraoxide contains 60%
by volume of nitrogen dioxide molecules. Calculate the percentage dissociation of
dinitrogen tetraoxide and equilibrium constant in terms of the partial pressures of the
two gases.
(b) Deduce the:
(ii) percentage dissociation of dinitrogen tetraoxide at the same temperature
when the gases are under a pressure of 6 atm.
(iii) the pressure at which dinitrogen tetraoxide would be dissociated to an
extent of 80% at the same temperature.
39. 1 mole of dinitrogen tetra oxide was allowed to dissociate to nitrogen dioxide in a 5
litre flask at 50℃. At equilibrium one mole of nitrogen dioxide was found to be
present. Calculate equilibrium constant for the reaction.
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40. Propene reacts with steam according to the following equation.

At a certain temperature and total pressure of 197.38 atmospheres, the equilibrium partial
pressures of propene and steam are 74.02 and 93.76 atmospheres respectively. Calculate
the value of at this temperature and state its units.
41. Nitrogen monoxide combines with oxygen according to the equation

A closed vessel of 500 containing 0.33 moles of nitrogen monoxide and 0.355 moles
of oxygen was heated. Equilibrium was established when 0.105 moles of oxygen had
reacted. Calculate the value of .
42. Carbon monoxide reacts with steam according to the reaction;

When of carbon monoxide were heated with of steam at ℃ until

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

equilibrium, of carbon dioxide was formed. Calculate the;
(a) volume of carbon monoxide and steam left at equilibrium.
(b) equilibrium constant, .
43. At ℃, the equilibrium constant for the reaction
is 1.4. Calculate the percentage by
volume of the gases in the equilibrium mixture at the same temperature when one
volume of carbon monoxide and two volumes of steam are mixed.
44. Sulphur dioxide dichloride dissociates when heated according to the equation:

When 1.33 moles of sulphur dioxide dichloride were heated in a 2 litre vessel,
equilibrium mixture contained 5.98% sulphur dioxide dichloride. Calculate the value of
equilibrium constant, .
45. Ammonium hydrogen sulphide was allowed to dissociated into ammonia and
hydrogen sulphide gases at 500 . At equilibrium the total pressure was measured and
found to be 0.6 atm. Calculate the:
(i) partial pressure of each gas at equilibrium.
(ii) pressure equilibrium constant

Determining equilibrium constants using partition coefficients

Iodine reacts with potassium iodide to form potassium triiodide according to the
equation;

The equilibrium constant for the above reaction is given by the expression below and is
measured by partition method.
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[ ]
[ ][ ]
A known mass of iodine is dissolved in a standard solution of potassium iodide and the
resultant mixture shaken with trichloromethane or trichloromethane or benzene or carbon
disulphide. Some iodine forms a complex with potassium iodide according to the above
equation and some iodine remains free in the solution. The free iodine then distributes
itself between the aqueous layer and the organic solvent used.
Aqueous layer

Trichloromethane layer
The concentration of iodine in the organic layer is obtained by titrating a portion of a
known volume of it with standard sodium thiosulphate solution.
The concentration of free iodine in the aqueous layer is then got from the expression
below, if the partition coefficient value is known;

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ]
[ ]
[ ] [ ] [ ]
The total concentration of iodine in the aqueous layer, [ ] is obtained by titrating a
portion of a known volume of it with standard sodium thiosulphate solution.
[ ] [ ] [ ]
Since [ ] is known, then [ ] can be obtained.
The total iodide ion concentration in the aqueous layer is obtained from the concentration
of potassium iodide used.
[ ] [ ] [ ]
Since [ ] is known, then[ ] can be obtained and the value of then
determined.
Example
4g of potassium iodide was dissolved in 500 of water and about 1g of iodine was
dissolved in 100 of benzene. The two solutions were then mixed and allowed to
stand. 10 of the benzene layer required 5.1 of 0.1M sodium thiosulphate
solution while 50 of the aqueous layer required 2.9 of 0.1M sodium
thiosulphate solution for complete reaction. The distribution coefficient of iodine
between benzene and water is 130. Calculate the value of the equilibrium constant
for the reaction:
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( )

( )
[ ]
[ ]
[ ]
[ ]

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )
[ ]
[ ] [ ] [ ]
[ ] [ ]
[ ]

( )
[ ] [ ] [ ]
[ ]
[ ]
[ ][ ]
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Questions
1. A solution containing 12.7g of iodine and 166.1g of potassium iodide in 1 litre of
water was shaken with 1 litre of benzene. If the partition coefficient of iodine between
benzene and water is 400 and the equilibrium constant for the reaction:
is 730. Calculate the concentration of:
(i) iodine in benzene
(ii) triiodide ions in water
Compare concentration equilibrium constant, and pressure equilibrium
constant,

Concentration equilibrium constant, Pressure equilibrium constant,

It can be measured for any reversible reaction Measured for only reversible reactions involving
gases
Expressed in terms of molar concentrations Expressed in terms of partial pressures
N.B The two equilibrium constants are always the same value at a given temperature for equilibria
where

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(
)

Interpretation of magnitude of or in relation to equilibrium

position
Consider the reversible reaction,
The proportion of products to reactants in the equilibrium mixture is described as the
position of the equilibrium.
The magnitude of the equilibrium constant, or indicates the extent to which a
reaction will proceed and the position of the equilibrium.

When or is small (k<1), it implies that the conversion of A and B into C and D is
small and the position of the equilibrium lies to the left.
When or is large(k>1), it implies that the equilibrium mixture is largely
composed of C and D is small and the position of the equilibrium lies to the right.
If K is about 1, the equilibrium is reached at some intermediate mixture.

Comparing the reaction quotient (Q) and to determine direction

of a chemical reaction
The reaction quotient( ) is defined as the ratio of the molar concentrations of the
product species over those of the reactant species involved in the chemical reaction,
taking stoichiometric coefficients of the reaction into account as powers of the
concentrations.
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The reaction quotient, Q, has the same mathematical form as the equilibrium-constant
expression, but Q is a ratio of the actual concentrations (not a ratio of equilibrium
concentrations).

For a given reaction,

The reaction quotient is given as;
[ ] [ ]
[ ] [ ]
 At equilibrium, Q , and this is defined as the equilibrium condition.
 If Q, the backward reaction is favoured, the reaction moves from right to left,
until equilibrium is established.
 If Q, the forward reaction is favoured, the reaction moves from left to right,
until equilibrium is established.
Examples
1. In the water–gas shift reaction, carbon monoxide produced by steam-reforming

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

reaction of methane reacts with steam at elevated temperatures to produce more
hydrogen:

If at 900 K and 0.010 moles of carbon monoxide and 0.010 moles of

water, 0.0080 moles of carbon dioxide, and 0.012 moles of hydrogen are injected into
a 4.0 litre reactor and heated to 900 K, will the reaction proceed to the left or to the
right ?
[ ] [ ]
[ ]
[ ] [ ]
[ ]

[ ]
, the reaction proceeds
[ ] from right to left, until equilibrium is
established.

2. Consider the following reversible reaction; .

At a certain temperature, the partial pressure were measured and found to be
for sulphur trioxide, for sulphur dioxide and for
oxygen. Predict the direction in which the reaction should proceed in order to
attain equilibrium.
( )
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( ) , the reaction proceeds

from right to left, until equilibrium is
( ) established.

Questions
1. For the reaction: , the equilibrium constant, , is
at 1500 K. Predict the direction the reaction will move in if the reactants
and products have the following concentrations: [ ] [ ]
, and [ ] .
2. For the reaction: , the equilibrium constant, , is
at 100°C. Predict the direction the reaction will move in if the
concentration of is and the concentration of is
3
3. 1 mole of Sulphur trioxide was introduced into a 1 dm vessel. The vessel was heated

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

to 1000K until equilibrium was attained. At equilibrium, 0.35 mole of Sulphur
trioxide was present.
(a) Write:
(i) equation for the decomposition of Sulphur trioxide
(ii) an expression for the equilibrium constant,
(b) Calculate the value of .
(c) 0.2 mole of Sulphur dioxide, 0.1 mole of oxygen and 0.7 mole of Sulphur
trioxide, were introduced into the vessel in (a) at 1000K. Calculate the new
value for the reaction.
(d) Using your answers in (b) and (c) above, state how the position of the equilibrium
was affected.

L ́ CHATELIER’S PRINCIPLE AND THE EFFECTS OF

VARIOUS FACTORS ON THE EQUILIBRIUM OF
REVERSIBLE CHEMICAL REACTIONS
L ́ Chatelier's Principle
The principle states that if a system in equilibrium is subjected to any change, the
equilibrium will shift if possible, to a direction which causes an opposite change.
or
If a system in equilibrium is subjected to a constraint, that change takes place which
tends to remove the constraint
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The system cannot completely cancel the change in the external factor, but it will move in
a direction that will minimize the change.
The external factor may be pressure, temperature, concentration, adding a noble gas
or a catalyst.
(a) Effect of pressure
Since pressure has a negligible effect on the volumes of solids and liquids, it only affects
reactions in which gases are involved.
Any reaction that occurs with an increase in volume is favoured by a decrease in
pressure.
A reaction that occurs with a decrease in volume is favoured by an increase in pressure.
Any change in pressure of the system changes the position of the equilibrium and the
rate of attainment of the equilibrium but has no effect on the equilibrium constant.
Sample questions

1. Nitrogen and hydrogen react according to the equation

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Explain how the position of the equilibrium, value of the equilibrium constant and
the rate of attainment of equilibrium would be affected if ;
(i) the pressure was decreased
Note that

There forward reaction occurs by a reduction in volume, hence favoured by an increase

in pressure.
A decrease in pressure shifts equilibrium from right to left since backward reaction
occurs by an increase in volume. Ammonia dissociates to form nitrogen and hydrogen,
keeping the equilibrium constant value unchanged. Rate of attainment of equilibrium
decreases because there are fewer gas molecules in a given volume, molecules are far
apart hence there are fewer chances of successful collisions between particles.

(ii) the pressure was increased

Increase in pressure shifts equilibrium from left to right since forward reaction occurs
by a decrease in volume. Nitrogen will react with hydrogen to form ammonia so as to
keep the equilibrium constant value unchanged. Rate of attainment of equilibrium
increases because there are more gas molecules in a given volume, molecules are closer
together hence there are more chances of successful collisions between particles.
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2. When hydrogen iodide is heated it decomposes according to the equation

Explain how the position of the equilibrium, value of the equilibrium constant and
the rate of attainment of equilibrium would be affected if the pressure of the
reaction was increased
Note that

Increase in pressure has no effect on position of equilibrium since both forward and
backward reactions proceed with no change in volume. Equilibrium constant remains
unchanged but the rate of attainment of equilibrium increases because there are more
gas molecules in a given volume, molecules are closer together hence there are more
chances of successful collisions between particles.

(b) Effect of concentration

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Increasing concentration of any reagent in an equilibrium mixture shifts the equilibrium
in the direction that converts some of the reagent into other products.

Addition of a reagent that reacts with one of the reactants/products, reduces the
concentration of the reactant/product in an equilibrium mixture and shifts the equilibrium
in the direction to which the reactant/ product is removed so that it is replaced.

Any change in concentration of one of the species in an equilibrium mixture changes the
position of the equilibrium and the rate of attainment of the equilibrium but has no
effect on the equilibrium constant.

Sample question

1. Sulphur dioxide reacts with oxygen according to the equation;

Explain how the position of the equilibrium, value of the equilibrium constant and
the rate of attainment of equilibrium would be affected if;
(i) more Sulphur dioxide was added
The concentration of sulphur dioxide increases and the excess sulphur dioxide reacts
with oxygen to produce sulphur trioxide, so as to keep the equilibrium constant value
the same. Equilibrium therefore shifts from left to right and equilibrium constant value
remains unchanged. The rate of attainment of equilibrium increases since there is an
increase in the number of particles in the reaction vessel.
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(ii) Sulphur trioxide was added.

The concentration of sulphur trioxide increases and the excess sulphur trioxide
dissociates to produce sulphur dioxide and oxygen, so as to keep the equilibrium
constant value the same. Equilibrium therefore shifts from right to left and equilibrium
constant value remains unchanged. The rate of attainment of equilibrium increases
since there is an increase in the number of particles in the reaction vessel.

(iii) Removing the Sulphur trioxide formed

Removing sulphur trioxide makes the sulphur dioxide to react with oxygen so as to
replace sulphur trioxide removed, keeping the equilibrium constant value unchanged.
Equilibrium therefore shifts from left to right. The rate of attainment of equilibrium
reduces since there is a reduction in the number of particles in the reaction vessel.

(c) Effect of temperature.

The effect of temperature on an equilibrium depends on whether the reaction is

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

endothermic ( or exothermic ( .
If the reaction is endothermic, increase in temperature favours it
If the reaction is exothermic, then it is favoured by lowering temperature.
Any change in temperature changes the position of the equilibrium, rate of attainment
of the equilibrium and also the value of the equilibrium constant.
Among all the factors, it is only temperature that affects the value of the equilibrium
constant.
For an exothermic reaction, increase in temperature favours backward reaction,
reducing the equilibrium constant value.
For an endothermic reaction, increase in temperature favours forward reaction,
increasing the equilibrium constant value.
Sample question
1. Ammonia is formed from nitrogen and hydrogen at 25°C and 10 atm.

Explain how the position of the equilibrium, value of the equilibrium constant and
the rate of attainment of equilibrium would be affected if the reaction is carried out
at a temperature of 250°C, while the pressure remains at 10 atm.
Since forward reaction is exothermic, increase in temperature from 25°C to 250°C will
make equilibrium shift from right to left, favouring the backward reaction which is
endothermic. The ammonia dissociates to form nitrogen and hydrogen according to L ́
Chatelier's Principle. This reduces the concentration of ammonia but increases the
concentrations of nitrogen and hydrogen, reducing the equilibrium constant.
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The rate of attainment of equilibrium increases because increase in temperature will

increase both the forward reaction rate and the reverse reaction rate and the collision
frequency between colliding particles.

2. Nitrogen reacts with oxygen according to the following equation

Explain how the position of the equilibrium, value of the equilibrium constant and
the rate of attainment of equilibrium would be affected if;
(i) the temperature was increased.
Increase in temperature will make equilibrium shift from left to right, favouring the
forward reaction which is endothermic. The nitrogen reacts with oxygen to form
nitrogen monoxide according to L ́ Chatelier's Principle. This reduces the
concentration of nitrogen and oxygen but increases the concentration of nitrogen
monoxide, increasing the equilibrium constant.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The rate of attainment of equilibrium increases because increase in temperature will
increase both the forward reaction rate and the reverse reaction rate the collision
frequency between colliding particles.

(ii) the temperature was decreased.

Decrease in temperature will make equilibrium shift from right to left, favouring the
backward reaction which is exothermic. The nitrogen monoxide dissociates to form
oxygen and nitrogen according to L ́ Chatelier's Principle. This increases the
concentration of nitrogen and oxygen but decreases the concentration of nitrogen
monoxide, reducing the equilibrium constant.
The rate of attainment of equilibrium decreases because decrease in temperature will
reduce the collision frequency between colliding particles.

(d) Effect of adding a noble gas

Addition of an inert gas for example argon to an equilibrium system does not affect the
equilibrium constant.
The noble gas effect can be investigated under two conditions i.e. constant volume
(where total pressure of the system increases) and at constant pressure( where the total
volume of the system increases).
When heated, carbon dioxide decomposes according to the equation:

Explain the effect on the equilibrium position and equilibrium constant and the rate
of attainment of equilibrium when;
(i) argon is added to the equilibrium at constant volume
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Argon being a noble gas, when added, the total pressure of the system increases, but
there is no change in partial pressure/ concentrations of the reactants and products.
The position of the equilibrium is not affected.
Since the concentration of argon does not apply in the or expression, the
equilibrium constant also remains unchanged.
The rate of attainment of equilibrium reduces since some of the particles on collision
do not react.
N.B Hence, when an inert gas is added to the system in equilibrium at constant
volume there will be no effect on the equilibrium position or equilibrium constant
but reduces the rate of attainment of equilibrium.
(ii) neon is added to the equilibrium at constant pressure
Neon being a noble gas, when added to the system at constant pressure, leads to an
increase in the total volume. As a result, partial pressures/ concentrations of the
reactants and products decrease. According to Le Chatelier's Principle, the equilibrium

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will be shifted from left to right (in that direction where there is an increase in number
of moles). The equilibrium constant remains unchanged since the partial
pressure/concentration of neon does not apply in the equilibrium constant expression.
The rate of attainment of equilibrium reduces as some of the particles on collision do
not react.
N.B Hence, when an inert gas is added to the system in equilibrium at constant
pressure, there will be a shift of the equilibrium position to a direction where the
number of moles increases, no effect on equilibrium constant but reduces the rate of
attainment of equilibrium.
(e) Effect of adding a catalyst
A catalyst is a substance which alters the rate of a chemical reaction but remains
unchanged in quantity at the end of the reaction or at equilibrium.

