REVIEW ON GENERAL CHEMISTRY

Chemistry- a science that deals with the properties, composition and structure of
substances (elements and compounds), the reactions and transformations they undergo,
and the energy released or absorbed during those processes.

A. THE BRANCHES OF CHEMISTRY

1. Inorganic Chemistry- the study of all the elements and their compounds with the
exception of carbon and its compounds, which fall under the category of organic
chemistry. Inorganic chemistry investigates the characteristics of substances that are
not organic, such as nonliving matter and minerals found in the earth’s crust.

2. Organic Chemistry- the study of the structure, preparation, properties, and

reactions of carbon compounds.

3. Biochemistry- the study of the substances and chemical processes that occur in
living organisms. It includes the identification and quantitative determination of the
substances, studies of their structure, determining how they are synthesized and
degraded in organisms, and elucidating their role in the operation of the organism.

4. Physical Chemistry- the study of the properties and behavior of chemical systems
primarily by physical theory and technique, as, for example, the thermodynamic
analysis of macroscopic chemical phenomena.

5. Analytical Chemistry- the branch of chemistry dealing with techniques that yields
any type of information about chemical systems.

6. Nuclear Chemistry- the study of the atomic nucleus, including fission and fusion
reactions and their product.

7. Others (Environmental Chemistry…etc…)

ANALYTICAL CHEMISTRY is divided into two branches:

1. Qualitative Chemistry deals with qualifying or identifying elements in an
unknown sample of matter.
2. Quantitative Chemistry deals with quantifying the elements present in an
unknown sample of matter.
 Matter
Compounds

Substances Mixtures

Elements Compounds Homogeneous Heterogeneous

Organic Inorganic

Metals Metalloids Nonmetals

B. THE LANGUAGE OF CHEMISTRY

DEFINITION OF IMPORTANT TERMS:

1. Chemical Nomenclature- the system of naming substances. The standards of

nomenclature are established by the IUPAC (International Union of Pure and
Applied Chemistry).

2. Chemical Formula- a notation that uses atomic symbols with numerical

subscripts to convey the relative proportions of atoms of the different elements in
a substance.

3. Chemical Symbol- the symbolic representation of elements; consists of either on

or two letters.

4. Chemical Compound- a substance formed from two or more elements.

5. Chemical Reaction- a process in which one or more substances are converted

into other substances; also called chemical changes.

6. Chemical Equation- a representation of a chemical reaction using the chemical

formulas of the reactants and the products. A balanced chemical equation contains
equal numbers of atoms of each element on both sides of the equation. In
balancing chemical equations, fractions can be used.
 7. Oxidation Number- a positive or negative whole number assigned to an element
in a molecule or ion on the basis of a set of formal rules. To some degree, it
reflects the positive or negative character of that atom. It is also referred to as
oxidation state.

8. Radical- a group of atoms that behave like a single atom. It is also called as
polyatomic ions.

9. Stoichiometric Coefficients- the coefficients used to balance an equation.

C. RULES IN WRITING FORMULA

1. A compound may be assumed to consist of a positive and a negative part. The

following combinations are possible:
POSITIVE NEGATIVE EXAMPLE
Element Element NaCl
Element Radical CaSO4
Radical Element (NH4)2O
Radical Radical C2H5C2H3O2

2. The convention is to write the symbol of the positive part before the symbol of the
negative part.

Example: Na+1 Cl-1→ NaCl Mg+2 O-2→MgO

Except: P-3 H+1 → PH3, N-3 H+1 →NH3

3. Since a compound is always neutral, i.e., the algebraic sum of the oxidation state
is always zero, the parts must be combined in such a ratio that the net oxidation
state is zero. To do this, crisscross the valences. The valence of the positive part
becomes the subscript of the negative part and the valence of the negative part
becomes the subscript of the positive part.
Example: Al+3 O-2 →Al2O3

4. Where the subscript is supposed to be one (1), it is no longer written after the
symbol. It is understood that there is only one atom of the element or a unit of the
radical present.
Example: Incorrect: Na1Cl1
Correct: NaCl

5. Since a compound shows the smallest whole number ratio in which the positive
and the negative parts are combined;

a. Omit writing subscripts whenever subscripts (by rule 3) are numerically

equal.
 Example: Mg2O2 → MgO

Except: Peroxide (O2-2) → H2O2

b. Whenever possible, reduce the subscripts to the simplest whole number

ratio. Be sure not to alter the correct formula of any radical.

Example: Si+4O-2 → SiO2

NH4+1O-2 → (NH4)2O

6. Whenever a radical needs a subscript (other than 1), enclose it first with a
parenthesis. If the original already contains a parenthesis, use a bracket.

Example: (NH4)2SO4 Fe2(CrO4)3 Ca3[Fe(CN)6]2

D. RULES IN NAMING COMPOUNDS

1. BINARY COMPOUND (+, -IDE)

A binary compound is one that contains only two different elements. To name,
give the name of the positive element and change the last letters of the negative
element to IDE.

Example: NaCl – SODIUM chlorIDE K2O – POTASSIUM oxIDE

CaF2 – CALCIUM fluorIDE AlBr3 – ALUMINUM bromIDE

2. COMPOUND WHOSE POSITIVE PART IS MULTIVALENT (can exist in

more than one oxidation state) may be named in such a way as to distinguish
between the two compounds composed of the same element by:

a. The Old Method – the use of the suffix OUS if the element exists in the lower
oxidation state and the suffix IC if the element exists in the higher oxidation state.
Latin names or Latin stems may be used; (Applicable only when the cation is a
metal)

Cu – cuprum Fe – ferrum Au – aurum Pb – plumbum

Ag – argentum W – wolfram Sn – stannum Sb – stibium
b. The Stock Method - the name of the positive element is given followed by its
oxidation state written in Roman numerals and enclosed in parenthesis and then
the name of the negative part with its last letters changed to IDE. (Applicable for
metal or nonmetal cation).