A catalyst has no effect on position of equilibrium and no effect on the value of

equilibrium constant but only alters the rate of backward and forward reaction
equally. A catalyst therefore increases the rate of attainment of equilibrium by
decreasing the activation energy.

The explanations given above are general. A question may require you just to state
the effect of a constraint. This may not require you to go into details of explaining.
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Questions

1. Sulphur dioxide reacts with oxygen according to the following equation.

(a) State what would be happen to the concentration of sulphur(VI) oxide in the
equilibrium mixture and give a reason for your answer if;
(i) the temperature was increased
(ii) nitrogen gas was added to the mixture at a constant pressure.
(iii) pressure was increased
(iv) more oxygen was added to system at equilibrium
(v) volume of the vessel in increased
2. The reaction between nitrogen and hydrogen at 25℃ and 10 atm takes place according
to the following equation.

What would happen to the concentration of ammonia and the value of the equilibrium

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

constant if;
(i) Helium was added to the equilibrium mixture at constant pressure?
(ii) the temperature was increased to 250℃ but the pressure remains at 10 atm?
(iii) Argon is added to the equilibrium mixture at constant volume?
(iv) some iron is added to the equilibrium mixture
3. Iodine is sparingly soluble in water but readily dissolves in potassium iodide
according to the following equilibrium

(a) Explain why iodine is sparingly soluble in water but very soluble in potassium
iodide
(b) (i) Write an expression for the concentration equilibrium constant, .
(ii) State any three characteristics of the above equilibrium.
(c) State and explain the effect of adding sodium thiosulphate solution to the
position of equilibrium.
4. Phosphorus pentachloride decomposes at high temperatures according to the
following equation.

State how the position of the equilibrium and the value of the equilibrium constant
would be affected and in each case give a reason for your answer if ;
(i) the pressure was increased
(ii) some chlorine was added to the equilibrium
(iii) some phosphorus(III) chloride was removed from the equilibrium mixture
(iv) the temperature was increased
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(v) volume of the container was decreased

(vi) adding a catalyst
5. (a) State three characteristics of a chemical equilibrium.
(b) Phosphorus(V) chloride when heated decomposes according to the following
equation.

(i) Write the expression for the equilibrium constant, .

(ii) When 1 mole of phosphorus(V) chloride was heated in a closed vessel at 350℃,
the equilibrium mixture was found to contain 38.4% of chlorine. Calculate the
equilibrium constant at 350℃.
(iii) The equilibrium constant at 250℃ was found to b 1.54. State whether the
reaction is exothermic or endothermic. Give a reason for your answer.
(c) State what would happen to the concentration of chlorine if the pressure in the
vessel was decreased while the temperature maintained at 350℃. Give a reason for
your answer.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

6. When heated at 1atm, carbon dioxide decomposes according to the equation:

State and explain the effect of ;

(i) heating the carbon dioxide at 2 atmospheres on the equilibrium concentration
of oxygen
(ii) carrying out the decomposition at a lower temperature on the value of the
equilibrium constant, .
7. Hydrogen and iodine were heated in a 1 litre vessel. Explain what would happen to
the equilibrium position of the reaction, equilibrium constant, and rate of attainment
of equilibrium if;
(i) sodium thiosulphate solution was added to the vessel.
(ii) the pressure was increased
(iii) concentration of iodine was increased
(iv) helium gas was added at constant volume.
8. The esterification reaction for formation of ethylethanoate from ethanoic acid and
ethanol is shown by the equation below.

State how the amount of ethylethanoate and position of the equilibrium would be
affected if:
(i) some ethanol is added to the system
(ii) some water is removed from the system
(iii) concentrated sulphuric acid is added
(iv) some sodium hydroxide solution is added
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(v) the temperature was increased

9. Nitrogen and oxygen react endothermically at high temperatures according to the
equation;

The equilibrium constant for the reaction at 2680K and 1 atm total pressure is
. Equal volumes of nitrogen and oxygen were mixed at 2680K and 1 atm total
pressure and allowed to react until equilibrium is reached.
(a) Calculate the:
(i) fraction of the original nitrogen used in the reaction
(ii) fraction of nitrogen(II) oxide in the reaction mixture
(b) State what will happen to the value in (a)(ii) above and give a reason(s) if:
(i) the pressure is increased to 10 atm
(ii) the temperature is raised to 2780K
(iii) a catalyst is added
10. Sulphur dioxide dichloride dissociates when heated according to the equation:

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(a) At a temperature of 375℃ and an overall pressure of 101325 , a sample of
sulphur dioxide dichloride in the gas phase was found to be 84% dissociated.
Calculate the value of equilibrium constant, .
(b) State, at constant temperature, the effect on the position of equilibrium and the
value in (a) above of:
(i) adding a catalyst
(ii) compressing the system
11. Ammonium carbamate decomposes according to the following
equation:

(a) Write the expression for the equilibrium constant

(b) At equilibrium, the total pressure of the system is 0.36 atm. at 40℃. Calculate
the value of for the reaction at 40℃ and indicate its units.
(c) State what happens to the calculated in (a) if :
(i) more solid ammonium carbamate is added to the equilibrium mixture.
(ii) the temperature is increased to 80℃.
12. Discuss the effect of each of the following factors on the position of equilibrium of a
reversible reaction, the rate of attainment of equilibrium and the value of equilibrium
constant.
(i) Temperature
(ii) Pressure
(iii) Catalyst
(iv) Concentration.
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INDUSTRIAL APPLICATION OF CHEMICAL EQUILIBRIUM

The knowledge of chemical equilibrium is applied industrially in the following processes;
 Haber process
 Contact process
 Ostwald process

1. Manufacture of ammonia (the Haber process)

The reaction between dry hydrogen (obtained from natural gas) and dry nitrogen (from
fractional distillation of liquid air) to form ammonia is exothermic and occurs with a
decrease in volume

According to L ́ Chatelier's Principle , the yield of ammonia will be greatest at low

temperature and high pressure.
At a low temperature however, rate of attainment of equilibrium is low and at high

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

temperature, the position of the equilibrium is over to the left.
At high pressure, the cost of the equipment and running costs are high.
Therefore, in practice, a compromise has to be struck. The conditions used in this process
are therefore;
 Pressures between 200-1000 atmospheres
 Temperature of about 450-550oC
 Finely divided iron catalyst
2. Manufacture of sulphuric acid (the Contact process)
The conversion of Sulphur dioxide (obtained by burning Sulphur in air, roasting
iron pyrites, copper pyrites or oxidation of zinc blende or burning hydrogen
sulphide from crude oil in air) and oxygen (obtained from fractional distillation of
liquid air) to Sulphur trioxide is an exothermic reaction and occurs with a decrease in
volume.

According to L ́ Chatelier's Principle , the yield of ammonia will be greatest at low

temperature and high pressure.
At a low temperature however, the rate of attainment of equilibrium is very slow.
Increase in pressure gives an increased yield of Sulphur trioxide but the effect is small
and the yield is good even at pressures just above atmospheric pressure but not as high as
those used in the Haber Process.
Still, at high pressures, sulphur dioxide liquefies.
Therefore, in practice, a compromise has to be struck. The conditions used in this
process are therefore;
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 Pressures between 1-3 atmospheres

 Temperature of about 450-500 oC
 Vanadium(V) oxide catalyst
Question
Sulphur dioxide is a raw material used in manufacture of sulphuric acid by the
contact process.
(a) With relevant equations, describe the various ways how sulphur dioxide used
in this process may be obtained on a large scale.
(b) Describe how sulphuric acid can be manufactured using one of the sources
above.
(c) Briefly describe how the sulphuric acid can be converted to superphosphate
fertilizer.
(a) Sulphur dioxide can be obtained by burning sulphur in air

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

or by roasting iron pyrites in air

or roasting zinc blende in air

or roasting copper pyrites

(b) Iron pyrites are roasted in air to form iron(III) oxide and sulphur dioxide.

The sulphur dioxide obtained above and oxygen obtained by fractional distillation of
liquid air are purified to clear them off any dust that may poison the catalyst and dried.
The purified gases are passed over Vanadium(V) oxide catalyst at temperatures about
450-500 oC and pressures between 1-3 atmospheres to form sulphur trioxide.

The sulphur trioxide is dissolved in concentrated sulphuric acid to form a fuming liquid
called oleum.

The oleum is carefully diluted with a correct amount of water to form 98% concentrated
sulphuric acid.

N.B. 1. Vanadium pentoxide is preferred over Platinum as catalyst because it is cheaper

and not commonly poisoned by impurities
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2. The sulphur trioxide is not dissolved in water because its reaction with water is highly
exothermic and it leads to formation of sulphuric acid sprays that damage plants and
animals
(c) Calcium phosphate is dissolved and stirred in about 65% sulphuric acid to form a
mixture calcium sulphate and calcium dihydrogen phosphate. The product is dried
and forms the superphosphate fertilizer.

N.B; The Single Superphosphate(SSP) fertilizer made above is less efficient because it is
contaminated with Calcium sulphate. A more efficient fertilizer called Triple
Superphosphate fertilizer is formed by using concentrated sulphuric acid instead.

Details of these process for conversion of ammonia formed by Haber process to nitric
acid are discussed in DEMISTYFYING INORGANIC CHEMISTRY under chemistry

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

of period 3 elements by the same author)
Questions

1. Ammonia is manufactured from hydrogen and nitrogen by the Haber process.

(a) Write the equation for the reaction.
(b) State one source of hydrogen and one source of nitrogen used in the above process
(c) Write an expression for the equilibrium constant, for the reaction.
(d) State Le Chatelier’s principle.
(e) The reaction in (a) above is exothermic. State and explain the effect on the above
equilibrium of:
(i) increasing pressure
(ii) removing ammonia from the mixture of gases
(f) Explain why the synthesis of ammonia is operated at a temperature of 400℃.
(g) (i) Name the catalyst used in the Haber process
(ii) Describe how the catalyst works
(iii) Explain the effect of the catalyst on the position of the equilibrium.
(h) Write equations to show how ammonia is converted to nitric acid.
2. Sulphur dioxide is a raw material used in manufacture of sulphuric acid by the contact
process. It is initially converted exothermically to sulphur trioxide during the process.
On industrial scale, this conversion carried out at 450℃ and 2 atmospheres in
presence of a catalyst.
(a) Write equation for formation of sulphur trioxide in the contact process
(b) Name the catalyst used
(c) State the reasons for the choice of the temperature and pressure used to convert
sulphur dioxide to sulphur trioxide.
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(d) Sulphur trioxide reacts with water to form sulphuric acid.

(i) Write equation for the reaction.
(ii) State the hazard of the reaction in d(i) above and describe how it is avoided in the
contact process.
(e) Concentrated sulphuric acid contains 98% of the acid. Calculate the mass of
concentrated sulphuric acid required to make 500 of 1.5M solution of
sulphuric acid.
(f) Name one reagent that can be used to identify the anion in sulphuric acid. State
what would be observed and write the equation for the reaction that takes place
when the reagent you have named is used.
(g) State two large scale uses of sulphuric acid.

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CHAPTER SEVEN
IONIC EQUILIBRIA
ACIDS, BASES AND SALTS
Acids and bases
Acids are characterized by a sour taste and their effect on litmus and changing colour of
indicators. They react with bases and also some other compounds to form salts. They
liberate carbon dioxide from carbonates and hydrogen when reacted with metals.
Bases are characterized by a soapy feel and detergent power. They react with acids to
form a salt and water.

There have been many attempts to define acids and bases. Early definitions considered
acids as substances that provide hydrogen ions when dissolved in water and bases as

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

substances that react with hydrogen ions to form a salt and water.

The concept of acids and bases according to various theories

Acids and bases have been defined according three theories which include the Arrhenius
theory, Bronsted-Lowry theory and the Lewis theory.

1. Acids and bases according to the Arrhenius theory.

According to this theory;
 An acid is a substance that on dissolving in water dissociates to produce
hydrogen ions

 A base is a substance which on dissolving in water dissociates to produce

hydroxyl ions.
̅
̅
Considering the reactions above when a base is reacted with an acid, a neutralisation
reaction occurs.
̅
Arrhenius theory however didn‟t explain bases which do not contain hydroxyl ions for
example basic oxides, carbonates, and ammonia. Ammonia neutralises acids by accepting
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hydrogen ions rather than providing hydroxide ions because undissociated ammonium
hydroxide is hypothesized.

The Arrhenius theory definitions of acids and bases only applied to aqueous solution. It
could not explain acid-base reactions other solvents unlike water.

2. Acids and bases according to Bronsted-Lowry theory

The Bronsted-Lowry theory catered for some of the setbacks of the Arrhenius theory
According to this theory;
 An acid is a substance that donates protons to a base
(i)
(ii)
is a hydrated proton and is called the oxonium ion, hydroxonium ion or
hydronium ion, and is also referred to as the hydrogen ion.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

 A base is a substance that accepts protons from an acid
(iii) ̅
(iv) ̅
(v) ̅
Note: In reaction(i), water accepts a proton from hydrochloric acid to form the
oxonium ion. Water behaves as a proton- acceptor(base)
In reaction(iv), water donates a proton to ethylamine to form the ethylammonium ion.
Water behaves as a proton- donor(acid)
Also note that strong acids and bases completely ionise in solution whereas weak acids
and bases partly ionise in solution.

3. Acids and bases according to Lewis theory

The Bronsted-Lowry theory of acids is based on protolysis. The Bronsted-Lowry acids
must therefore contain hydrogen according to the theory. However, there are substances
also react as acids and change the color of indicators even in dry state but they do not
contain hydrogen. The Lewis theory catered for this shortcoming.
According to the Lewis theory;
 An acid is any substance that can accept a lone pair of electrons.
 A base is any substance that can donate a lone pair of electrons.
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Examples of Lewis acids and bases include

Lewis acids Lewis bases
Aluminium chloride, Iron(III) chloride, Water, ammonia, triethylamine,
Boron trifluoride, Boron trichloride and trimethylamine and alcohols
Beryllium chloride
Hydrogen ion, aluminium ion, Hydroxyl ion, chloride ion and
iron(III) ion and copper(II) ion cyanide ion
Silicon(IV) chloride and Ethene and ethyne
phosphorus(V) chloride

[ ]

[ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

or

or

or

or

Conjugate acid and bases

Benzoic acid ionises in its aqueous solution according to the equation;

In the equilibrium above, the benzoate ion is a conjugate base of benzoic

acid. Benzoic acid is a conjugate acid of the benzoate ion and the two form a conjugate
acid-base pair.
The conjugate base is formed when an acid loses a proton and when the conjugate base
gains a proton, it forms its conjugate acid.
Acids and bases can therefore be neutral molecules, positive ions or negative ions.
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Examples of conjugate acid-base pairs include;

Conjugate acid Conjugate base

Try to write equations showing how the conjugate base is formed from the
conjugate acid for each of the above conjugate acid-base pairs.

Classification of strong acids and bases, weak acids and bases

A strong acid is an acid which ionises completely in its aqueous solution and easily

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

releases protons
A weak acid an acid which partly ionises in its aqueous solution and does not easily
release protons
Examples include;
Strong acid Weak acid
Hydrochloric acid Ethanoic acid
Hydrobromic acid Methanoic acid
Hydroiodic acid Hydrocyanic acid
Nitric acid Hydrofluoric acid
Sulphuric acid Butanoic acid
Chloric(VII) acid Carbonic acid

A strong base is a base which ionises completely in its aqueous solution and easily
accepts protons
A weak base is a base which partly ionises in its aqueous solution and does not easily
accept protons
Examples include;
Strong bases Weak bases
Potassium hydroxide Aqueous ammonia
Sodium hydroxide Aqueous methylamine
Barium hydroxide Aqueous phenylamine
Lithium hydroxide Aqueous triethylamine
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Relative strength of Bronsted-Lowry acids and bases

The strength of different acids in an aqueous solution under similar conditions can be
compared using their degrees of dissociation( ) and acid dissociation constants( ),
(for weak acids) at the same dilution and temperature.
(a) Using degrees of dissociation
 The higher the degree of dissociation at a given temperature and dilution, the stronger
the acid
 The degree of dissociation of an acid increases with dilution and all acids become
equally stronger and infinite dilution because they become completely dissociated.
 The degree of dissociation for an acid that ionises endothermically increases with
increase in temperature hence the acid releases more hydrogen ions as the temperature
increases, becoming stronger with increase in temperature.
 The degree of dissociation for an acid that ionises exothermically decreases with
increase in temperature hence the acid releases fewer hydrogen ions as the

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

temperature increases, becoming weaker with increase in temperature.
Acid Degree of dissociation
for a solution for a solution
0.82 0.96
0.79 0.92
0.51 0.65
0.004 0.013
(b) Using acid dissociation constants
The strengths of weak acids are compared using more conveniently by use of their
dissociation constants.
The higher the acid dissociation constant, the stronger the acid. The strength can then be
explained by use of other terms like electronegativity of bonded atoms, inductive
effect and number of oxygen atom (for oxo-acids of chlorine) in relation to polarity
of the oxygen-hydrogen bond hence the bond strength.
N.B. Inductive effect is the ability of an atom or group of atoms to donate electrons
towards a neighbouring atom or ability to withdraw electrons from the neighbouring
atom.
An atom or group of atoms that donate electrons to a neighbouring atom have positive
inductive effect. These include all alkyl groups.
An atom or group of atoms that withdraws electrons from a neighbouring atom have
negative inductive effect. These include all halogen atoms,
.
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The nature of the groups attached to the carboxyl group has a great effect on the acid
strength therefore due to inductive effect.
Electron withdrawing groups make carboxylic acid stronger by making the
oxygen-hydrogen bond becomes more polar and weak hence release of hydrogen ions in
aqueous solution.
Electron donating groups makes carboxylic acid weaker by making the oxygen-hydrogen
bond less polar and strong hence release of few hydrogen ions in aqueous solution.
Examples
1. The table below shows acid dissociation constants, , of group VII hydrides.
Hydride HF HCl HBr HI
O
( )at 25 C
Explain the trend in values of the hydrides.