COMPOUND OLD METHOD STOCK SYSTEM

Hg2O mercurOUS oxIDE MERCURY (I) oxIDE
HgO mercurIC oxIDE MERCURY (II) oxIDE
FeCl2 ferrOUS chlorIDE IRON (II) chlorIDE
FeCl3 ferrIC chlorIDE IRON (III) chlorIDE
PbO plumbOUS oxIDE LEAD (II) oxIDE
Pb2O plumbIC oxIDE LEAD (IV) oxIDE

c. Stoichiometric Proportions – may be denoted by the use of the Greek or Latin

prefixes (mono, di, tri, tetra, penta, hexa, hepta, octa, nona, deca, undeca, dodeca).
This indirectly indicates also the oxidation state of the positive element.
(Applicable only when the cation is a nonmetal).

COMPOUND NAME
CO carbon MONOxide
CO2 carbon DIoxide
NO2 nitrogen DIoxide
N2O4 DInitrogen TETRoxide
PCl5 phosphorous PENTAchloride
PCl3 phosphorous TRIchloride
P2O5 DIphosphorous PENToxide
P2O3 DIphosphorous TRIoxide

3. ACIDS – compounds that corrode metals; tastes sour; turns blue litmus paper to
red; has a pH range from 1-6.

a. Binary Acids – an acid composed of hydrogen and a negative element. To

name, use the prefix HYDRO and the suffix IC for the negative element,
then followed with the word ACID. (H+, element)

HCl – HYDROchlorIC ACID HBr – HYDRObromIC ACID

H2S – HDROsulfurIC ACID

b. Oxyacid – an acid that contains oxygen in the radical. To name, use the
suffix IC for the acid-forming element or radical followed by the word
ACID.

H2CO3 – carbonic ACID H2C2O4 – oxalic ACID

c. Oxyacid whose acid-forming element is multivalent – use the suffix

OUS for the acid-forming element if it occurs in the lower state and IC if
in the higher oxidation state followed by the word ACID. (H+, radical with
oxygen).

HNO2 – nitrOUS ACID HNO3 – nitric ACID

d. If more than two acids can be formed from the same elements because
of Multivalency – use the prefix HYPO for the lowest oxidation state and
PER for the highest oxidation state followed by the word ACID.
HClO – HYPOchlorous ACID HClO3 – chlorIC ACID
HClO2 – chlorOUS ACID HClO4 - PERchloric ACID
 4. Salts of Oxyacids – H+ of Oxyacid is replaced by a metal cation. To name, give
the name of the positive element or radical and follow it with the name of the
negative radical.

K3PO4 – potassium phosphate (NH4)2CrO7 – ammonium dichromate

5. Bases – compound that burns the skin; tastes bitter; turns red litmus paper to blue;
has a pH range from 8-14. To name, give the name of the positive element or
radical and follow with the name of the negative radical HYDROXIDE.

NaOH – sodium HYDROXIDE Ca(OH)2 – calcium HYDROXIDE

E. CHANGES IN MATTER

1. Physical Change – a change in matter which does not alter the chemical
properties of matter.

Example: carving of wood

2. Chemical Change - a change in matter that transforms a substance into a

chemically different substance. It is also known as chemical reaction.

Example: Burning of wood

a. Indicators of chemical change or chemical reaction

(1) Formation of precipitate

(2) Evolution of gas or formation of bubbles
(3) Disappearance of reactants and formation of new products
(4) Evolution of heat and light
(5) Change in color
(6) Production of mechanical energy
(7) Production of electrical energy
b. Types of Chemical Reactions

Any chemical reaction or change may be classified as one of the

following reaction type:

(1) Direct Combination or Synthesis – a type of reaction

wherein a single more complex product is formed by the
combination of two or simpler substances. Generally
represented as:

A + B → AB
CaO + HOH → Ca(OH)2
2Na + Cl2 → 2NaCl
 (2) Decomposition or Analysis - a reaction wherein a
compound is broken down into two or more simpler
substances. Generally represented as:

AB → A + B
2KClO3 → 2KCl + 3O2
CaCO3 → CaO + CO2

↑ - evolution of gas
↓ - formation of precipitate
∆ - heat or electricity
(3) Single Displacement – a reaction wherein an element or
an ion displaces another element or ion in a compound.
Generally represented as:

AB + C (metal) → CB + A
2HCl + Mg → MgCl2 + H2↑

AB + C (nonmetal) → AC + B
4CH3 + 7O2 → 4CO2 + 6H2O
(4) Double displacement or Metathesis – a reaction wherein
compounds interchange ions and radicals. Compounds
exchange positive and negative parts and results in the
formation of different compounds. Generally represented
as:

AB + CD → AD + CB
AgNO3 + NaCl → AgCl + NaNO3

F. CHEMICAL EQUATION – a shorthand representation of a chemical change

1. Methods of balancing chemical equations

a. Inspection Method – trial and error

Example: 2Na + HOH → 2NaOH + H2 ↑

H2SO4 + 2Al → Al2(SO4)3 + H2 ↑
2H3PO4 + 3Ba(OH)2 → 6HOH + Ba3(OH)2

b. Algebraic Method
Steps:
(1) Assign literal coefficients to all reactants and products.
 (2) Form algebraic equations by doing balances on each
element in the chemical equation.
(3) Choose one literal coefficient to be equated to 1. This is
done because the number of equation is less than the
number of unknowns or literal coefficients.
(4) Solve the rest of the algebraic equation.
(5) Finally, replace all literal coefficients by their equivalents
in the chemical equation.
(6) If fraction appears, eliminate them by multiplying the
whole chemical equation by the LCD of all fractions.