The values increase in the order indicating that acid

strength increases in the same order. The strength of an acid depends on how easily it

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

releases protons. This is because atomic radius of the halogen atoms increases from
fluorine to iodine. This makes the hydrogen-halogen bond length longer, reducing the
bond strength from the hydrogen-fluorine bond to hydrogen-iodine bond, releasing
many hydrogen ions in solution.

Hydrofluoric acid is the weakest acid because the fluorine atom has the highest
electronegativity due to a very small atomic radius. Therefore the hydrogen- fluorine
bond is highly polar and very strong making the acid to dissociate to a considerably
smaller extent.
2. The acid strength of the oxo-acids of chlorine increases in the order
. Explain this observation.

The strength of an acid depends on how easily it releases protons. The acid strength
increases depending on the number of oxygen atoms that exert a negative inductive
effect in each molecule of the acid, increasing the polarity of the oxygen-hydrogen
bond. This is because oxygen is more electronegative than chlorine. In chloric(VII)
acid, 3 oxygen atoms exert a negative inductive effect on the O-H bond making it very
weak and breaks to release very many hydrogen ions making it stronger than chloric(V)
acid in which two oxygen atoms exert a negative inductive effect making the O-H bond
weaker than in chloric(III) acid in which only one oxygen atom has a negative inductive
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effect. Chloric(I) acid has the strongest oxygen-hydrogen bond because no oxygen atom
has a negative inductive effect in it.

3. The table below shows acid dissociation constants, for some acids at a
particular temperature.
Acid
( )
State and explain the trend in acid strength of the acids.
Acid strength decreases in the order

The strength of an acid depends on how easily it releases a proton. Methanoic acid has
a hydrogen atom instead of an alkyl group attached to the carboxyl group, which has no
inductive effect hence the oxygen-hydrogen bond in it is the weakest, easily breaks to
release many hydrogen ions. The alkyl groups in ethanoic acid and propanoic acid have
a positive inductive effect which decreases the polarity of the oxygen-hydrogen bond,

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

making it not easy break. The strength of the oxygen-hydrogen bond increases as the
positive inductive effect increases with the increase in number of carbon atoms in the
alkyl groups attached to the carboxyl group.

4. The table below shows acid dissociation constants, for some acids at a
particular temperature.
Acid
( )
State and explain the trend in acid strength of the acids.
Acid strength increases in the order

The strength of an acid depends on how easily it releases a proton. Ethanoic acid has a
methyl group attached to the carboxyl group, which has a positive inductive effect hence
the oxygen-hydrogen bond in it has lowest polarity, making it the strongest hence does
not easily break to release hydrogen ions. The chlorine atoms in chloroethanoic acid,
dichloroethanoic acid and trichloroethanoic acid are more electronegative than carbon
and have a negative inductive effect which increases the polarity of the oxygen-
hydrogen bond, making it weak and easy to break. The strength of the oxygen-hydrogen
bond decreases as the negative inductive effect increases with the increase in number
of chlorine atoms in the chain attached to the carboxyl group.
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5. The table below shows acid dissociation constants, for some acids at a
particular temperature.
Acid ( )

State and explain the acid strengths of the acids.

Ethanoic acid is the weakest acid among all the acids. For the other acids, acid strength
decreases in the order
The strength of an acid depends on how easily it releases a proton. Ethanoic acid has a
methyl group attached to the carboxyl group, which has a positive inductive effect hence

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

the oxygen-hydrogen bond in it has lowest polarity, making it the strongest hence does
not easily break to release hydrogen ions. For the halogen substituted acids, the halogen
atoms are more electronegative than carbon and have a negative inductive effect.
However, the negative inductive effect decreases with the decrease in electronegativity
from fluorine to iodine, decreasing the polarity of the oxygen-hydrogen bond, making it
stronger and not easily broken from fluoroethanoic acid to iodoethanoic acid.

The strength of different bases in an aqueous solution under similar conditions can also
be compared using their degrees of dissociation( ) and base dissociation constants( ),
(for weak bases) at the same dilution and temperature.

(a) Using degrees of dissociation

The higher the degree of dissociation at a given temperature and dilution, the stronger the
base

Base Degree of dissociation

0.95
0.93
0.90
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(b) Using acid dissociation constants

The strengths of weak bases are compared using more conveniently by use of their base
dissociation constants.
The higher the base dissociation constant, the stronger the base.
Electron withdrawing groups make bases weaker by making the lone pair of electrons
less available to accept protons.
Electron donating groups makes bases stronger by making the lone pair of electrons
readily available to accept protons.
Example
1. The table below shows the base dissociation constants of different bases in
aqueous solutions.
Base Base dissociation constant,

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(a) Compare and explain the basic strength of ammonia, methylamine and
ethylamine
Basic strength increases in the order;

The basic strength of amines depends on the availability of lone pair of electrons on the
nitrogen atom. Ammonia is the weakest base because the hydrogen atoms attached to
the nitrogen atom, have no inductive effect. The alkyl groups attached to the nitrogen
atom in methylamine and ethylamine have a positive inductive effect which increases the
electron density on the nitrogen atom, making the lone pairs of electrons readily
available for protonation. The positive inductive effect increases with the increase in
number of carbon atoms in the alkyl groups attached to the nitrogen atom hence
ethylamine is a stronger base than methylamine.
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(b) Compare and explain the basic strength of methylamine, dimethylamine and
trimethylamine
Basic strength increases in the order;

The basic strength of amines depends on the availability of lone pair of electrons on the
nitrogen atom. The three methyl groups attached to the nitrogen atom in
trimethylamine, have the greatest positive inductive effect but due to steric hindrance to
the approach of a proton towards the nitrogen atom and poorest solvation due to lack
of nitrogen-hydrogen bonds, trimethylamine is the weakest base. The methyl groups
attached to the nitrogen atom in methylamine and dimethylamine have a positive
inductive effect which increases the electron density on the nitrogen atom, making the
lone pairs of electrons readily available for protonation. Methylamine and
dimethylamine also have nitrogen-hydrogen bonds which increase their solvation. The
positive inductive effect and solvation increase with the increase in number of alkyl
groups attached to the nitrogen atom and number of nitrogen-hydrogen bonds

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

respectively hence dimethylamine is a stronger base than methylamine.

(c) Compare and explain the basic strength of ammonia, ethylamine and aniline
Basic strength increases in the order;

The basic strength of amines depends on the availability of lone pair of electrons on the
nitrogen atom. Aminobenzene is the weakest base because the lone pairs of electrons on
the nitrogen atom interact with the delocalised pi- electrons in the benzene ring. This
reduces the electron density on nitrogen atom, making the lone pair of electrons less
available for protonation. Ammonia is a stronger base than aminobenzene because the
hydrogen atoms attached to the nitrogen atom, have no inductive effect. Ammonia also
has more nitrogen-hydrogen bonds hence more solvated than aminobenzene. The ethyl
group attached to the nitrogen atom in ethylamine has a positive inductive effect which
increases the electron density on the nitrogen atom, making the lone pair of electrons
readily available for protonation.

Note; Amides ( ) are negligibly basic or neutral in aqueous solution compared

to aliphatic amines( ) because the lone pair of electrons on the nitrogen atom in
amides is partially involved in bonding to the carbon of the carbonyl group and
therefore less available for protonation

2. Explain why ethylamine is a stronger base than ethanamide,

although both compounds have an amino group
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The ethyl group attached to the nitrogen atom in ethylamine has a positive inductive
effect which increases the electron density on the nitrogen atom, making the lone pair
of electrons readily available for protonation. In ethanamide, the lone pair of electrons
on the nitrogen atom interacts with the pi-electrons of the carbonyl group therefore less
available for protonation.

Questions

1. The oxy-acids of chlorine include; .

(a) Write the name of each oxo-acid.
(b) Draw the structure and name the shape of each of the acids
(c) Arrange the acids in order of decreasing acid strength and explain your answer.
2. (a) What do you understand by the term inductive effect?
(b) The carboxylic acids below have the following values for the acid dissociation
constant,

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Acid
℃

Explain the observations in the acid dissociation constants

(c) (i) Amines are basic in nature. Explain the role of inductive effect of the alkyl
groups on the strength of bases.
(ii) How do you account for the fact that amides though having a group are not
basic in nature.
3. Ethylamine, dimethylamine and ammonia are weak bases in aqueous solution.
(a) (i) Arrange the compounds in order of increasing basic strength
(ii) Suggest why the basic strength is in that order.
(b) (i) Name a reagent that can be used to identify the functional group of the bases.
(ii) State what is observed when each of the bases is separately treated with the named
reagent.
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Derivation of expressions for acid dissociation constant, and base

dissociation constant,

Calculations involving
Calculations involving

The auto ionisation ( self-ionisation ) of water

The concept of
The is the negative logarithm to the base ten of the hydrogen ion concentration in
moles per litre of a solution.
[ ]
Since at ℃, of water contains approximately of hydrogen
ions. The of water at ℃ is given by:

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The higher the concentration of hydrogen ions, the lower the hence the stronger the
acid.
The of an aqueous solution of an acid or base depends on the concentration and the
degree of ionisation.
Just like , is related to the hydroxyl ion concentration by the expression;
[̅ ]
The is also related to the ionic product of water by:

Therefore from the ionic product of water;

[ ][ ̅ ]
[ ][ ̅ ]
[ ] [̅ ]

At ℃

The above equation can be used for aqueous solutions including water at ℃.

The scale
The scale ranges from 1 to 14 depending on the hydrogen ion concentration in the
solution. It is summarised below:

[ ]
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
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Neutral
Strong acids Weak acids Weak bases Strong bases

Calculations involving for strong acids and bases

The relationship between and for an acid-base conjugate

Considering an acid-base conjugate pair of and , in aqueous solution, the

equilibria involved for the acid, and its base, are:

̅
For the first equilibrium;
[ ][ ]
[ ]
For the second equilibrium;
[ ][ ̅ ]
[ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

[ ][ ] [ ][ ̅ ]
[ ] [ ]
[ ] [̅ ]
[ ] ̅
[ ]

Expression of for weak acids and bases

calculations for weak acids and weak bases

BUFFER SOLUTIONS
Water and other simple aqueous solutions do not retain a constant hydrogen ion
concentration, hence their pH values since they dissolve such as carbon dioxide from the
air or silicates from the walls of glass containers.
To obtain solutions that maintain their pH fairly constant, buffer solutions are used.

A buffer solution is a solution which resists changes in pH when a small amount of

acid or alkali is added to it.

-volume curves for acid-base titrations

Sparingly soluble salts/ electrolytes
Many salts such as lead(II) sulphate, calcium carbonate, silver chloride and others are
described as insoluble in water. There is however, in practice, no substance completely
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insoluble but some substances dissolve to a very small extent that their solubility cannot
be determined by the ordinary method already described.
Electrolytes that dissolve only slightly in water are called sparingly soluble electrolytes.

Solubility product
Consider a sparingly soluble electrolyte, . The ions of the electrolyte in its
saturated solution will be in equilibrium with the undissolved solid at a given
temperature.

From the law of mass action:

[ ] [ ]

Since the concentration of a solid remains constant, then;

[ ] [ ]

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The constant, is called the solubility product of the sparingly soluble electrolyte,
.
Solubility product is therefore defined as the product of the molar concentrations of the
ions of a sparingly soluble electrolyte in its saturated solution raised to appropriate
powers at a given temperature.

Expressions for solubility product

Consider each of the sparingly soluble electrolytes below. For each the equation for
solubility in water and the solubility product expression is written.
(i) Silver bromide
(ii) Silver ethanedioate
(iii) Calcium phosphate

(i) Silver bromide

Equation :
[ ][ ]

(ii) Silver ethanedioate

Equation :
[ ] [ ]

(iii) Calcium phosphate

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Equation :
[ ] [ ]

(a) Using conductivity measurements

Excess solid calcium hydroxide is added to a given volume of distilled water in a
container.
The mixture is shaken for some time and left to settle at a given temperature to attain
equilibrium.
The mixture is filtered to obtain a saturated solution of calcium hydroxide as filtrate.
The electrolytic conductivity of the saturated solution, is
measured using a conductivity meter.
The electrolytic conductivity of water, at the same temperature is
obtained from books
Also the molar conductivities at infinite dilution of calcium ions and hydroxide ions

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

are read from the tables.
Treatment of results
The electrolytic conductivity of calcium hydroxide is then obtained by;

The molar conductivity of calcium hydroxide at infinite dilution is obtained by the

equation;
̅
, where is molar conductivity of calcium hydroxide

̅
[ ]

[ ] [ ]
̅
[̅ ] [ ]
[ ][ ̅ ]

This method can be used for any electrolyte whose solution cannot be titrated with any
suitable reagent.
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CHAPTER NINE
ELECTROCHEMISTRY
Electrochemistry is the branch of chemistry that deals with chemical changes that are
produced by passing electric current into a chemical system or the generation of
electricity by spontaneous chemical reactions.
MODES OF CONDUCTION OF SUBSTANCES
The substances that allow electric current to flow through them are called conductors.
Those that do not allow electric current to flow through them are called non-conductors
or insulators. The conductors are classified into two type i.e. metallic conductors and
electrolytic conductors.
1. Metallic conductors
Metals or alloys allow electric current to flow through them without undergoing any
chemical change. The metals conduct electric current by use of free mobile electrons

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(delocalised electrons). These include copper, silver, aluminium and others. This mode
of conduction is called electronic conduction.
2. Electrolytic conductors
These include aqueous solutions of electrolytes or molten electrolytes. They are
compounds and chemical changes occur when they conduct electricity. The electrolytes
conduct electric current by use of free mobile ions. Examples include dilute hydrochloric
acid, aqueous sodium chloride, molten lead(II) bromide and others. This mode of
conduction is called electrolytic conduction.

ELECTROLYSIS
Electrolysis is the decomposition of a compound in its molten state or in solution by
passage of an electric current through it.
or
The overall chemical change that occurs at the electrodes when an electric current
passes through a fused electrolyte or its aqueous solution
The electrolyte, solvent or electrode may all be involved in the electrolytic reaction
The common terms used in electrolysis
1. Electrolytes
These are compounds which conduct electric current in solution or in molten state and are
decomposed by it.
A non-electrolyte is a substance which does not conduct electric current in molten state or
aqueous solution and cannot be decomposed by electric current. For example sucrose
Electrolytes can be salts, acids or bases.
Electrolytes can be classified as strong or weak.
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(i) Strong electrolytes

These are electrolytes which almost completely ionise in solution. Their solutions do not
contain unionized molecules.
They include most salts, strong acids and strong alkalis.
(ii) Weak electrolytes
These are electrolytes which partly ionise in solution. Their solutions contain ions in
equilibrium with unionized molecules.
They include most organic acids and bases and ammonia.
Examples of strong and weak electrolytes
Strong electrolytes Weak electrolytes
Sodium chloride Ethanoic acid
Calcium chloride Ammonia solution
Sodium hydroxide Ethylamine
Hydrochloric acid Carbonic acid

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Electrolytes can as well be ionic or covalent.
(i) Ionic electrolytes
These electrolytes are made up of ions in the solid state but the ions are not free to move.
For example sodium chloride, .
When ionic electrolytes are heated, sufficient energy is absorbed to break the crystal
lattice so that the ions are free to move within the molten electrolyte.
When ionic electrolytes are dissolved in water (or any other ionizing solvent), the crystal
lattice is broken, the ions become free to move. The ions are hydrated (solvated,
completely surrounded by water molecules)
(ii) Covalent electrolytes
These electrolytes do not contain ions so they conduct electricity in the liquid state as
ionic electrolytes do. The covalent electrolytes usually contain polar bonds such as
or bonds. They react with water or any other ionizing solvent to
form hydrated ions. These include all mineral acids.
2. Electrodes
These are conductors which carry electricity into and out of the cell. The electrodes
include the anode and the cathode.
(i) Anode
This is the electrode at which oxidation takes place
(ii) Cathode
This is the electrode at which reduction takes place
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Explaining the changes that take place during electrolysis

Electrolysis is generally carried out in an electrolytic cell as shown below.