Example: HNO3 + H2S → S + NO + H2O

a HNO3 + b H2S → cS + d NO + e H2O

H bal: a + 2b = 2e → eqn. 1
N bal: a = d → eqn. 2
O bal: 3a = d + e → eqn. 3
S bal: b = c → eqn. 4
Let a = 1

in eqn. 2 in eqn. 3 in eqn. 1 in eqn. 4

a=d 3a = d + e a + 2b = 2e b = c
d=1 3(1) = 1 + e 1 + 2b = 2(2) c = 3/2
e=2 b = 3/2

2[1HNO3 + 3/2H2S → 3/2S + 1NO + 2H2O]

Ans. 2HNO3 + 3H2S → 3S + 2NO + 4H2O

MnO + PbO2 + HNO3 → HMnO4 + Pb(NO3)2 + H2O

a MnO + b PbO2 + c HNO3 → d HMnO4 + e Pb(NO3)2 + f H2O

Mn bal: a = d → eqn. 1
Pb bal: b = e → eqn. 2
O bal: a + 2b +3c = 4d + 6e + f → eqn. 3
H bal: c = 2d + f → eqn. 4
N bal: c = 2e → eqn. 5

Let a=1
in eqn. 1 eqn. 5 in eqn. 2 eqn. 5 in eqn. 4
a=d 1 + 2b + 3c = 4d + 6e + f c = d + 2f
d=1 1 + 2b + 3c = 4d + 6(c/2) + f 2e = 1 + 2f → eqn. 7
2b – f = 3 → eqn. 6
eqn. 2 in eqn. 7 eqn. 6 – eqn. 7 in eqn. 4
2e = 1 + 2f 2b - f = 3 c=d+f
2b = 1 + 2f → eqn. 8 2b – 2f = 1 c = 1+2(2)
0+f=2 c=5
f=2

in eqn. 6 in eqn. 3
e=c/2 b=e
e=5/2 b=5/2

2[1 MnO + 5/2 PbO2 + 5 HNO3 → 1HMnO4 + 5/2 Pb(NO3)2 + 2 H2O]

Ans. 2 MnO + 5 PbO2 + 10 HNO3 → 2HMnO4 + 5 Pb(NO3)2 + 4 H2O

c. Redox Method

Reduction – process where an atom gain e- resulting to decrease in the

atom’s oxidation number

Oxidation - process where an atom gives up e- resulting to increase in

the atom’s oxidation number

Note: Reduction and Oxidation occur simultaneously, one could not

happen without the other.

Steps:
(1) Assign the oxidation number of all elements in the given equation.
(2) Look for those elements that changed in oxidation number. There
are at least two; one undergoes reduction and the other undergoes
oxidation. If there are more than two elements, it is a multiple redox
equation.
(3) Write the partial ionic equation of the element referred to in b.
(4) Balance the ionic equation as to:
(a) number of atoms
(b) number of charges (you may only add e)
(5) Balance the number of e- in (2).
(6) Balance the rest of the overall equation by inspection with H and O
the last ones to be balanced.

Example:
2 + 12 – 14 = 0 4 – 4 = 0 1 + 5 – 6 = 01 + 5 – 6 = 03 + 15 – 18 = 0 2–2=0
+1 +6 - 2 +4 -2 +1 +5 -2 +1 +5 -2 +3 +5 -2 +1 -2

K2Cr2O7 + NO2 + HNO3 → KNO3 + Cr(NO3)3 + H2O

Oxidation
Reduction
12 + 6e- → 6
(2Cr+6 + 6e- → 2Cr+3) x 1
2Cr+6 + 6e- → 2Cr+3

12 → 15 + 3e-
(3N+4 → 3N+5 + 3e-) x 2
6N → 6N+5 + 6e-

1 K2Cr2O7 + 6 NO2 + ? HNO3 → 2 KNO3 + 2 Cr(NO3)3 + ? H2O

by inspection:
K bal: 2=2
Cr bal: 2=2
N bal: 6 + ? = 2 + 6;? = 2
H bal: 2 =2?; ?=1
O bal: 7 + 12 + 6=6 + 18 + 1; 25 = 25

Ans: K 2Cr2O7 + 6 NO2 + 2 HNO3 → 2 KNO3 + 2 Cr(NO3)3 + H20

Example:
1+5–6=0 2–2=0 2–2=0 2–2=0
+1 +5 -2 +1 -2 0 +2 -2 +1 -2

HNO3 + H2S → S + NO + H2O

Oxidation
Reduction
5 + 3e- → 2
(N+5 + 3e- → N+2) x 2
2 N+5 + 6e- → 2 N+2

2 → 0 + 2e-
(S-2 → 3S0 + 2e-) x 3
3S-2 → 3S0 + 6e-

2 HNO3 + 3 H2S → 3S + 2 NO ? H2O

by inspection:
N bal: 2 = 2
S bal: 3=3
H bal: 2 + 6 = 2?;? = 4
O bal: 6 = 2 + 4; 6 = 6

Ans: 2 HNO3 + 3 H2s → 3S + 2 NO + 4 H2O

 IONS AND CHARGES

CATIONS – ions which are positively charged

Ammonium NH4+1 Copper (II) Cu+2 Antimony (III) Sb+3

Copper Cu+1 Iron (II) Fe+2 Arsenic (III) As+3
Hydronium H3O+1 Lead (II) Pb+2 Bismuth (III) Bi+3
Potassium K+1 Magnesium Mg+2 Chromium Cr+3
Silver Ag+1 Manganese (II) Mn+2 Gold (III) Au+3
Sodium Na+1 Mercury (II) Hg+2 Iron (III) Fe+3
Barium Ba+2 Nickel (II) Ni+2 Platinum (III) Pt+3
Calcium Ca+2 Tin (II) Sn+2 Silicon Si+4
Carbon (II) C+2 Zinc Zn+2 Tin (IV) Sn+3
Cobalt Co+2 Aluminum Al+3 Tungsten W+6

ANIONS – ions which are negatively charged

Acetate C2H3O2-1 Cyanate CNO-1 Iodate IO3-1

Aluminite AlO2-1 Cyanide CN-1 Iodite IO2-1
Bicarbonate HCO3-1 Formate HCOO-1 Metaborate BO2-1
Bisulfate HSO4-1 Fluoride F-1 Metaphosphate PO3-1
Bisulfite HSO3-1 Hydride H-1 Metarsenite AsO2-1
Bromate BrO3-1 Hydroxide OH-1 Nitrate NO3-1
Bromide Br-1 Hypochlorite ClO-1 Nitrite NO2-1
Chlorate ClO3-1 Hypobromite BrO-1 Perchlorate ClO4-1
Chloride Cl-1 Periodate IO4-1 PermanganateMnO4-2
Chlorite ClO2-1 Thiocyanate SCN-1 Argenticyanide Ag(CN)2-1
Carbonate CO3-2 Stannite SnO2-2 Borate BO3-3
Chromate CrO4-2 Sulfate SO4-2 Ferricyanide Fe(CN)6-3
Dichromate Cr2O7-2 Sulfite SO3-2 Nitride N-3
Manganate MnO4-2 Tetraborate B4O4-2 Phosphide P-3
Metasilicate SiO3-2 Tetrathionate S4O6-2 Phosphate PO4-3
Molybdate MoO4-2 Thiosulfate S2O3-2 Phosphite PO3-3
Oxalate C2O4-2 Zincate ZnO2 -2
Ferrocyanide
Fe(CN)6-4
Oxide O-2 Aluminate AlO3-3 Orthosilicate SiO4-4
Peroxide O2-2 Arsenate AsO4-3 Pyroarsenate As2O7-4
Plumbite PbO2-2 Arsenite AsO3-3 Pyrophosphate P2O7-4
Stannate SnO3-2 Bismuthate BiO4-3 Silicate
SiO4-4
 COMMON ELEMENTS AND THEIR OXIDATION STATES

MONOVALENT DIVALENT MULTIVALENT

1 1 and 2 2, 3 and 4
H – Hydrogen Cu – Copper Ti - Titanium
Li – Lithium Hg – Mercury
Na – Sodium 2, 3 and 6
K – Potassium 1 and 3 Cr - Chromium
Ag – Silver Au - Gold
2, 3, 4 and 7
2 2 and 3 Mn - Manganese
Be – Beryllium Fe – Iron
Mg – Magnesium Ni – Nickel 2, 4 and 6
Ca – Calcium Co – Cobalt S - Sulfur
Sr – Strontium
Ba – Barium 2 and 4 +-1, 5 and 7
Zn – Zinc C – Carbon Cl - Chlorine
Cd – Cadmium Pb – Lead I - Iodine
Pt - Platinum
3 Si – Silicon Noble Gases:
Al – Aluminum Sn – Tin He - Helium
B – Boron Ne - Neon
3 and 5 Ar - Argon
-1 P – Phosphorous Kr - Krypton
F- Fluorine As – Arsenic Xe - Xenon
Br – Bromine Sb – Antimony Rn - Radon
Bi – Bismuth
 SOLUTIONS

Chemical reactions usually take place between two mixtures of substances

rather than between two pure substances. One common type of mixture is the solution. In
nature, most reactions take place in water solutions (aqueous solutions). The body fluids
of both plants and animals are water solutions of numerous solutions. In the human body,
the nutrients are transported in solution while waster products are removed as solutions.
In the soil, the main reactions take place in thin layers of solution adsorbed on solids,
even in desert regions. Atmosphere, oceans, lakes and soil are examples of solutions.
Solutions are about us at all times.

Solution- a homogeneous mixture of two or more substances

Components of solution:
Solute – the substance which is dissolved
Solvent – the substance that does the dissolving

Types of solutions as based on the nature of the solvent: gaseous, liquid, solid solutions

Table 1.1: Examples of different types of solutions based on the nature of the solvent

SOLUTE SOLVENT EXAMPLE

Solid Liquid Table sugar in water
Liquid Liquid Alcohol in water
Gas Liquid Shaving cream
Solid Gas Dust in air
Liquid Gas Water vapor in air
Gas Gas Oxygen is dissolved in air
Solid Solid Metal alloys
Liquid Solid Water in activated charcoal
Gas Solid Marshmallow

NOTE: The most common type of solution is the liquid solution with solid solute.