Battery
Flow of current Flow of electrons
Anode Cathode

Electrodes
Electrolyte

The electrolytic cell is set up as shown above. The electrolyte contains both cations and
anions. During electrolysis, the anions migrate to the anode and lose electrons
(are oxidised) to form neutral elements or new molecules.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The cations migrate to the cathode and combine with the electrons there (are reduced) to
form neutral elements or new molecules.

Principles of electrolysis (selective discharge of ions)

Under similar conditions, when two or more ions with a similar charge are present in a
solution, i.e. and or and ̅ , one ion is preferentially selected for
discharge at each electrode and the selection of the ion depends on the following factors:
(i) Position of the ion in the electrochemical series
(ii) Concentration of the ions in solution
(iii) Nature of the electrode.
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(i) Position of the ion in the electrochemical series

Cations (move to cathode) Anions (move to anode)

Increasing ease of discharge at

Increasing ease
of discharge at
anode
cathode
̅

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

If all the other factors (stated above) are constant, any ion is discharged from solution in
preference to the ions above it in the electrochemical series.
For example in electrolysis of sodium hydroxide solution, the solution contains the
cations; from water and . The hydrogen ion discharges in preference to the
sodium ion at the cathode. Hydrogen gas is formed at the cathode.

During electrolysis of silver nitrate solution, the solution contains the anions; ̅ from
water and . The hydroxide ion is discharged in preference to the nitrate ion at the
anode. Oxygen gas is formed at the anode.
̅
Note: The order of preferential discharge given in the table above only applies for
discharge from aqueous solutions containing ions at comparable concentrations
approximately 1M. Sometimes exceptions arise as a result of large differences in
concentration.
(ii) Concentration of the ions in solution

An ion present at a lower concentration is more difficult to discharge than an ion present
at a higher concentration.
The electrolysis of sodium chloride solution liberates chlorine at the anode during
manufacture of chlorine. This is because although the solution contains the anions; ̅
and . The chloride ion is discharged because it is present in a higher concentration
than the hydroxide ion.
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The electrolysis of concentrated hydrochloric acid liberates chlorine at the anode for the
same reason as in the case above.

(iii) Nature of the electrode.

Inert electrodes like platinum may not affect the products of electrolysis. Some
electrodes may affect the products of electrolysis. For example:
(a) Electrolysis of concentrated sodium chloride solution (saturated brine) using
platinum cathode and mercury cathode.
When a platinum cathode is used, hydrogen ions are discharged in preference to sodium
ions because hydrogen is lower than sodium in the electrochemical series. Hydrogen gas
is therefore formed at the platinum cathode.

When a mercury cathode is used, sodium ions are discharged in preference to hydrogen
ions because the discharge of sodium ion requires less energy than the discharge of

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

hydrogen ions. Sodium amalgam is therefore formed at the mercury cathode by the
reaction between sodium and the mercury cathode.

(b) Electrolysis of copper(II) sulphate solution using platinum anode and copper
anode.
When a platinum anode is used, hydroxide ions are discharged in preference to sulphate
ions because the hydroxide ion is lower than the sulphate ion in the electrochemical
series. Oxygen gas is therefore formed at the platinum anode. The solution at the anode
also becomes acidic due to the reaction between hydrogen ions and sulphate ions to form
sulphuric acid.
̅

When a copper anode is used, neither the hydroxide ions nor the sulphate ions are
discharged but instead the copper anode dissolves in the solution to form copper(II) ions.
The electrolysis is merely a transfer of copper from the anode to the cathode.

Laws of electrolysis
Micheal Faraday studied the quantitative relationships between the electricity passed
through an electrolyte and the amount of material liberated or deposited at the electrodes.
1. Faraday‟s first law of electrolysis states that the mass of the substance liberated at an
electrode during electrolysis is directly proportional to the quantity of electricity
passed through the electrolyte.
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Where; is the mass of substance consumed or produced at an electrode

is the quantity of charge passed in Coulombs
is the current in amperes
is the time in seconds for which the current was passed.
is a proportionality constant called the electro-chemical equivalent.

2. Faraday‟s second law of electrolysis states that the quantity of electricity required to
liberate one mole of any element is proportional to the charge number of its ion.
The charge number of an ion, represented by is the number of positive or negative
charges which the ion possesses. It can be positive or negative. For example for
, for , for and for .
The magnitude of the charge number is usually equal to the number of moles

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

electrons required for the ion to be discharged.

Note that

Experiment to determine the Faraday constant by electrolysis of copper(II) sulphate

using copper electrodes.
d.c power supply
Arrange the apparatus as shown
Variable The variable resistor is used to keep the current
Ammeter
resistor constant
Weigh the mass of the pure copper anode 𝑥 𝑔
and pure copper cathode 𝑦 𝑔 separately
Copper anode Copper cathode Pass a constant electric current 𝐼 𝐴𝑚𝑝𝑒𝑟𝑒𝑠 for a
measured time interval 𝑡 𝑠𝑒𝑐𝑜𝑛𝑑𝑠
Remove the cathode and anode and wash them
with distilled water and then propanone and dry
|

Copper(II) sulphate solution them.

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The washed and dried cathode and anode are weighed again and their new masses
and recorded respectively.
Treatment of results
Mass of copper removed from the anode
Quantity of charge passed,

( )

( )

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

Trial question;
A student passed a constant electric current of 0.15A through a solution of silver nitrate
using pure silver electrodes for exactly 45 minutes. The mass of the anode decreased by
0.45g. Use this data to calculate the charge on a mole of electrons.
Calculations of electrolysis
Examples
1. Calculate the quantity of charge required to deposit 40.5g of aluminium during
electrolysis of a solution of aluminium ions.

( )

2. When current was passed through a solution of silver nitrate for 10 minutes,
0.54g of silver was deposited at the cathode. Calculate the current.
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( )

3. Determine the time taken to deposit 1.0g of chromium when a current of 0.120A
flows through a solution of chromium(III) sulphate.

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

4. Calculate the mass of lead deposited at the cathode during electrolysis when a
current of 1.50A flows through molten lead(II) bromide for 20 minutes.

( )

5. An electric current was passed through a solution of copper(II) sulphate

electrolyzed using platinum electrodes for 1 hour.
(a) Calculate the strength of the current used to deposit 0.106g of copper.
(b) If the electrolytic cell above was in series with a silver nitrate cell. Calculate
the mass of silver deposited on the cathode of the second cell.

(a)

( )
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(b)

( )

6. A current of 89.6mA was passed through an electrolytic cell containing dilute

sulphuric acid electrolyzed between platinum electrodes for 1 hour. Calculate the
total volume of gas measured at 15℃ and 100kPa liberated.
̅

( )

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

( )

7. Calculate the volume of oxygen liberated at anode at s.t.p in the electrolysis of

copper(II) sulphate solution when a current of 1500 milliamperes is passed for 10
minutes.

( )

8. (a) A current of 32.2A was passed through molten lead(II) bromide for 5 hours
and the bromine liberated reacted with 94g of hydroxybenzene. Calculate the
number of moles of ;
(i) bromine liberated
(ii) hydroxybenzene that reacted
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(b) State what is observed and write equation for the reaction that took place
between bromine and hydroxybenzene in (a) above.
(a) (i)

( )

(ii)

(b) Observation: White precipitate

Equation: 𝐵𝑟 𝐵𝑟

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

𝐵𝑟

9. 20 of 0.05M aqueous phenylamine was mixed with 50 of 1M sodium

bromide and electrolyzed at current of 0.2A. The first permanent bromine
colour was observed after 48.25 minutes and then electrolysis was stopped.
.
(i) Calculate the moles of bromine that reacted with 1 mole of phenylamine
(ii) Hence write equation of the reaction between bromine and phenylamine.
Name the product

(i)

Hint: Electrolysis of sodium

bromide yields bromine at the
anode. The sodium bromide was
such an excess such that
( ) enough bromine is liberated to
react with all the phenylamine.
The first bromine colour only
( ) appears if just enough bromine
has been formed to react with
all the phenylamine present.
( )
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(ii) Observation: White precipitate

Equation: 𝐵𝑟 𝐵𝑟

𝐵𝑟
Name of product: 2,4,6-Tribromoaminobenzene

10. A direct current of 0.45A was passed through a dilute solution of copper(II)
sulphate using graphite electrodes for 5.96 hours.
(a) Write equation for the reaction at the:
(i) cathode
(ii) anode
(b) If 3.1767g of copper was deposited and 560 of oxygen at stp were evolved,
calculate the quantity of electricity required to produce 1 mole of each
substance at their respective electrodes.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(a) (i) At cathode:
(iii) At anode: ̅
(b)

( )

( )

Questions
1. 3 Faraday are needed to electroplate a given amount of metal using a current of 5.0A.
How long will it take to electroplate the metal?
2. Calculate the mass of copper deposited at the cathode when a current of 1.0A was
passed through copper(II) sulphate solution for 10 minutes.
3. Calculate the mass of silver deposited at the cathode during electrolysis when a
|

current of 1.80A flows through an aqueous solution of silver nitrate for 45.0 minutes.

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4. The same current was passed through molten sodium chloride and through molten
cryolite containing aluminium oxide. If 4.60g of sodium were liberated in one cell.
Calculate the mass of aluminium liberated in the other cell.
5. During the extraction of aluminium, a current of 0.2 ampere was passed for one hour
through aluminium sulphate solution.
(a) Write an equation for the reaction that took place at each electrode
(b) Calculate the mass of aluminium produced
6. Calculate the mass of chlorine that can be produced by the electrolysis of molten
sodium chloride with a current of 5.5 amperes for 25 minutes.
7. Calculate the mass of lead deposited when 0.2 moles of electrons are passed through
lead(II) nitrate solution during electrolysis.
8. Calculate the volume of oxygen liberated at anode at s.t.p in the electrolysis of
copper(II) sulphate solution when a current of 1500 milliamperes is passed for 10
minutes.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

9. Calculate the volume of chlorine liberated at standard temperature and pressure by
passing 0.2 moles of electrons during electrolysis sodium chloride solution.
10. Determine the mass of hydrogen liberated by passing 0.5 moles of electrons during
electrolysis sodium chloride solution.
11. If a current is passed through a cell for 2 hours deposits 0.4818g of silver. Calculate
the volume of oxygen that would be liberated in the same circuit where dilute
sulphuric acid is electrolysed.

12. Calculate the volume of oxygen produced at room temperature when a concentrated
aqueous solution of sulphuric acid is electrolyzed for 30 minutes using a current of
0.50A.
13. During the electrolysis of a 1M copper(II) sulphate solution at ℃, a current of 0.1A
was passed for one hour through the electrolyte. The mass of the copper cathode
increased by 0.118g. State how the change in mass would be affected if the
experiment was repeated:
(a) at a current of 0.2A
(b) at ℃
(c) with a 2M copper(II) sulphate solution
(d) for a time of 2 hours
14. (a) An aqueous solution of copper(II) sulphate was electrolyzed between copper
electrodes.
Write equation for the reaction at the;
(i) Cathode
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(ii) Anode
(b) (i)Identify the species which carry the current through the solution and state their
direction of flow.
(ii) Explain the changes in the mass of each electrode and in the concentration
of copper(II) sulphate near the anode.
(iii) Calculate the change in mass of the anode if a current of 1.0A is maintained
for one hour.
(c) During the electrolysis of aqueous hydrogen chloride between silver electrodes,
the anode mass increases and a white coating form on it. Explain this observation.

The applications of electrolysis in industry

The elements potassium, calcium, sodium, magnesium and aluminium being very
reactive, are never found as free elements. They are extracted by electrolysis.
Potassium is extracted from fused potassium hydroxide. Sodium from molten sodium
chloride, calcium from fused calcium chloride and aluminium from Bauxite.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

1. Extraction of sodium by electrolysis of molten sodium chloride in the Down’s
process. (The same process is used for manufacture of chlorine)
Sodium is extracted by electrolysis of molten sodium chloride in the Down’s cell.
A carbon anode is used and an iron cathode and are separated from each other by an
iron gauze diaphragm.
Calcium chloride is added to the electrolyte to lower its melting point of sodium
chloride from about 800℃ to about 600℃.
Sodium chloride is decomposed by electric current to form sodium ions and chloride
ions.

Sodium ions are preferentially discharged at the cathode at the temperature used
forming sodium.

Chloride ions migrate to the anode and form chlorine gas which escapes from the cell.

2. Anodisation of aluminium

Aluminium is normally covered by a thin coating of aluminium oxide to protect it from

corrosion and to make it resistant from chemical attack. The thickness of the oxide layer
is increased by electrolyzing dilute sulphuric acid or chromic(VI) acid with the
aluminium made the anode. The oxygen liberated at the anode reacts with the aluminium
to form the protective layer of aluminium oxide.
̅
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3. Electroplating
This is the electrical coating of one metal with another metal to make it resistant to
corrosion and improve its appearance. The metal to be electroplated is made the cathode
and the electroplating metal made the anode. The electrolyte must contain a solution of
ions of the electroplating metal.

4. Manufacture of sodium chlorate(I) and sodium chlorate(V) by electrolysis of

concentrated sodium chloride solution.
A cold concentrated solution of sodium chloride is electrolyzed using platinum
electrodes placed close together. The chlorine liberated at the anode combines with the
hydroxyl ions left at the cathode to form sodium chlorate(I).
̅
If the electrolysis is done using a hot concentrated solution of sodium chloride at ℃
The chlorine liberated at the anode combines with the hydroxyl ions left at the cathode to
form sodium chlorate(V).

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

̅
5. Extraction of aluminium by electrolysis of molten aluminium oxide
6. Manufacture of sodium hydroxide by electrolysis of concentrated sodium
chloride solution (saturated brine) using a mercury cell (Castner-Kellner cell) or
a diaphragm cell.
(The same process can as well be used for manufacture of chlorine)
7. Refining of copper
(Check for the details of 5, 6 and 7 in Demystifying Inorganic Chemistry by the
same author)

CONDUCTIVITY OF SOLUTIONS OF ELECTROLYTES

When electric current flows through an electrolyte, there is resistance to the flow of
current. The current that flows through a given solution under given conditions is
inversely proportional to the reciprocal of resistance.

The common terms used

1. Conductance
Conductance is the reciprocal of resistance of an electrolytic solution.

The SI unit of conductance is the siemens although it used to be measured in

reciprocal ohms . Therefore .
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High resistance means low conductance and low resistance means high conductance.

2. Resistivity
To compare resistances of different electrolytic solutions, the idea of resistivity is used.
Resistivity is the resistance of a solution placed between two parallel electrodes of
cross-sectional area and separated by a distance of apart.
Resistance of an electrolytic solution is directly proportional to the length between
the electrodes;

The resistance of an electrolytic solution is also inversely proportional to the cross sectional
area of the electrodes;

Combining (i) and (ii);

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Where is resistance
is resistivity
is length between the electrodes
is the cross sectional area of the electrodes
From (iii) , then Resistivity,

Since R is measured in ohms , is Area is measured in and length in metres ,

then the SI unit of resistivity is ohm metre . But can also be used.

3. Electrolytic conductivity
It is also called specific conductivity or specific conductance.
To compare conductance of different electrolytes, electrolytic conductivity is used.
Electrolytic conductivity is defined as the conductivity of a solution of an electrolyte
placed between two parallel electrodes of cross-sectional area and separated by a
distance of apart.
or
It is the reciprocal of resistivity.

⁄
The SI unit of electrolytic conductivity is siemen per metre . But can
also be used.
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4. Cell constant
From , the cell constant is the value of . Its units are or can be .
and for any cell are constant.

Cell constant is therefore the distance between two parallel electrodes of a cell divided
by the cross sectional area of one electrode.
Therefore,
Also
or ⁄
5. Molar conductivity
It is also called molar conductance.
Molar conductivity is the conductivity of a solution of containing 1 mole of an
electrolyte placed between two parallel electrodes of cross-sectional area and
separated by a distance of apart.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

or
It is the electrolytic conductivity divided by concentration.

since , then
The two above formulae show the relationship between electrolytic conductivity and
molar conductivity.
The SI unit of molar conductivity is . But can also be used.

The formula of molar conductivity used in calculations depends on the units of and
given.The formula used is intended to make units consistent.
If unit of is If unit of is
The expression is
and that of is then; and that of is only and only used if the
then; units are consistent.

Note: When the definitions are stated in terms of formulae, each term in the formula
should be well defined.
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Measurement of conductivity of solutions

Variable condenser
Conductivity cell Variable resistance
Head phones
A B (detector)
X

a.c source
A solution of the electrolyte of known concentration is prepared using conductivity water
(demineralized water or water purified by ion exchange)
A known volume of the standard solution of the electrolyte is then pipetted and placed in
a conductivity cell.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The conductivity cell and its solution is connected in a Wheatstone bridge circuit where
it‟s made the unknown resistance.
A rapidly alternating current is applied from a small induction coil or a vacuum tube
oscillator.
The variable resistance and the position X along wire AB are changed until no current
passes through the head phones
At this balance point the buzzing sound in the head phones (used as detector) is a
minimum.
The distances and at balance point are measured.
The area of the electrodes in the conductivity cell and their distance of separation
is also measured.
Treatment of results
At the balance point ;

The resistance of the solution is then calculated and used to find conductance from; |

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Calculations involving electrolytic conductance

Examples
1. (a) State what is meant by the term cell constant.
(b) The resistivity of 0.02M potassium chloride solution is 361 and a
conductivity cell having such a solution was found to have a resistance of
550 .
(i) Calculate the cell constant
(ii) if the same cell was filled with 0.1M zinc sulphate solution had a resistance of
72 . Calculate the conductivity of 0.1M zinc sulphate solution.

(b) (i) (ii)

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

2. (a) A conductivity cell with electrodes in area and apart has a
resistance of 7.25 when filled with 5 percent potassium chloride solution.
Calculate the:
(i) cell constant
(ii) the conductivity of the potassium chloride solution.
(b) If the same cell was filled with 0.02M potassium chloride with a resistivity of
361 . Calculate the resistance.

(a) (i) (b)

(ii)

3. The resistance of a 0.01M sodium chloride solution in a conductivity cell was

found to be 210 . The specific conductance of the solution is .
Determine the cell constant.
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4. A conductivity cell has electrodes of cross sectional area and apart.

The cell is filled with pure water of conductivity and a potential
difference of 10V applied. Calculate the current that would flow through the cell.

5. A 0.1M solution of ethanoic acid when placed between two electrodes , each
in area and separated by has a resistance of 6956 ohms.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Calculate the:
(i) specific conductivity,
(ii) molar conductivity of the solution.

(ii)
(i)

6. The molar conductivity of 0.1M ethanoic acid solution is .

Calculate the:
(i) electrolytic conductivity
(ii) resistivity.
(i) (ii)

7. The resistance of a conductivity cell of a conductivity cell when filled with 0.05M
solution of an electrolyte is 100 at 40℃. The same conductivity cell when
filled with 0.01M solution has a resistance of 50 . If the electrolytic
conductivity of 0.05M is . Calculate the:
(i) electrolytic conductivity of 0.01M solution
(ii) molar conductivity of 0.01M solution
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(i)

(ii)

8. Calculate the mass of ethanoic acid that must be dissolved in a litre of water to
make a solution of molar conductivity and electrolytic
conductivity .

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Questions
1. A conductivity cell with electrodes in area and apart has a resistance of
35.6 when filled with 2.085 percent barium chloride solution. Calculate the:
(i) cell constant
(ii) the electrolytic conductivity of the barium chloride solution.
2. A conductivity cell has electrodes of cross-sectional area of in area and
apart. Calculate the cell constant of the conductivity cell.
3. A conductivity cell has electrodes of cross-sectional area of in area and
apart. Calculate the cell constant of the conductivity cell.
4. The electrolytic conductivity of 2M potassium chloride solution of .
The resistance of 2M potassium chloride solution in a conductivity cell is 1.5 .
Calculate the cell constant of the conductivity cell.
5. The conductivity of an aqueous solution of sodium chloride in a cell is
92 .The resistance offered by the cell is 247.8 ohm. Calculate the cell
constant.
6. The molar conductance of 2M potassium chloride solution is .
Calculate the specific conductance of the solution.
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7. A 0.05M sodium hydroxide solution offered a resistance of 31.6 in a conductivity

cell at 298K. If the cell constant of the cell is 0.367 .Calculate the molar
conductivity of the sodium hydroxide solution.
8. (a) Define the terms;
(i) conductivity
(ii) conductance
(b) Using the same conductivity cell, the resistance of potassium chloride solution
and 0.1M chloroethanoic acid solution were found to be 24.9 and 66.5 ohms
respectively at 25℃. The conductivity of potassium chloride at 25℃ is
.
(i) Calculate the cell constant
(ii) Calculate the conductivity of 0.1M chloroethanoic acid.

Factors affecting electrolytic conductivity of electrolytes

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

The factors affecting electrolytic conductivity include:
(i) Concentration
(ii) Temperature

(i) Concentration
For a strong electrolyte, as concentration increases, conductivity increases up to a
maximum and then decreases.
Explanation;
As concentration increases, the total number of conducting ions per unit volume
solution increases. This increases the conductivity. As concentration increases further,
the total number ions in solution increases further since the electrolyte is completely
ionized at all concentrations, inter-ionic distance decreases, ionic interference increases
and ionic mobility decreases. This decreases the electrolytic conductivity.

For a weak electrolyte, as concentration increases, conductivity increases up to a

maximum and then decreases.
Explanation;
As concentration increases, the total number of conducting ions per unit volume
solution increases. This increases the conductivity. As concentration increases further,
the total number unionized molecules of the electrolyte increases, degree of dissociation
decreases and the number of conducting ions per unit volume of solution decreases.
This decreases the electrolytic conductivity.
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(ii) Temperature
For a strong electrolyte, conductivity increases with increase in temperature.
Explanation;
As temperature increases, the average kinetic energy of the conducting ions increases.
The viscosity of the water decreases and the ionic mobility increases.
For weak electrolytes, the effect of temperature depends on the enthalpy change which
accompanies ionization.
For a weak electrolyte that ionizes exothermically, increase in temperature decreases
the degree of dissociation according to Le Chatelier‟s principle. Hence the number of
conducting ions per unit volume of solution decreases. This decreases the electrolytic
conductivity.
For a weak electrolyte that ionizes endothermically, increase in temperature increases
the degree of dissociation according to Le Chatelier‟s principle. Hence the number of
conducting ions per unit volume of solution increases. This increases the electrolytic
conductivity.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Factors affecting molar conductivity of electrolytes
The factors affecting molar conductivity include:
(i) Temperature of the solution
(ii) Magnitude of the charge on the ions
(iii) Ionic radius
(iv) Viscosity of the solvent
(v) Concentration of the solution

(i) Temperature of the solution

For a strong electrolyte, molar conductivity increases with increase in temperature.
Explanation;
As temperature increases, the average kinetic energy of the conducting ions increases.
The viscosity of the water decreases and the ionic mobility increases.
For weak electrolytes, the effect of temperature depends on the enthalpy change which
accompanies ionization.
For a weak electrolyte that ionizes exothermically, increase in temperature decreases
the degree of dissociation according to Le Chatelier‟s principle. Hence the number of
conducting ions per unit volume of solution decreases. This decreases the molar
conductivity.
For a weak electrolyte that ionizes endothermically, increase in temperature increases
the degree of dissociation according to Le Chatelier‟s principle. Hence the number of
conducting ions per unit volume of solution increases. This increases the molar
conductivity.
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Question
(a) Distinguish between electrolytic conductivity and molar conductivity
(b) The molar conductivity of ethanoic acid containing is 8.50
units at 18℃ and 14.7 units at 100℃. Explain the difference in molar
conductivities at the two temperatures.

(ii) Magnitude of the charge on the ions

Molar conductivity increases with increase in the magnitude of ionic charge. Ions with
high charges are more strongly attracted by the oppositely charged electrode and move
faster.

(iii) Ionic radius

Molar conductivity increases with increase in ionic radius. The higher the ionic radius,
the lower the charge density and the less hydrated the ion. The less hydrated ions move
faster than heavily hydrated ions hence ions with smaller ionic radius are more

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

conducting than ions with higher ionic radius.

Question; Explain why the:

(a) magnesium ion has a higher molar conductivity than the sodium ion
(b) sulphate ion has a higher molar conductivity than the chloride ion.
(c) the molar conductivity of the lithium ion is smaller than that of the sodium
ion

(iv) Viscosity of the solvent

The higher the viscosity of the solvent, the lower the ionic mobility hence the lower the
molar conductivity.

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(v) Concentration of the solution

The sketches below show the variation of molar conductivity with the square root of
concentration for both a strong electrolyte and a weak electrolyte.

𝑴𝒐𝒍𝒂𝒓 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒊𝒗𝒊𝒕𝒚
𝑺𝒄𝒎𝟐 𝒎𝒐𝒍 𝟏

Ethanoic acid

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𝟏
𝟑 𝟐
√𝑪𝒐𝒏𝒄𝒆𝒏𝒕𝒓𝒂𝒕𝒊𝒐𝒏 𝒎𝒐𝒍𝒅𝒎
Explanation of the shapes of the graphs
For potassium chloride, as concentration increases, molar conductivity decreases.
Potassium chloride is a strong electrolyte. As concentration increases, the total number
of conducting ions per unit volume increases, inter ionic distance decreases, ionic
interference increases and ionic mobility decreases.
At zero concentration (infinite dilution), molar conductivity reaches a maximum value
called molar conductivity at infinite dilution because ionic interference is negligible.
N.B Molar conductivity at infinite dilution is obtained from the graph by extrapolation.

For Ethanoic acid, as concentration increases, molar conductivity decreases.

Ethanoic acid is a weak electrolyte. As concentration increases, the degree of
dissociation decreases and the number of conducting ions per unit volume of solution
decreases.
Instead of concentration, reciprocal of concentration( ), also called dilution can be used.
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The sketches below show the variation of molar conductivity with the dilution for
both a strong electrolyte and a weak electrolyte.

Potassium
Potassium chloride
chloride Note that neither the
graphs against
concentration nor those
𝑴𝒐𝒍𝒂𝒓 𝒄𝒐𝒏𝒅𝒖𝒄𝒕𝒊𝒗𝒊𝒕𝒚
against dilution begin from
𝑺𝒄𝒎𝟐 𝒎𝒐𝒍 𝟏 Ethanoic acid
Ethanoic acid the origin.
The graphs do not coincide
anywhere too

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

𝒐𝒓 𝒅𝒊𝒍𝒖𝒕𝒊𝒐𝒏 𝒎𝒐𝒍𝒅𝒎 𝟑 𝟏
𝒄
Explanation of the shapes of the graphs
For potassium chloride, as dilution increases, molar conductivity increases to a
maximum value at which it remains constant at infinite dilution.
Potassium chloride is a strong electrolyte. As dilution increases, inter-ionic distance
increases, ionic interference decreases and ionic mobility increases.
At zero concentration (infinite dilution), the ionic interference is negligible.
N.B Molar conductivity at infinite dilution is obtained from the graph by extrapolation.
For Ethanoic acid, as dilution increases, molar conductivity increases.
Ethanoic acid is a weak electrolyte. As dilution increases, degree of dissociation
increases and the number of conducting ions per unit volume of solution increases.
Questions
1. The table below shows values of molar conductivity of ethanoic and potassium
chloride at different concentrations.
Concentration 0.0001 0.001 0.01 0.1 1 2 3
107.0 41.0 14.3 4.6 1.32 0.80 0.54
129.1 127.3 122.4 112.0 98.3 92.6 88.3

(a) Complete the table above.

(b) On the same axes, plot graphs for molar conductivity against the square root of
concentration.
(c) State and explain the shapes of the graphs in (b) above.
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2. The table below shows values of molar conductivity of hydrochloric acid and
ammonia solution at different concentrations at ℃.
Concentration 0.001 0.01 0.1 1 3
377 370 351 301 215
28 9.6 3.3 0.89 0.36

(a) Complete the table above.

(b) On the same axes, plot graphs for molar conductivity against dilution.
(c) State and explain the shapes of the graphs in (b) above.
3. The table below shows values of molar conductivity of sodium chloride solution at
different concentrations at ℃.
Concentration 0.2 0. 1 0.05 0.02 0.01 0.005 0.001
Molar conductivity of 0.01015 0.0107 0.0111 0.0116 0.0118 0.0122 0.0124
sodium chloride

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

√
(a) Complete the table above.
(b) On different axes, plot a graph for:
(i) molar conductivity against dilution.
(ii) molar conductivity against √
(c) From each of the graphs determine the molar conductivity at infinite dilution of
sodium chloride.
(d) Explain the shape of each of the graphs in (b) above.
4. The table below shows values of molar conductivity of ethanoic acid solution at
different concentrations at ℃.
Concentration 0.001 0.01 0.1 1.0 3.0
41.00 14.30 4.60 1.32 0.54
( )

(a) Complete the table above.

(b) On different axes, plot a graph for:
(i) molar conductivity against the square root of concentration.
(ii) molar conductivity against dilution
(c) Explain the shape of each of the graphs in (b) above.
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5. (a)Define the term molar conductivity

(b) On the same sketch, draw a graph to show variation of molar conductivity of
aluminium sulphate and ethanoic acid.
(c) Compare and explain the shape of your graph for:
(i) ethanoic acid
(ii) aluminium sulphate

Kohlrausch’s law of independent migration of ions and its application

Kohlrausch Friedrich investigated the molar conductivity at infinite dilution of a large
number of electrolytes and found that it was a sum of two quantities.
Kohlrausch’s law states that the molar conductivity at infinite dilution of an electrolyte
is equal to the sum of the molar conductivities at infinite dilution of the ions produced
by the electrolyte.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Applications of Kohlrausch’s law
(i) Indirect determination of molar conductivity at infinite dilution for weak
electrolytes.
(ii) To determine solubility of sparingly soluble electrolytes
(iii) To determine solubility product of sparingly soluble electrolytes
(iv) To determine degree of dissociation and equilibrium constant of a weak
electrolyte

(i) Indirect determination of molar conductivity at infinite dilution for weak

electrolytes.
The molar conductivity at infinite dilution of a weak electrolyte can be obtained if the
molar conductivities of selected strong electrolytes are known.
For ethanoic acid, the molar conductivity at infinite dilution can be obtained from the
molar conductivities at infinite dilution of hydrochloric acid, potassium ethanoate and
potassium chloride.
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Since equation (iv) can be obtained by adding (i) and (ii) and subtracting equation (iii);
Therefore;
[ ] [ ] [ ]

Examples
1. Given that the molar conductivities at infinite dilution of some electrolytes are as
shown below;
Compound
Sodium chloride 113
Ammonium chloride 134.1
Sodium hydroxide 225.2
Sodium methanoate 101.2
Hydrochloric acid 397.8

(a) Calculate the molar conductivity at infinite dilution of:

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(i) methanoic acid
(ii) ammonia solution
(iii) ammonium methanoate
(b) Explain the differences in your answers in a(i) and (iii) above
(i)

(ii)

(iii)

(b) The molar conductivity at infinite dilution of methanoic acid is higher than that of
ammonium methanoate because the hydrogen ion in methanoic acid has a higher
molar conductivity than the ammonium ion in ammonium methanoate.

2. The molar conductivity at infinite dilution of the sulphate ion is 160

. If the molar conductivity at infinite dilution of aluminium
sulphate is 858 , calculate the molar conductivity at infinite
dilution of the aluminium ion.
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(i) Determining solubility and solubility product of sparingly soluble

electrolytes
The solubility of a sparingly soluble salt can be determined from the molar conductivity
of its saturated solution using the steps below:
The electrolytic conductivity of the saturated solution is measured using a
conductivity meter.
Using a known value of , the electrolytic conductivity of the electrolyte is then
obtained from the expression;

The molar conductivity at infinite dilution of the electrolyte is obtained from the
known values molar conductivity at infinite dilution of its constituent ions or from the
known values molar conductivity at infinite dilution of selected electrolytes using
Kohlrausch‟s law. Since the solution is very dilute then; .
The expression; is then used to calculate the

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

solubility, depending on the units of .
The stoichiometry of reaction is then used to determine the solubility product, .

Experiment to determine solubility and solubility product of silver chloride

Excess solid silver chloride is added to a given volume of distilled water in a container.
The mixture is shaken for some time and left to settle at a given temperature to attain
equilibrium.
The mixture is filtered to obtain a saturated solution of silver chloride as filtrate.
The electrolytic conductivity of the saturated solution, is
measured using a conductivity meter.
The electrolytic conductivity of water, at the same temperature is
obtained from books
Also the molar conductivities at infinite dilution of silver ions and chloride ions are
read from the tables.
Treatment of results
The electrolytic conductivity of silver chloride is then obtained by;

The molar conductivity of silver chloride at infinite dilution is obtained by the equation;

, where is molar conductivity of silver chloride

[ ]
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[ ] [ ] [ ]
[ ][ ]

(Revisit the experiments on solubility product in the topic IONIC EQUILIBRIA for
more experiments on solubility product)
Examples
1. The electrolytic conductivity of a saturated solution of silver chloride at ℃ is
.The molar conductivities at infinite dilution of silver and
chloride ions are and
respectively.
The electrolytic conductivity of pure water at ℃ is
Calculate the:
(a) solubility of silver chloride at ℃ in grams per litre
(b) solubility product of silver chloride

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(a)

Solubility in

(b)
[ ][ ]

2. The electrolytic conductivity of a saturated solution of silver bromide at ℃ is

. The electrolytic conductivity of pure water at ℃ is
. Calculate the solubility product of silver bromide.
(The molar conductivities at infinite dilution of potassium bromide, silver nitrate
and potassium nitrate at infinite dilution are 137.4, 133 and 131
respectively at ℃)

[ ][ ]
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3. (a) Calcium phosphate is sparingly soluble in water.