As to amount of solute (normally used for liquid solutions):

1. Unsaturated solutions – when the solution has dissolved the material
below its maximum level.
2. Saturated solutions – when no more solute can be dissolved in the solvent.
3. Supersaturated solutions – when the solute dissolved is beyond the
maximum level.
4. Dilute solution – 10% by weight or less.
5. Concentrated solution – greater than or equal to 95% by weight solute.
 Solubility of a substance refers to the maximum amount of solute that can be
dissolved in a unit amount of solvent at a given temperature or the amount of
solute needed to make a saturated solution.

Factors that affect solubility:

1. Pressure
2. Temperature
3. Nature of solute and solvent
4. Surface area

Solubility Rule:
Like dissolves like, that is, a polar solvent such as water will readily dissolve a
polar solute like NaCl and a non-polar solvent such as carbon tetrachloride will readily
dissolve a non-polar solvent such as gasoline.

 Concentration – concerns to the amount of solute dissolved in a known quantity of

solution or solvent.

Ways of Expressing Concentrations of Solutions

I. Physical methods (% by volume, % by weight, pph, ppt, ppm, ppb)
II. Chemical methods – molarity (M), normality (N), molality (m). mol fraction,
% by mol

Molarity (M) of a solution – the number of moles of a solute per liter of solution
Normality (N) of a solution – the number of equivalents of solute per liter of solution
Molality m) of a solution – the number of moles of solute per kilogram solvent

NOTES:
a) specific gravity of a substance is numerically equal to density of substance in
units of grams/ml
b) density of a dilute aqueous solution is approximately that of water which is 1
gram/ml
c) ppm of a solute in a dilute aq. sol’n = milligrams solute/liter sol’n

Additional Topics on Concentrations: DILUTION

DILUTION – the process of adding more solvent (usually water) to a concentrated

solution the purpose of which is to decrease the concentration of the solution

Illustration:
Water
↓
Concentrated Solution → mixing → Diluted Solution
V1 V2
C1 C2
Where V1, V2 – volumes of… respectively (in any units)
C2, C2 – concentrations of … respectively (in M or N)
Dilution Formula: V1C1 = V2C2
REACTION RATES AND EQUILIBRIUM

REACTION RATE – also rate of chemical reaction or velocity of a chemical reaction

- the amount of chemical change which takes place in a given interval of
time usually expressed in unit of moles of substance used up or formed
per liter of solution • unit time like:
Mole/li • sec or M/sec

Example: Find the reaction rate in terms of A, B and C.

A + 2B → 3C
t=0 5M 3M 0
t=5mins 1m 2M 3M

RA = ∆C = 1–5 RC = 3 - 0
∆t 5–0 5 -0
RA = -0.80 M/s RC = 0.60 M/t

RB = ∆C = 2–3 **A negative value means it is being

∆t 5–0 consumed and positive value means
It is formed.
RB = -0.20 M/s

Factors which influence the speed of reactions:

 Nature of reacting substances - the more reactive the reactants, the faster the
reaction rate.
Examples:
a. active metals displace hydrogen vigorously and rapidly from acids, while less
active metals act slowly
b. nitrogen is inert, it combines very slowly with other elements
c. halogens combine with most of the other elements readily

 Temperature – increase in temperature will speed up an endothermic reaction

and slows down an exothermic reaction. For most reactions, the speed is
approximately doubles for each 10-degree rise in temperature.
Example:
a. If a solution containing highly colored permanganate ions is added to an acid
solution of oxalate ions, the reaction proceeds so slowly a t room temperature that
several minutes are requires for the permanganate color to disappear. If the
oxalate solution is heated nearly to boiling before the permanganate is added, the
rate of reactions is speeded up to such extent that the permanganate color
disappears almost instantaneously.
  Presence of catalyst/s – a positive catalyst increases the rate of reaction while a
negative catalyst reduces the rate of reaction.

 Concentration – increase in the concentration of the reactants increases the rate

of formation of products.

Temperature:
A + B + HEAT → C
** An increase in temperature forwards the reaction rate; endothermic

A + B → C + HEAT
** An increase in temperature slows down the reaction rate; exothermic

Concentration:
A + B → C (+ 2A)
** An increase in concentration increases the rate of reaction/ formation of products

Law of Mass Action

The law of mass action states that the rate of chemical reaction is directly proportional to
the product of the molar concentrations of the reacting substances, each raised to the
power indicated by the number of ions or molecules appearing in the balanced equation
for the reaction.

Illustration: 2A + 3B → 4C
Rate of forward reaction = k [A] 2[B] 2 where k = specific reaction rate constant

CHEMICAL EQUILIBRIUM
 It is an apparent state of rest in which two opposing chemical reactions are
proceeding in opposite directions at the same speed. (note: only reversible
reactions attain chemical equilibrium)
 It is a state of reversible reaction where the rates of forward and backward
reactions are equal.

Consider: aA + bB cC + dD
Rate of forward reaction = rf = k1 [A]a [B]b
Rate of backward reaction = rb = k2[C]c [D]d

At equilibrium: rate of forward reaction = rate of backward reaction

rf = rb
k1 [A] [B] = k2[C]c[D]d
a b

Chemical Equilibrium Law

 This law states that for a reversible reaction at a fixed temperature and in a
state of equilibrium, the product of the molar concentrations of the substances formed
in the reaction divided by the product of the molar concentrations of the reactants,
each raised to the power indicated by the number of ions or molecules in the
balanced equation is equal to a CONSTANT.

Le Chatelier’s Principle
This state that when a stress is applied to a system in equilibrium whereby the
equilibrium is altered, the equilibrium will shift in such a manner as to relieve or
neutralize the effect of the added stress.

Stresses which may be imposed on a system in Chemical Equilibrium

 Pressure change - no significant effect upon equilibria involving solid and liquid
solutions; only gaseous solutions are effected; increase in pressure would cause
the equilibrium to shift to that side of the equation with lower number of moles of
gas (or lower volume).
 Temperature change – for endothermic reactions, an increase in temperature
will cause the equilibrium to shift to the right, a decrease in temperature will
produce a shift to the left. The opposite is expected for exothermic reactions.
 Concentration change – an increase in concentration of the reactants will cause
the equilibrium to shift to the right; it is also to the left when the concentrations of
the reactants are decreased.

Note: A catalyst cannot change the numerical value of the equilibrium constant and hence
the relative amounts of reactants and products present at equilibrium. However, it may
greatly reduce the time necessary for the establishment of equilibrium (therefore, only the
value of the rate of chemical reaction is affected by a catalyst.)

Applications of the Law of Chemical Equilibrium

 Ionization of weak electrolytes - belongs to homogeneous equilibria. A
homogeneous ionic system implies a condition where there is uniform mixture of
ions and undissociated molecules of a weak electrolyte in one phase, namely, in
aqueous solution.
 Ionization of slightly soluble electrolytes – belongs to heterogeneous equilibria.
A heterogeneous system is one in which more than one phase is present, as for
example, a saturated solution of ions in contact with excess of the solid solute.
The application of the law of chemical equilibrium to a heterogeneous system is
known as the solubility product principle.
Applications of the Law of Chemical Equilibrium
1. Ionization of weak electrolytes
2. Ionization of slightly soluble electrolytes

Ionic equilibria - a type of chemical equilibrium involving ions

Most reactions of acids, bases and salts are brought in water solutions, and these
necessarily involve the interaction of ions. Such processes are reversible, at least to some
extent and, as a result, equilibrium conditions are quickly established.

Ionization – process of forming charged particles (or ions) from a substance by the
action of a solvent commonly water

In the discussions to follow, we shall consider the ionic equilibria in aqueous solutions.
The concepts of ionic equilibria are particularly valuable in analytical chemistry, but they
also find application in many other areas – for example, ion exchange in resins and gels,
biological processes involving body fluids, acidity or basicity of soils, and so on.

Some postulates on modern view of ionization:

1. Electrolytes, when dissolved in water or any other ionizing medium, produce
electrically charged particles called ions – the cations (+) and the anions (-).
2. Electrolytes are compounds whose water solutions conduct electricity due to the
presence of ions.

2 kinds of electrolytes:
a.) Strong electrolytes - they are completely or 100% ionized in water; they have more
ions in water; good conductor of electricity.
Ex: strong acids, strong bases, salts like NaCl, KCl, CaCl2, BaCl2, K2SO4, all nitrates.

b.) Weak electrolytes – they are slightly (or incompletely) ionized in water; produces
few ions in water; poor conductor of electricity.
Ex: b-1) weak acids, weak bases (listed in table A-5 and A-6)
b-2) salts listed in table A-9

 The production of ions from a weak electrolyte is reversible reaction; the law of
chemical equilibrium is applicable. Ionization of strong electrolyte is irreversible
and is not covered by chemical equilibrium.

Ionization Constants
The Law of Chemical Equilibrium is applicable to ionic as well as molecular reactions.
The equilibrium constants for weak acids and weak bases, usually written as Ka for weak
acids and Kb for weak bases, are termed the ionization constants.
Keq, Kw and pH
As H2O is the medium of biological systems one must consider the role of this molecule
in the dissociation of ions from biological molecules. Water is essentially a neutral
molecule but will ionize to a small degree. This can be described by a simple equilibrium
equation:

H2O → H+ + OH- Eqn. 1

This equilibrium can be calculated as for any reaction:

Keq = [H+] [OH-]/ [H2O] Eqn. 2

Since the concentration of H2O is very high (55.5M) relative to that of the [H+] and
[OH-], consideration of its generally removed from the equation by multiplying both
sides by 55.5 yielding a new term, Kw:

Kw = [H+] [OH-] Eqn. 3

This term is referred to as the ion product. In pure water, to which no acids or bases have
been added:

Kw = 1x10-14 M2 Eqn. 4

As Kw is constant, if one considers the case of pure water to which no acids or bases have
been added:

[H+] = [OH-] = 1x10-7 M Eqn. 5

This term can be reduced to reflect the hydrogen ion concentration of any solution. This
is termed the pH, where:

pH = -log[H+] Eqn. 6

pKa

Acids and bases can be classified as proton donors and proton acceptors, respectively.
This means that the conjugate base of a given acid will carry a net charge that is more
negative than the corresponding acid. In biologically relevant compounds, various weak
acids and bases are encountered, e.g. the acidic and basic amino acids, nucleotides,
phospholipids, etc.

Weak acids and bases in solution do not fully dissociate and, therefore, there is
equilibrium between the acid and its conjugate base. This equilibrium can be calculated
and is termed the equilibrium constant = Keq. This is also sometimes referred to as the
dissociation constant as it pertains to the dissociation of protons from acids and bases.