Write:
(i) equation for the solubility of calcium phosphate in water
(ii) the expression for the solubility product of calcium phosphate
(b) The molar conductivities of calcium chloride, sodium phosphate and sodium
chloride at infinite dilution at ℃ are 271.8, 390.3 and 126.5
respectively. Calculate the:
(i) molar conductivity of calcium phosphate at infinite dilution at ℃.
(ii) solubility product of calcium phosphate at ℃.
(Electrolytic conductivity of calcium phosphate is )

(a) (i)
(iii) [ ] [ ]

(b) (i)

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[ ]

(ii)

[ ] [ ]
[ ] [ ]
[ ] [ ]

(ii) Determining degree of dissociation and equilibrium constant of a weak

electrolyte

The degree of dissociation of a weak electrolyte can be obtained if the molar

conductivity at a given concentration and the molar conductivity at infinite
dilution are known.
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The acid dissociation constant, of a weak acid can then be obtained from the
expression;

However, if is small compared to 1, then is approximately equal to one, so

that;
The concentration of hydrogen ions is obtained from the expression [ ] and the
can be calculated.
The base dissociation constant and hydrolysis constant for salts.

Examples
1. The electrolytic conductivity of a 0.16M ethanoic acid solution at ℃ is
. The molar conductivity at infinite dilution of hydrogen ion and
ethanoate ion are and
respectively. Calculate the:

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(i) degree of dissociation , of ethanoic acid.
(ii) acid dissociation constant, , at ℃.

(i) (ii) Since is very small

compared to one, (0.3486%)

2. (a) (i) Define the term “molar conductivity at infinite dilution, ”.

(ii) State how you would expect the molar conductivity of sodium chloride
solution to vary as the dilution of the solution is increased. Give a
reason for your answer.
(b) The values of at ℃ for some electrolytes are as follows;

Electrolyte
104.7
126.5
426.2
(i) Calculate at ℃ for methanoic acid.
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(ii) If the value of molar conductivity, , for 0.01M methanoic acid is

50.5 at ℃. Calculate the acid dissociation constant, ,
for methanoic acid.
(b) (i) (ii) The value of is not very small
as compared to one(12.49%) so
cannot be used in the
calculation.

3. The molar conductivity of a 0.093M solution of ethanoic acid at ℃ is

. The molar conductivity at infinite dilution of hydrogen
ion and ethanoate ion are and

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

respectively. Calculate the:
(i) molar conductivity of ethanoic acid at infinite dilution.
(ii) degree of dissociation , of ethanoic acid.
(iii) acid dissociation constant, , at ℃.
(iv) of the acid.
(i) (ii)

(iii) The value of very small as compared to (iv) [ ]

one(1.5%) so can be used in the
calculation. [ ]

4. The conductivity of a 0.063M solution of 2-hydroxypropanoic acid was found to

be . The molar conductivity of the acid at infinite dilution at
℃ is . Calculate the of the solution and the acid
dissociation constant.

( ) [ ]
[ ]
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5. The molar conductivities at infinite dilution of the ammonium ion and the
chloride ion are and respectively. The
electrolytic conductivity of a 0.1M ammonium chloride is .
Calculate the hydrolysis constant of ammonium chloride.

The value of is not very small as compared to

one(86%) so cannot be used in the
calculation.

Questions

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

1. Calculate the molar conductivity of water at infinite dilution at ℃ if at the same
temperature, ,
and .
2. Calculate the molar conductivity at infinite dilution of ethanoic acid from the
following data.
Compound
Hydrochloric acid 426
Sodium chloride 126
Sodium ethanoate 91

3. The molar conductivity at infinite dilution of sodium ion and the carbonate ion
respectively are 50.11 and 144 respectively. Calculate the molar
conductance at infinite dilution of sodium carbonate.
4. (a) State Kohlrausch‟s law of independent conductivity of ions.
(b) Some ionic conductivity at infinite dilution at ℃ are shown below:
Ion Ionic conductivity
̅ 198.6
76.4
73.6
50.1
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Calculate the molar conductivity at infinite dilution of:

(i) Sodium hydroxide
(ii) Ammonium chloride
5. The electrolytic conductivity of a saturated solution of silver chloride at ℃ after
deducting the electrolytic conductivity of water is .The molar
conductivities at infinite dilution of silver and chloride ions are and
respectively at ℃. Calculate the:
(a) solubility of silver chloride at ℃
(b) solubility product of silver chloride ℃.
6. (a) Explain what is meant by solubility product
(b) The electrolytic conductivity of a saturated solution of silver chloride in pure
water at ℃ is and the electrolytic conductivity of pure
water is . The molar conductivities at infinite dilution of
the following salts are given as:

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Salt
Molar conductivity 133.4 145.0 149.9
Calculate the solubility product of a saturated solution of silver chloride at ℃.
7. (a) Define the following terms in relation to an aqueous solution of an electrolyte;
(i) specific conductance
(ii) molar conductance
(b) The electrolytic conductivity of an aqueous saturated solution of at ℃ is
. The molar conductivities at infinite dilution of
, sodium hydroxide and sodium chloride are 273, 248 and 126
respectively. Calculate the:
(i) molar conductivity at infinite dilution of
(ii) the solubility of in water at ℃ in
8. The conductivity of dichloroethanoic acid at a dilution of is .
The molar conductivity at infinite dilution for the acid is . Calculate
the degree of ionization of the acid at a concentration of .
9. The conductivity of a 0.01M ethanoic acid at is . The molar
conductivities of hydrogen ion and ethanoate ion at infinite dilution are
and respectively. Calculate the acid dissociation
constant, , of ethanoic acid.
10. The electrolytic conductivity of a solution containing 6.66g of ethanoic acid per litre
is at ℃. The molar conductivity of the acid at infinite dilution at
this temperature is . Calculate the degree of dissociation of
ethanoic acid.
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11. (a) Write an equation for the:

(i) acid dissociation constant, , for ethanoic acid
(ii) relationship between acid dissociation constant, , and degree of ionisation
of an acid.
(b) The electrolytic conductivity of a at ℃ is
and its molar conductivity at infinite dilution is
. Calculate:
(i) the molar conductivity of the ethanoic acid at ℃
(ii) the degree of ionisation of the acid at ℃
(iii) the of the acid
(c) Besides concentration, state one other factor that can affect the of the acid.
12. (a) State factors that can affect molar conductivity of an electrolyte.
(b) The molar conductivities at infinite dilution at ℃ for some electrolytes are
given in the table below.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Electrolyte ℃
Sodium nitrate 122
Nitric acid 421
Sodium ethanoate 91

Calculate the molar conductivity at infinite dilution for ethanoic acid.

(c) The molar conductivity of a aqueous solution at ℃ is
. Calculate the acid dissociation constant ( for ethanoic acid).
13. (a) Explain why hydrogen fluoride is a weaker acid than hydrogen chloride.
(b) Molar conductivities at infinite dilution at ℃ for some compounds are shown
in the table below.
Compound ℃
Nitric acid 0.0421
Potassium nitrate 0.0145
Potassium fluoride 0.0129
The conductivity of a aqueous solution of hydrogen fluoride is
. Calculate the:
(i) molar conductivity of solution
(ii) degree of ionization of hydrogen fluoride.
14. (a) Explain the molar conductivity of an electrolyte.
(b) Sketch a graph to show the variation of conductivity of a strong electrolyte with
dilution.
(c) Briefly explain the shape of the graph in (b) above.
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(d) The molar conductivities of nitric acid, potassium nitrate and potassium fluoride
are 421, 145 and 129 respectively at infinite dilution. Calculate
the:
(i) molar conductivity of hydrofluoric acid at infinite dilution
(ii) dissociation constant of , of 0.1M hydrofluoric acid solution.
(Electrolytic conductivity of hydrofluoric acid is )
15. (a) Define the terms:
(i) conductivity
(ii) molar conductivity
(iii) conductance
(b) The table below shows the molar conductivities of aqueous potassium hydroxide
at given dilutions.

Dilution 100 25 11.11 6.25 4.0 2.8

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Molar conductivity 239 228 224 215 210 201
(i) Plot a graph of molar conductivity against dilution
(ii) Use the graph to determine molar conductivity of potassium hydroxide at
infinite dilution.
(iii) Explain the shape of the graph
(c) (i) Draw a sketch graph to show change in conductivity with volume of aqueous
sodium hydroxide when of a 0.1M propanoic acid is titrated with 0.1M
sodium hydroxide solution.
(ii) Explain the shape of the graph.
(d) The conductivity of a saturated solution of silver phosphate at 25℃ is
and that of pure water is . If the molar
ionic conductivities of phosphate ions and silver ions are 240 and 62
at infinite dilution at 25℃ respectively, calculate the:
(i) solubility of silver phosphate at 25℃
(ii) solubility product of silver phosphate at 25℃ and give its units.

Application of conductance (conductivity measurements)

The applications of conductivity measurements include:
(i) To determine solubility of sparingly soluble salts
(ii) To determine solubility product of sparingly soluble salts
(iii) To determine degree of dissociation of weak electrolytes
(iv) To determine the ionisation constant of a weak electrolyte
(v) To determine ionic product of water
(vi) To determine formulae of complexes
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(vii) Conductimetric titrations

Conductimetric titrations
The conductivity of a solution changes during an acid-base titration. The change in
conductivity of the solution can be measured. There is a sharp change in conductivity at
the end point. Such a titration is called a conductimetric titration.
The different velocities of the ions are used to ascertain the end point of a titration.
1. Titration of a strong base against a strong acid (sodium hydroxide solution against
hydrochloric acid)

A
Conductivity
𝟏
𝒄𝒎 𝟏 C

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Volume used at
B end point

Volume of sodium hydroxide solution added 𝒄𝒎𝟑

Explanation of shape of the graph
Initially, conductivity is high at A due to very many fast moving and highly conducting
hydrogen ions from the strong completely ionized hydrochloric acid.
Conductivity decreases along AB as sodium hydroxide solution is added because the
fast moving highly conducting hydrogen ions are being neutralized to form water and
being replaced by the slow moving less conducting sodium ions.

At B, the end point is reached. Conductivity is low and is due to the sodium ions and
chloride ions from the sodium chloride salt formed.
Along BC, conductivity increases because the concentration of sodium ions is being
increased and also the fast moving hydroxyl ions are being added.
Note: The volume at end point is usually obtained by extrapolation since the minimum
point from plotted graphs is not usually as shown on the sketch above. The point where
two extrapolated lines meet gives the end point.
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2. Titration of a weak base against a strong acid (ammonia solution against sulphuric
acid or hydrochloric acid)

A
Conductivity
𝟏
𝒄𝒎 𝟏

B C

Volume of ammonia solution added 𝒄𝒎𝟑

Explanation of shape of the graph
Initially, conductivity is high at A due to very many fast moving and highly conducting

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

hydrogen ions from the strong completely ionized sulphuric acid.
Conductivity decreases along AB as ammonia solution is added because the fast moving
highly conducting hydrogen ions are being replaced by the slow moving less
conducting ammonium ions.

At B, the end point is reached. Conductivity is low and is due to the ammonium ions
and sulphate ions from the ammonium sulphate salt formed.
Along BC, conductivity remains almost constant because the ionization of the excess
weak ammonia solution added is suppressed by the ammonium ions from the
completely ionized ammonium sulphate salt formed. This makes the conductivity of
hydroxyl ions negligible.
Note: Using data obtained practically, when a graph is plotted, the conductivity may
slightly increase along BC but the explanation still holds.
3. Titration of a strong base against a weak acid (sodium hydroxide solution against
ethanoic acid)
D

Conductivity C
𝟏
𝒄𝒎 𝟏

A
|

B
Volume of sodium hydroxideWhatsApp:
solution added 𝒄𝒎𝟑
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Explanation of shape of the graph

Initially, conductivity is low at A due to very few fast moving, conducting hydrogen ions
from the weak partially ionized ethanoic acid.
Conductivity slightly decreases along AB as sodium hydroxide solution is added
because the few fast moving highly conducting hydrogen ions are being neutralized to
form water and being replaced by the slow moving less conducting sodium ions.
Also the ethanoate ions from completely ionised sodium ethanoate salt formed suppress
the ionisation of the weak ethanoic acid.

Conductivity gradually increases along BC due to increase in number of conducting

ethanoate ions and sodium ions from completely ionized sodium ethanoate formed.
At C, the end point is reached. Conductivity is only due to the sodium ethanoate salt
formed.
Along CD, conductivity rapidly increases because excess fast moving hydroxyl ions are

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

being added.
4. Titration of a weak base against a weak acid (ammonia solution against ethanoic
acid)

Conductivity
𝟏 C D
𝒄𝒎 𝟏

A
B
Volume of ammonia solution added 𝒄𝒎𝟑
Explanation of shape of the graph
Initially, conductivity is low at A due to very few highly conducting hydrogen ions from
the weak partially ionized ethanoic acid.
Conductivity slightly decreases along AB as ammonia solution is added because the
ethanoate ions from ammonium ethanoate formed suppress the ionisation of the weak
ethanoic acid.
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Conductivity gradually increases along BC due to increase in number of conducting

ethanoate ions and ammonium ions from completely ionized ammonium ethanoate
formed.
At C, the end point is reached. Conductivity is only due to the ammonium ethanoate
salt formed.
Along CD, conductivity remains almost constant because the ionization of the excess
weak ammonia solution added is suppressed by the ammonium ions from the
completely ionized ammonium ethanoate salt formed.

However, conductimetric titration is not only confined to acids and bases. Copper(II)
sulphate can be titrated with sodium hydroxide, sodium ethanoate with hydrochloric acid,
etc.
Explain why in the conductimetric titration of aluminium nitrate solution against
sodium hydroxide solution, the conductivity of the mixture decreases to a minimum
value, then increases gradually and finally increases rapidly with excess base.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Aluminium ions react with hydroxide ions to form insoluble aluminium hydroxide.
̅
The reaction reduces the concentration of aluminium ions in solution and conductivity
decreases to a minimum on complete precipitation.
The aluminium hydroxide reacts with more hydroxide ions to form a soluble complex
of tetrahydroxoaluminate(III) ions hence a gradual increase in conductivity.
̅
The conductivity then increases rapidly due to excess mobile highly conducting
hydroxide ions.

Questions
1. The conductivity of of copper(II) sulphate solution varies with the volume of
0.1M sodium hydroxide solution added as shown by the graph below;

P
R
Electrolytic
conductivity

20.0
|

Volume of sodium hydroxide solution 𝒄𝒎𝟑

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(a) Define the term electrolytic conductivity

(b) Give a reason why:
(i) conductivity is high at point P.
(ii) conductivity increases along QR
(c) Calculate the initial concentration of copper(II) sulphate solution
(d) (i) The electrolytic conductivity at P was at ℃.
Determine the molar conductivity of the copper(II) sulphate solution.
(ii) State and explain the effect of dilution on the answer in d(i) above.
2. The molarity of a sample of hydrochloric acid about 0.1M was determined accurately
by measuring the conductivity of the solution as 1.0M sodium hydroxide solution was
added to of the acid. The results were as shown below:
Conductivity 4.1 3.3 2.4 1.7 1.5 1.8 2.2 2.5
Volume of 1.0M sodium hydroxide 1 2 3 4 5 6 7 8

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(a) Plot a graph of conductivity against volume of 1.0M sodium hydroxide
(b) Determine from the graph, the volume of sodium hydroxide used to reach end
point
(c) Calculate the molarity of hydrochloric acid
(d) Explain the shape of the graph
(e) (i) Distinguish between solubility and solubility product.
(ii) Describe an experiment to determine the solubility product of calcium
phosphate in the laboratory.
3. The table below shows the conductivity of a solution of when a small volume of
sodium hydroxide solution was added to of 0.1M hydrochloric acid.
Volume of sodium 0 1 2 3 4 5 6 7 8 9 10
hydroxide
Conductivity 3.90 3.35 2.80 2.27 1.72 1.11 0.62 0.76 1.19 1.62 2.0

(a) (i) Plot a graph of conductivity against volume of sodium hydroxide

(ii) Use your graph to determine the volume of sodium hydroxide used to
neutralize the acid
(iii) Calculate the molarity of sodium hydroxide
(iv) Explain the shape of the graph
(b) State one other application of conductivity measurements.
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4. (a) The ionic radii and ionic conductivities at infinite dilution of some ions are shown
in the table below:

Ion Ionic radius Ionic conductivity

0.060 38.7
0.095 50.1
0.133 73.5
Explain the results in the table

(b) The diagram below shows curves A and B obtained when aqueous sodium
hydroxide was gradually added separately to equimolar
solutions of hydrochloric and ethanoic acid separately

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Molar conductivity

Volume of sodium hydroxide added

Explain the shape of the curves:
(i) Curve A
(ii) Curve B
5. (a)The conductimetric curve for titration of ethanoic acid and ammonia solution is
given below:

Conductivity
Y Z

W
X
Volume of ammonia solution 𝒄𝒎𝟑

Explain the shape of the graph.