In the reaction of a weak acid:

HA → H+ + A- Eqn. 7

The equilibrium constant can be calculated from the following equation:

Ka = [H+][A-]/[HA] Eqn. 8

As in the case of the ion product:

pKa = -logKa Eqn. 9

Therefore, in obtaining the –log of both sides of the equation describing the dissociation
of a weak acid, we arrive at the following equation:
-logKa = -log [H+] [A-]/ [HA] Eqn. 10

Since as indicated above, -logKa = pKa and taking into account the laws of logarithms:

pKa = -log[H+]-log[A-]/[HA] Eqn. 11

pKa = pH-log[A-]/[HA] Eqn. 12

From this equation, it can be seen that the smaller pKa value, the stronger is the acid. This
is due to the fact that the stronger an acid, the more readily it will give up H + and,
therefore, the value of [HA] in the above equation will be relatively small.

I. Ionization of monoprotic weak acids

Ex: acetic acid, benzoic acid, hydrofluoric acid, lactic acid, nitrous acid

H → H+ + A- (general representation)

HC2H3O2 + H2O → H3O + C2H3O2-

Kc = [H2O][C2H3O2]
[HC2H3O2][H2O]
But [H2O] = 55.5M & Kc x 55.5 = Ka

Ka = [H3O][C2H3O2] = [H+][C2H3O2]
[HC2H3O2] [HC2H3O2]

In general representation

HA → H+ + A-

Ka = [H+] [A-]
 [HA]

II. Ionization of polyprotic weak acids

Ex: phosphoric acid, phosphorous acid, carbonic acid, oxalic acid, hydrogen sulfide

K1: H3PO4 H+ + H2PO-4

K2: H2PO4 H+ + HPO4-2
K3: HPO4 H+ + PO4-3
Koverall: H3PO4 3H+ + PO4-3

H2S – hydrosulfuric acid or hydrogen sulfide (a gas)

- the most important weak polyprotic acid in qualitative analysis
- precipitating agent for Group II cations
K1: H2S H+ + HS-
K2: HS H+ + S-2
+
Koverall: H2S 2H + S-2

By chemical equilibrium law:

K1 = [H+] [A-] K2 = [H+] [A-] Koverall = [H] [A]

[HA] [HA] [HA]
= K1 x K2 = 6.84 x 10-23

 A saturated solution of H2S at 25 degrees Celsius(room temp.) has a conc. of 0.1F

Ionization of weak bases:

Base – defined as proton acceptor

Ex: NH3 + HOH → NH4+ + OH-

Keq = [NH4+] [OH-] but [HOH] = 55.5M

[NH3][HOH] and Keq x 55.5M = Kb

Kb = [NH4+][OH-]
[NH3]

General Representation: B + HOH → BH+ + OH-

+ -
Kb = [BH ][OH ]
[B]
Ionization of water (Kw)
 Pure water is a very poor conductor of electricity. Pure water is electrolyte which
ionizes as follows:
HOH + HOH → H3O+ + OH-
Kc = [H3O+] [OH-] but Kc x [H2O] [H2O] = Kw
[H2O][H2O]
 Kw = [H3O+] [OH-]
= [H+] [OH-]
For neutral water:
[H+] = 1 x 10-7 M
[OH-] = 1 x 10-7 M
Kw = 1 x 10-14 M

pH - a convenient way of expressing the Hydronium ion [H3O+] concept.

 Water has a pH of &; neutral solutions have pH of 7

 Acidic solutions have a pH less than 7
 Basic solutions have pH greater than 7
pH + pOH = 14
pH = -log[H+]
pH = log[1/H+]

pH Meter – used to measure in the laboratory pH of solutions with an accuracy

approaching 0.01 in the range from 0-14. This device is essentially an electrolytic ell in
which voltage varies with H+ concentration.

Applications of pH
 A careful control of pH is important in many biological processes. Most of the
body fluids in a healthy person have a pH very near to 7. The gastric juices are
an exception, with a pH of about 2.
 pH is important in the growth of bacteria, and certain pH values represent
optimum conditions for growth.
 The utility of a soil for growing crops depends on its acidity or basicity (its pH
or pOH). In very humous soil with decay and carbonic acid formation, a slight
acidity is build up, and this is suitable for certain plants such as rhododendrons,
azaleas and blueberries. Most grasses require a pH above 5.5 for optimum
growth. “Liming” of soil by ground limestone (CaCO3) increases the pH by
reaction with H+ to form CO2 and H2O. Very few plants survive in soils of pH
greater than 8.5.
 The pH of aqueous solutions is also important in cooking foods. Meat may be
tenderized with acidic juices, such as tomato and vinegar. In baking, dough of
pH above 7 yields a crumbly and less moist cake or bread.

Indicators – substance that undergo a change in color at a definite pH values. Most

common indicators are phenolphthalein, methyl orange, and litmus paper. The rest are
listed in Table 4-2, p. 69 of the textbook.
 Common Ion Effect

The effect of ionizing the concentration of a certain ion usually in acid solutions
and … in alkaline solutions) through the addition of a salt to a solution such that salt and
the solution have common ion. The common ion increases the concentration while that of
uncommon ion decreases.

Ex: a) Addition of NaC2H3O2 to HC2H3O2 solution

b) Addition of NH4C2H3O2 to NH4OH solution
c) Addition of Na2SO4 to H2SO4 solution

 All salts that are strong electrolytes ionize completely (100%) and reactions are
irreversible.
Ex: salts of strong electrolytes
- NH4Ac, NaAc, Na2SO4, KAc, HCl, NaOH, KOH, HNO3, KI, NaCl, all
nitrate compounds such as KNO3, NaNO2.