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(b) The molar conductivities of nitric acid, sodium bromoethanoate and sodium nitrate
are and respectively at infinite dilution at 25℃.
Calculate the:
(i) molar conductivity of bromoethanoic acid at infinite dilution
(ii) dissociation constant, , of a 0.1M bromoethanoic acid solution.
(Electrolytic conductivity of bromoethanoic acid is
6. (a) The conductimetric curve for the titration of ethanoic acid and sodium hydroxide
is given below.
S

Electrolytic
conductivity
𝟏 R
𝒄𝒎 𝟏

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

P
Q
Volume of sodium hydroxide solution added 𝒄𝒎𝟑
Explain the shape of the curve PQRS
(b) The molar conductivity of silver nitrate, potassium nitrate and potassium
chloride are 134.0, 143.2 and 140.8 respectively at infinite
dilution and 25℃. Calculate the:
(i) molar conductivity of silver chloride at infinite dilution at 25℃
(ii) solubility product, Ksp of silver chloride at 25℃ .(The electrolytic
conductivity of water and that of a saturated solution of silver chloride are
respectively)
(c) The molar conductivities of sodium bromoethanoate, hydrochloric acid and
sodium chloride are and respectively at infinite
dilution at 25℃. Calculate the:
(i) degree of ionization of 0.1M bromoethanoic acid solution at 25℃.
(The molar conductivity of 0.1M bromoethanoic acid solution is
)
(ii) ionisation constant, , of a 0.1M bromoethanoic acid solution at 25℃.
7. (a) Define the terms:
(i) electrolytic conductivity
(ii) molar conductivity
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(b) Draw a sketch graph to show how molar conductivity varies with concentration
for:
(i) hydrochloric acid
(ii) ethanoic acid
(c) Explain the shape of the curve in each case.
(d) 25 of 0.1M ethanoic acid was titrated with sodium hydroxide solution.
(i) Draw a sketch graph to show how conductivity of the solution changes
when sodium hydroxide is added to the acid
(ii) Explain the shape of the graph.

ELECTRODE POTENTIAL AND ELECTROCHEMICAL CELLS

ELECTRODE POTENTIAL

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

A metal rod consists of metal ions and a cloud of delocalized valence electrons. If the
metal is dipped in a solution of its ions, some of the cations dissolve leaving up an excess
of electrons on the surface of the metal.

The metal will become negatively charged with respect to the solution sorrounding it.
The tendency of the metal to lose ions to the sorrounding solution is known as
electrolytic solution pressure.

Metal rod(negative electrode potential)

+ +
+ +
+ + Solution of the metal ions
+ +
++++

Alternatively, metal ions may take electrons from the strip of the metal and get
discharged as metal atoms.

In this case, the metal becomes positively charged with respect to the solution
surrounding it.
The tendency of the ions to deposit on the metal from a solution is called the deposition
pressure.
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Metal rod(positive electrode potential)

+ +
+ +
+ + Solution of the metal ions
+ +
+

The potential difference between the strip of the metal and the solution depends on the
nature of the metal and on the concentration of the ions in equilibrium with the metal
surface.
For a zinc rod dipped in a solution of zinc ions, the zinc has a negative electrode
potential because it has a greater tendency to dissolve to form ions (greater electrolytic

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

solution pressure) and a smaller tendency to be deposited as a metal (lower deposition
pressure). The zinc rod is said to be a negative electrode.
For a copper rod dipped in a solution of copper(II) ions, the copper has a positive
electrode potential because it has a greater tendency to be deposited as a metal (higher
deposition pressure) and a smaller tendency to dissolve to form ions (lower electrolytic
solution pressure). The copper rod is said to be a positive electrode.
An equilibrium is established when the rate at which electrons are gained is equal to the
rate at which electrons are lost.

The position of equilibrium differs for different combinations of metals placed in

solutions of their ions.

Electrode potential is the potential difference developed between a metal placed in

contact with a solution of its ions.
Its symbol is (measured in volts, ).
By IUPAC convention, the term electrode potential means reduction electrode potential.
Therefore in most of the work hereafter we shall deal with reduction potentials.
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Electrochemical series
The electrochemical series is an arrangement of elements in increasing order of their
electrode potential. Reduction potentials are used in the arrangement.
Reduction equation Electrode potential,

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Note:
1. The elements with more negative values of electrode potential are highly
electropositive metals i.e. Lithium, potassium, sodium and magnesium.
2. The elements with more positive values of electrode potential are strongly
electronegative elements i.e. Bromine, chlorine and fluorine.
3. From the half-cell reactions, any reagent on the right is a reducing agent and any
reagent on the left is an oxidizing agent.
4. Any species on the right for a reaction with a lower (more negative) electrode
potential is a stronger reducing agent than a species with a higher(less negative or
more positive) electrode potential. Lithium is the strongest reducing agent and the
fluoride ion is the weakest reducing agent. On the other hand, fluorine, with a more
positive electrode potential is the strongest oxidizing agent and the lithium ion is the
weakest oxidizing agent.
5. The more positive (or less negative) the electrode potential, the easier it is to reduce

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

the ions on the left. So the metal on the right is relatively unreactive and is a relatively
poor reducing agent. For example:
6. The more negative (or less positive) the electrode potential, the more difficult it is to
reduce the ions on the left. So the metal/ species on the right is relatively reactive and
is a relatively good reducing agent. For example:

7. The Lithium electrode can as well be written as . The process is a

reduction and the electrode potential is a reduction potential.

Question
The standard electrode potentials of some half-cell reactions are given below:

State which species is the:

(a) strongest reducing agent
(b) strongest oxidizing agent
(c) most difficult to reduce
(d) most reactive metal
(e) easiest to reduce
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Absolute and relative electrode potential

Absolute electrode potential is the potential difference developed between a metal surface
and the solution with which it is in contact.
The relative electrode potential is the potential difference developed between a metal
surface and the solution with which it is in contact relative to a reference electrode. The
standard hydrogen electrode is the commonest reference electrode used.
Other reference electrodes include the saturated calomel electrode, the quinhydrone
electrode, the silver/ silver chloride electrode and the glass electrode.
It is impossible to measure the absolute potential difference of a metal with respect to
its solution because it is necessary to have a second electrode which also has its own
potential difference with respect to its solution.

The structure and functioning of the Standard Hydrogen Electrode (SHE)

Structure
Platinum wire

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Hydrogen gas at 298K and
1 atm

Platinised platinum
1M hydrochloric
acid solution
The standard hydrogen electrode consists pure hydrogen gas continuously bubbled over
the surface of a platinum foil coated with platinum black at 298K and 1 atmosphere.
The platinized platinum is dipped in 1M solution of hydrogen ions.

Functioning
The hydrogen is adsorbed on the platinum black and equilibrium is set up between the
adsorbed layer of hydrogen and the hydrogen ions in the solution.

The platinum black is inert hence does not take part in the reaction and is finely divided
platinum to catalyse the set up of this equilibrium. There will be an electrode potential
between the adsorbed hydrogen and the solution which is arbitrary taken as .
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This fixes a scale against which other standard electrode potentials are measured by
combining the standard hydrogen electrode with other electrodes and measuring the
emf of the cell formed.

Standard electrode potential,

When the standard hydrogen electrode is used in conjunction with a metal electrode
placed in a solution containing 1M of the ions of the metal at 298K and 1 atmosphere, the
electromotive force (emf) obtained is called the standard electrode potential.
Standard electrode potential is the potential difference or reduction potential
established when a metal electrode is dipped in a 1 molar solution of its ions measured
relative to the standard hydrogen electrode at 25 oC and 1 atmosphere.
Experiment to measure standard electrode potential of a metal
Considering an iron electrode;

Potentiometer

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Hydrogen gas at 1 Iron rod
atm and 298K Salt bridge

1M solution of hydrogen
ions
1M Iron(II) sulphate
Platinised 298K solution
platinum
An iron rod is dipped in a 1molar solution of iron(II) sulphate
The iron half-cell is connected externally by electric wires to a standard hydrogen
electrode via a high resistance voltmeter or a potentiometer to measure the emf of the
cell.
The iron half-cell is connected to the standard hydrogen electrode internally by means of
a salt bridge to allow exchange of ions without mixing of the two solutions in the half-
cells.
The temperature of the solution is maintained at 298K
Since the standard hydrogen electrode has a standard electrode potential of , the
reading on the voltmeter/ potentiometer is the standard electrode potential of the iron
electrode.
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NOTE:
(i) The emf of the cell is measured without passing any current so that the
composition of the chemicals in the cell is not changed.
(ii) The salt bridge consists of a bent glass tube containing some inactive solution
such as saturated potassium chloride or a folded filter paper saturated with
potassium chloride.
(iii) A standard hydrogen electrode is not easy to use because it is bulky, slow to
reach equilibrium and susceptible to presence of impurities. It is also not easy to
maintain a stream of hydrogen at 1 atmosphere.
(iv) Electrode potentials of other metals are measured in the same way
(v) A porous partition may be used instead of a salt bridge

Factors affecting magnitude of electrode potential

When a metal rod is dipped or a gas is bubbled in/through a solution of its ions, it
undergoes the energy changes. First, it‟s converted to free gaseous atoms. Electrons are

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

then removed from the gaseous atoms to form gaseous ions. The gaseous ions then
combine with water molecules to form hydrated ions. The energy changes involved are
summarized below for a divalent metal, ;

→ → →
Therefore the enthalpy change associated with the reaction;

Therefore the factors that affect the magnitude of electrode potential include;
(i) Atomization energy
(ii) Ionization energy
(iii) Hydration energy
(iv) Concentration of the solution of the electrolyte

Note that any endothermic process decreases the electrode potential (makes it less
negative or more positive) and any exothermic process increases the electrode potential
(makes it more negative or less positive.
(i) Atomization energy
Atomisation energy is endothermic. The higher the atomisation energy, the lower (more
positive ) the electrode potential. This is because it becomes difficult to convert an
element into its gaseous atoms.
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(ii) Ionization energy

Ionization energy is endothermic. The higher the ionization energy, the lower (more
positive) the electrode potential. This is because it becomes difficult to form gaseous ions
from gaseous atoms.
(iii) Hydration energy.
Hydration is an exothermic reaction. The higher the hydration energy the higher(more
negative ) the electrode potential. This is because more energy is given off when gaseous
ions are completely surrounded by water molecules.

Variation of electrode potential in group II and period 3

1. The table below shows the standard electrode potential values of Group II
elements.

Element Be Mg Ca Sr Ba
-1.70 -2.37 -2.87 -2.89 -2.90

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Standard electrode potential( ) (Volts) for

(a) Name with reasons;

(i) the strongest reducing agent
(ii) the weakest reducing agent
(b) Explain the general trend in standard electrode potential of the elements
(c) explain why beryllium has an abnormally less negative value

(a) (i) Barium (but not Ba) Because it has the most negative standard electrode potential
(ii) Beryllium (but not Be) Because it has the least negative standard electrode potential

(b) Standard electrode potential generally becomes more negative from beryllium to
barium because ionic radius increases, ionisation energy decreases, atomisation
energy decreases and hydration energy also decreases. However, the decrease in
ionisation energy and atomisation energy is more rapid than decrease in hydration
energy.
(c) Beryllium has an abnormally less negative value because the beryllium ion has the
smallest ionic radius, highest charge density and highest polarising power, thus
attracting many water molecules, giving off highest amount of hydration energy that
counterbalances its high positive ionization energy and its high atomisation energy.
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2. The table below shows the standard electrode potential values of some of the
elements in Period 3 of the Periodic Table.

Element Na Mg Al Cl
Standard electrode potential( ) (V) for -2.71 -2.37 -1.66 +1.36

(a) State;
(i) the factors that affect the magnitude of standard electrode potential
(ii) with a reason, name the strongest reducing agent
sodium because it has the most negative standard electrode potential
(iii) with a reason, name the strongest oxidizing agent
chlorine because it has a positive standard electrode potential
(a) Explain the trend in standard electrode potential of the metallic elements
Standard electrode potential becomes less negative(decreases) from sodium to

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

aluminium because ionic radius decreases, ionization energy increases, atomization
energy increases and hydration energy also increases. However, the increase in
ionization energy and atomization energy is more rapid than increase in hydration
energy.
3. Although standard electrode potentials of alkali metals and alkaline earth metals
become more negative down the groups, the standard electrode potentials of
Lithium and beryllium are most negative in the respective groups.

ELECTROCHEMICAL CELLS
An electrochemical cell is a cell that converts chemical energy into electricity. Examples
of electrochemical cells include a Daniel cell, dry cells, Lead-acid battery cell and fuel
cells.
The cell consists two metal/ metal ion convention half cells.
Metal/ metal ion convention cells (RHE and LHE)
When a metal rod is dipped in a 1 molar solution of its ions, the cell generated is called a
half cell.
A magnesium half-cell is made by dipping a pure magnesium rod in a 1M solution of
magnesium ions ( for example a 1M magnesium sulphate solution) at 298K. The
magnesium half-cell is represented as

A silver half-cell is made by dipping a pure silver rod in a 1M solution of silver ions ( for
example a 1M silver nitrate solution) at 298K. The silver half-cell is represented as;
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The Magnesium half cell

Magnesium rod

1M solution of magnesium ions.

The Silver half cell

Silver rod
+
+
+

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

1M solution of silver ions.

To construct an electrochemical cell, the two half cells above are made by dipping the
metal rods in 1 molar solution of their ions in separate beakers.
The two half cells are then connected using electric wires to connect the metal rods via a
high resistance voltmeter.
A salt bridge is used to complete the internal circuit and allowing the movement of ions
between the two half-cells so that ionic balance is maintained.

How do you come up with the conventional arrangement of the cell?

The reduction equations and reduction potentials for the half-cells can be represented by
the following half-equations:

The relative values of these voltages show that ions are more difficult to reduce
than ions. So ions will accept electrons from the half-cell
and magnesium will lose electrons to the half-cell.
By convention, the electrode with a negative standard electrode potential constitutes
the Left Hand Electrode (LHE). This electrode is also called the negative electrode or
the anode.
The electrode with a positive standard electrode potential constitutes the Right Hand
Electrode (RHE). This electrode is also called the positive electrode or the cathode.
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The electrochemical cell can be drawn as shown below:

Flow of electrons
Voltmeter

Magnesium rod Silver rod

(anode(-)) Salt bridge (cathode(+))

1M magnesium
1M Silver
sulphate
nitrate solution
solution

If a porous partition is used instead of a salt bridge, then the cell has the structure
below:

Porous partition

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Magnesium rod Silver rod
(anode(-)) (cathode(+))

1M magnesium 1M Silver
sulphate nitrate solution
solution

Construction of a Daniel cell

A Daniel cell consists of a zinc half-cell made by dipping a pure zinc rod in a 1M
solution of zinc ions and a copper half-cell made by dipping a pure copper rod in a 1M
solution of copper(II) ions in separate beakers at 298K.
The two half cells are then connected using electric wires to connect the metal rods via a
high resistance voltmeter.
A salt bridge is used to complete the internal circuit to allow the movement of ions
between the two half-cells without the two solutions mixing.
The zinc electrode constitutes the Left Hand Electrode and the copper electrode
constitutes the Right Hand Electrode.
Electrons move from zinc rod to copper rod. The sulphate ions move from the cathode to
the anode to maintain the charge balance throughout the cell
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The Structure of the Daniell cell:

High resistance voltmeter

Porous partition
Zinc rod (-) Copper rod (+)

1M Zinc sulphate 1M Copper(II) sulphate

solution solution

The cell notation/cell convention

Symbolic representation used to represent an electrochemical cell is called the cell
notation.
The following steps are followed to come up with a cell notation of any cell:

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

1. Make sure the electrode potentials given are reduction potentials. i.e. The equations
show reduction( electrons on left hand side). If instead oxidation potentials are
given, reverse the reactions to make them reduction equations and also the sign of
electrode potential. For example;

The electrode potentials given above are reduction potentials and require no
changes.

The electrode potentials given above are oxidation potentials and both equations
and the values should be reversed to make them reduction reactions and potentials
as shown below;

Recall:
OIL RIG – Oxidation is loss of electrons, Reduction is gain of electrons
LEORA says GEROA- loss of electrons is oxidation (Reducing agent). Gain of
electrons is reduction (Oxidising agent)
In some cases, one electrode potential can be given as reduction and the other
oxidation. In such a case, only one equation is reversed.
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2. Identify the reaction that takes place at the anode (left hand electrode, negative
electrode) and the cathode (right hand electrode, positive electrode). Use the table
below to guide you.
Given two reduction potentials and equations;

One reduction potential Negative electrode potential Represents reaction at

positive and one negative anode(LHE)
Positive electrode potential Represents reaction at
cathode(RHE)
Less positive electrode Represents reaction at
Both reduction potentials potential anode(LHE)
positive More positive electrode Represents reaction at
potential cathode(RHE)
More negative electrode Represents reaction at
Both reduction potentials potential anode(LHE)
negative

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Less negative electrode Represents reaction at
potential cathode(RHE)
3. After step 2, write down the equation at the anode (negative electrode) and equation
at the cathode (positive electrode). Equation at the anode should be oxidation (gain
of electrons)and that at the cathode should be reduction(loss of electrons)
RED CAT and AN OX- Reduction occurs at the cathode, Anode is for oxidation.

Consider the reactions;

Following step 2 shows that;

Anode(LHE)
Cathode(RHE)
Equation at anode (oxidation reaction) is
Equation at cathode (reduction reaction) is
4. Write cell notation following the following guidelines;
(i) Use a vertical line to separate different phases e.g. (aq) from (s) , (s) from
(l), (aq) from (g) or (s) from (g). However, (l) and (aq) are the same phase
and cannot be separated by a line.
(ii) Use a comma to separate similar phases e.g (s) from(s) or (aq) from (l)
(iii) Double vertical lines show the salt bridge
(iv) The anode is written on the left and the cathode on the right
(v) For half-cells that do not contain a solid metal electrode, platinum, is
introduced as an inert electrode.
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Using the equations above, the cell notation is:

𝑷𝒕 𝒔 𝑺𝒏𝟐 𝒂𝒒 𝑺𝒏𝟒 𝒂𝒒 𝑩𝒓𝟐 𝒍 𝑩𝒓 𝒂𝒒 𝑷𝒕 𝒔

The cell notation, if well written can guide you on how to draw a well labelled diagram
of the electrochemical cell.
More examples
1. The standard electrode potentials of two half cells are given below.

(a) Write ionic equation for the:

(i) reaction at the cathode
(ii) reaction at the anode
(iii) overall equation for the reaction

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(b) Write the cell notation for the cell made by combining the two half cells.
Hint: The negative electrode potential shows the reaction that will take place at the anode,
where oxidation (loss of electrons) should occur. The other reaction obviously should occur at the
cathode and should be reduction (gain of electrons)

(a) (i)
(ii)
( )

(iii)
(b)

2. The Daniell cell has copper and zinc half cells as shown below:

(a) Write ionic equation for the:

(i) reaction at the negative electrode
(ii) reaction at the positive electrode
(iii) overall equation for the reaction
(b) Write the cell notation for the Daniell cell.

Hint: The negative electrode potential shows the reaction that will take place at the negative
electrode (anode), where oxidation (loss of electrons) should occur.

(a) (i)
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(ii)

(iii)
(b)

3. The electrode potentials of some half cells are given below.

(a) Write ionic equation for the:

(i) reaction at the cathode
(ii) reaction at the anode
(iii) overall equation for the reaction
(b) Write the cell notation for the cell made by combining the two half cells.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Hint: The electrode potentials given are oxidation potentials as there in increase in oxidation state in
each case. Standard reduction potentials should be obtained first reversing the equations and the
symbols of the electrode potentials too.

(a) (i)
(ii)
(iii)
(b)

The platinum electrode is introduced as an inert electrode in the cathode half-cell because
there is no solid metal electrode.

4. The convention of a cell is given below

.
(a) Write equation for the half-cell reaction at the:
(i) anode
(ii) cathode
(b) Write the overall equation for the cell reaction
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Hint: When the cell notation is already given, well balanced half-cell equations are written directly
from it.

(a) (i)
(ii)
(b)

Calculation of cell emf and prediction of spontaneity/feasibility of a

reaction
The emf of a cell, is given by the expression;

The values substituted in the above expression must be reduction potentials.

The final answer should have a charge which should never be a superscript or subscript.
Wrong answers Correct answers

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

-
-1.20, 1.20V, -1.20V
+0.45, +0.45V, +0.45V

 If the calculated value of emf is positive, the reaction is spontaneous/ feasible

 If the calculated value of emf is negative, the reaction is not feasible
Examples
1. The standard electrode potential for some half cells are shown below:

(a) What is meant by the term standard electrode potential

(b) (i) Write the cell convention and the equation for the overall reaction that
occurs when electrode potentials in (a) are combined.
(ii) Calculate the overall electrode potential for the cell
(iii) State whether the reaction in b(i) is feasible or not. Give a reason for
your answer.
Hint: Electrode potentials are both positive. The less positive electrode potential shows the
reaction that will take place at the anode, where oxidation (loss of electrons) should occur. The other
reaction obviously should occur at the cathode and should be reduction (gain of electrons)
(b) (i)
Overall equation;
(ii)
(iii) The reaction is feasible, because the emf of the cell is positive.
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2. The standard electrode potential for some half cells are shown below:

(a) Write the:

(i) cell convention
(ii) equation for the reaction that takes place at the anode and cathode
(iii) equation for the overall cell reaction
(b) (i) Calculate the emf of the cell.
(ii) State whether the reaction in a(iii) is feasible or not. Give a reason for
your answer.
(a) (i)
(ii)

(iii)
(b) (i)

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(ii) The reaction is feasible because the emf of the cell is positive.

3. The standard electrode potential for some half cells are shown below:

(a) Write the cell notation

(b) Calculate the emf for the cell
(c) State whether the cell reaction in (a) is feasible or not. Give a reason for
your answer.
Hint: The negative electrode potential shows the reaction that will take place at the anode.
The other reaction obviously should occur at the cathode and should be reduction (gain of electrons)
(a)
(b)
(c) The reaction is feasible, because the emf of the cell is positive.

4. A galvanic cell consists of the following electrodes.

At 25℃, the emf of the cell was found to be .

(i) Write the overall cell equation
(ii) Calculate the standard electrode potential for the
electrode.
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Note; The reactions given are already reactions at the electrodes. However for calculations, the
electrode potential at the LHE should be made a reduction one.

(i)
(ii)

Gibb’s free energy, , as a measure of spontaneity

The Gibb‟s free energy, of a cell is given by the expression;

where is number of electrons taking part in the process

is the Faraday‟s constant
is the emf of the cell
 The value of n is simply the number of electrons involved in writing the overall
reaction.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

 If the calculated value of is negative, the reaction is spontaneous/ feasible
 If the calculated value of is positive, the reaction is not feasible
 Gibb’s free energy is also a measure of maximum useful work done by the cell.
Examples
1. The electrode potentials of and are
and respectively.
(a) Write an equation for the reaction that occurs at the:
(i) anode
(ii) cathode
(b) Write the:
(i) cell notation
(ii) overall cell reaction
(c) Calculate the :
(i) emf of the cell generated from the cell reaction in c(ii) above.
(ii) Gibb’s free energy for the cell
(iii) State whether the above cell reaction is feasible or not. Give a reason
for your answer.

(a) (i)
(ii)
(b) (i)
(ii)
(c) (i)
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(ii)
(iii) The reaction is feasible because the value of Gibb’s free energy of the cell is
negative.

2. The convention of a cell was set up as shown below

.
(a) Write equation for the half-cell reaction at the:
(i) anode
(ii) cathode
(b) Write the overall equation for the cell reaction.
(c) The reduction potentials for the reactions in (a)(i) and (ii) above respectively
are and respectively. Predict the spontaneity of the cell
reaction.
(a) (i)
(ii)

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(b)
(c)

Since the emf of the cell is negative, giving a positive value of Gibb’s free energy, the reaction
is not spontaneous.

Applications of electrode potentials

(i) Predicting feasibility of a reaction
(ii) Calculating emf of electrochemical cells
(iii) Determining equilibrium constant
(iv) Determining solubility of a sparingly soluble salt.

Questions
1. The diagram below shows an electrochemical cell designed to calculate the standard
electrode potential of zinc.

(a) Name the apparatus labeled A and state a characteristic it should have
(b) (i) Name B and state its purpose.
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(ii) State how part B is prepared

(c) Identify C
(d) Name part D and explain its function.
(e) State three standard conditions for measuring of standard electrode potential.
2. The figure below shows a voltaic cell set up between two electrodes

Zinc
1M Iron(III) chloride solution
1M Zinc sulphate solution

Platinum
(a) (i) Define the term voltaic cell

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(ii) Name Y and state its role in the above set up
(b) The reading on the voltmeter above was volts.
(i) Write the equation for the redox reaction that takes place
(ii) State whether the reaction in b(i) is feasible . Give a reason for your
answer.
(c) Calculate the electrode potential of the left hand electrode if the electrode potential
of the right hand electrode is
(d) Write the cell convention of the voltaic cell above.
3. Calculate the emf, write the cell notation, equation at each electrode and overall
equation for each of the following cells
(a)

(b)

(c)

(d)

(e)

(f)
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(g)
̅
(h)

4. (a) State factors that can affect standard electrode potential of an element.
(b) The standard electrode potential for group II elements are given in the table below
Element Be Mg Ca Sr Ba
Electrode potential
(i) State and explain the trend in variation of standard electrode potential
(ii) Explain why the values of standard electrode potentials are negative
(c) Electrode potentials for some half cells are given below:
Half cell

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(i) Write the equations for the reactions that take place at anode and cathode
(ii) Write the overall cell reaction
(iii) Calculate the emf of the cell
(d) State whether the reaction in c(iii) is feasible or not. Give a reason for your
answer.
5. Calculate the standard electrode potential of the electrode if the
electrode potential of the cell given below is . .

6. Two half cells are given below where combined:

(a) State which half-cell is suitable to make the:

(i) negative electrode
(ii) positive electrode
(b) Write the equation for the cell reaction.
(c) If the emf of the cell is and . Calculate the
standard electrode potential for the cobalt half-cell.
7. Equations for some half-cell reactions are given below.

(a) Write the convention for the cell.

(b) Write equation for the overall reaction.
(c) Calculate the cell voltage.
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8. Half equations for some cell reactions and the electrode potentials are given below:

(a) Write:
(i) the cell notation of the cell formed when the half cells are combined.
(ii) the overall cell reaction
(b) Calculate the emf of the cell
(c) Predict the feasibility of the reaction and give a reason for your answer.
9. The standard electrode potentials for some half cell reactions are given below:

(a) Write the overall equation for the cell reaction that occurs when the half cells are
combined.
(b) (i) Calculate the Gibbs free energy for the cell reaction.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(ii) State whether the cell reaction is feasible or not and give a reason for your
answer.
10. (a) Explain what is meant by the terms
(i) standard electrode potential
(ii) standard hydrogen electrode
(b) The standard electrode potentials for some half-cells are shown below.
Half cell

State what is observed at the:

(i) positive electrode
(ii) negative electrode
(c) Write:
(i) the cell convention for the combined cell
(ii) the equation for the cell reaction that would take place if the half cells are
combined.
(d) Calculate;
(i) the electrode potential for the cell
(ii) the work done by the cell
11. The following half-cell reactions are given:
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(a) Write the cell notation for the cell formed by combining the two half cells.
(b) State what will be observed and write equations for the reactions that take place at:
(i) anode
(ii) cathode
(c) Calculate the emf of the cell.
12. The standard electrode potentials for some half cells, in volts are shown below:
A.
B.
C.
D.
E.
F.
G.
H.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(a) State the species that is the most powerful oxidizing agent and give a reason for
your answer.
(b) State what would be observed and write equation for the reaction that would take
place if the half cells:
(i) A and E are connected
(ii) B and G are connected
(c) Calculate the emf of the cell in a(i)
(d) Write the cell notation for the cell in (b)(ii) above
(e) Explain why hydrochloric acid is not used to acidify titrants in volumetric
analysis involving potassium manganate(VII) solution.
(f) Write the cell convention when half cells C and D are combined.
13. (a)(i) Distinguish between electrolytic conductivity and molar conductivity of
a solution.
(ii) Write the equation to show the relationship between electrolytic
conductivity and molar conductivity of a solution.
(b) The table below gives the molar conductivity of a solution of ethanoic acid at
298K.
[ ] 0.001 0.01 0.1
Molar conductivity 50 16 5
(i) Give a reason for the decreasing values of molar conductivity of ethanoic acid
with increase in concentration.
(ii) Calculate the and ionization constant, of 0.01M ethanoic acid.
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(The molar conductivity of ethanoic acid at infinite dilution is

)
(c) (i) Define the term standard electrode potential.
(ii) Discuss the factors that affect the value of standard electrode potential.
(iii) State two applications of standard electrode potential.
(d) The standard electrode potentials of systems, and
are and respectively.
(i) Write equation for the overall cell reaction.
(ii) Calculate the maximum energy obtained from the cell.

14. (a) State three factors which determine the magnitude of electrode potential of a metal
(b) The standard electrode potentials for the following reactions are given

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

Write;
(i) the cell notation for the cell formed when the two half cells are connected.
(ii) the equation for the overall cell reaction
(c) (i) Calculate the emf of the cell.
(ii) What deduction do you make from your answer in (c)(i)?
(d) When dilute sulphuric acid is added to copper(I) oxide, a brown solid and a pale blue
solution were formed. Explain the observation.
15. The standard redox potentials of and are
and respectively.
(a) Write the cell convention for the combined cell
(b) Write an equation for the half-cell reaction at the:
(i) cathode
(ii) anode
(c) Write the overall cell reaction equation.
(d) State two conditions under which the electrode potentials above are measured
(e) Deduce if the overall reaction is feasible or not. Give a reason for your answer.
(f) State one application of electrode potentials
16. The standard electrode potentials for some systems are given below:

(a) Write the convention for the cell

(b) Write the equation for the overall reaction
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(c) (i) Calculate the cell voltage

(ii) What conclusion can you draw from the emf value in c (i) above
17. The standard electrode potentials of lead and magnesium are given below:

(a) Write the convention for the cell that can be formed
(b) Write the equation;
(i) for the reaction taking place at each electrode
(ii) for the overall reaction
(c) Calculate the emf of the cell
18. (a) (i) Define the term standard electrode potential.
(ii) Give reasons why it is not possible to measure standard electrode potential
absolutely.
(iii) Explain the factors that affect the value of standard electrode potential.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

(b) Describe:
(i) the structure of a standard hydrogen electrode.
(ii) how you would measure standard electrode potential of magnesium in a
solution of its ions.
(c) The standard electrode potential of copper and zinc are given below.

Write the cell notation for a zinc-copper cell and calculate the emf of the cell.
(d) State two ways by which an electrolytic cell differs from an emf cell.
19. Given the following electrode potentials.

(a) Arrange the electrodes in order of reducing power starting with the least reducing
(b) (i) Which two electrodes will form a cell of maximum emf ?
(ii) Write the cell notation for the cell you gave in b(i) above.
(iii) Write the overall cell reaction for the cell in b(i).
20. (a)(i) What is meant by the term “standard electrode potential”?
(ii) Write down the factors that affect the magnitude of standard electrode
potential.
(b) (i) With the aid of a labeled diagram, describe how the standard electrode potential
of a metal can be measured.
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(ii) State two applications of standard electrode potentials.

(c) Some half equations and their standard electrode potentials are given below:

(i) Name the species that is the strongest reducing agent. Give a reason for
your answer.
(ii) Write the cell notation of the cell made by combining half cells of
dichromate(VI) and chlorine and calculate the emf of the cell. Draw a well
labeled diagram for the cell arrangement.
(iii) Calculate the energy given out by the cell in (c)(ii) above. Comment on
your answer.
(iv) Using the standard electrode potentials given, explain why hydrochloric
acid cannot be used to acidify aqueous manganate(VII) solutions.

DEMYSTIFYING PHYSICAL CHEMISTRY | by Joseph Jobs Kayiira

21. Draw a well labeled diagram of a half cell consisting of;
(a) a half-cell and a half-cell.
(b) a half-cell and a half-cell.
22. (a) The molar conductivity of a carboxylic acid, at infinite dilution at ℃
is and the acid dissociation constant, .
(i) Define the term molar conductivity
(ii) Calculate the molar conductivity of a 0.01M solution of .
(b) The zinc/ silver oxide cell used in hearing aids and electric watches has the
following electrode potentials.

̅
(i) Calculate the emf of the zinc/silver oxide cell
(ii) Write the overall redox reaction that generates the emf calculate in b(i) above
(iii) Draw a well labeled diagram to show the zinc/ silver oxide cell can be set
up and the emf measured.
23. (a) State and discuss three factors that affect the value of standard electrode potential
(b) Draw a well labeled diagram to show how the standard electrode potential of the
zinc electrode can be determined.
(c) The electrode potentials of some half cells are given below;

Write the:
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(i) cell notation for the cell formed when the two half cells are combined.
(ii) equation at the anode, cathode and overall cell reaction.
(d) Calculate the emf of the cell in (c)(i)
(e) (i) State Faraday‟s law of electrolysis.
(ii) How long will it take of hydrogen at room temperature and
pressure when acidified water is electrolyzed using a current of .
Assignment:
Batteries
 Research, read and make notes about batteries (dry cells, mercury cell, Nickel-
Cadmium cell and fuel cells)
 Uses of batteries
 Explain the functioning of a battery
 Explain the conversion of one form of energy to another

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