 All compounds of Na and K are strong electrolytes.

Le Chatelier’s Principle
 Common ion effect disturbs the equilibrium by increasing the concentration of the
common ion. The equilibrium shifts to that side that suppresses ionization.
Spectator ion – ion that has no effect on the ionization

Phosphate ion – controls the body pH

Buffer Solution

It is a solution which resists change in pH when an appreciable amount of either strong

acid or base is added to the solution. It is usually a mixture of a weak acid and its salt.

Ex: a) HAc and NaAc

b) HAc and NH4Ac
c) H2CO3 and NaHCO3

A mixture of weak base and its salt

Ex: a) NH4OH and NH4Cl
b) NH4OH and NH4Ac

HAc – NaAc buffer maybe prepared by the ff:

1) Adding NaAc directly to HAc
2) Reacting HAc and NaOH in such a way as to leave some of the HAc unreacted:
HAc + NaOH NaAc + HOH
3) Reacting NaAc and HCl in such a way as to leave a part of the NaAc unreacted:
HCl + NaAc Na+ + Cl- + HAc

NH4OH – NH4Cl buffer may be prepared by any of the ff:

1) Adding NH4Cl directly to NH4OH
2) Reacting NH4OH and HCl in such a way as to leave part of the NH4OH unreacted:
NH4OH + HCl NH4Cl + HOH
3) Reacting NaOH and NH4Cl in such a way as to leave part of the NH4Cl unreacted:
NaOH + NH4Cl Na+ + Cl- + NH4OH

Uses of buffered solutions:

 Buffered solutions are used extensively in analytical chemistry, biochemistry, and
bacteriology, as well as in photography and the leather and dye industries. In each
of these areas, particularly in biochemistry and bacteriology, certain rather narrow
pH ranges may be required for optimum (or best results). If during the course f a
chemical reaction, the concentration of acids (or bases) is allowed to increase, an
undesirable reaction may occur or the desired reaction may be inhibited. The
activity of enzymes, the growth of bacterial cultures, and other biochemical
processes depend upon the control of pH by buffered systems.
 Buffered solutions in the body: Intracellular and extra cellular fluids in living
organisms contain conjugate acid-base pairs that function as buffers at the pH of
the fluids. The major intracellular buffer is the dihydrogen phosphate –
monohydrogen phosphate, H2PO4 - HPO4-2, conjugate acid-base pair. This latter
buffered system helps maintain the pH of the blood at nearly constant value, close
to 7.4, even though acidic and basic substances continually pass into the
bloodstream. If the pH-regulating mechanisms of the body fail, as may happen
 during illness, and if the pH of the blood falls below 7.0 or rises above 7.8,
irreparable body damage may result.

Notes:
a) The catalytic activity of enzymes is extremely sensitive to small changes in pH.
Their activity declines sharply on the high or low side of 7.4. A change in [H+] of
as little as 2.5 times (say, from 7.4 to 7.0) can be fatal, thus buffer solutions are
useful for enzymes to maintain the required pH.
b) Blood, milk, digestive juices and other fluids that are produced or used, in living
tissues are highly buffered solutions.
 SOLUBILTY PRODUCT PRINCIPLE
It is an application of the law of chemical equilibrium to heterogeneous equilibria
produced by solids in equilibrium with ion in solution or more specifically to equilibria
produced by saturated solution of difficultly or slightly soluble electrolytes.

Statement of the principle: in a saturated solution of a difficultly or slightly soluble

electrolyte, the product of the formal concentrations of the ions, each ion raised to the
power equal to the number of times it occurs in the formula, is a constant at a given
temperature.

In a saturated solution of difficultly or slightly soluble electrolyte, there is equilibrium

with solid electrolyte with its ions in solution. This is a heterogeneous system in which
the chemical constant takes a new name, which is solubility product constant or Ksp.
Recall that previous topics of ionization involved homogeneous systems (that is, the
substance and its ions are all in one phase, liquid) in which the chemical equilibrium
constant takes the name ionization constant (Ka and Kb).

When a relatively insoluble salt (or difficultly or slightly soluble salt), such as AgCl, is
shaken with water, ions from the crystal lattice of the solid pass into solution until the
solution becomes saturated. In the saturated solution thus formed, equilibrium exists
between the ions in solution and the ions in the solid. For AgCl its ionization is shown as
follows:
AgCl (s) Ag+ (aq) + Cl- (aq)

Applying the law of chemical equilibrium to the above ionization, we may write:
Ksp = [Ag+] [Cl-]

Since the concentration of any pure solid is constant (it is equal to its density to its
molecular weight), [AgCl] is a constant and may be incorporated in the Keq to give it a
new name Ksp.

Ksp = Keq x [AgCl] = [Ag+] [Cl-] note that the concentration in brackets are those
in equilibrium, that is, in saturated solutions.

Applications of solubility product principle

1. Prediction of solubilities (solubility is the maximum amount of solute that can dissolve
in a given amount of solvent at a specified temperature; in short, solubility refers to the
amount of solute present in a saturated solution)
2. Prediction of whether a precipitate will form or not when two solutions are mixed.
3. Prediction of the amount of a substance needed to precipitate another substance.
4. Prediction of the maximum concentration of a substance that can coexist with another
substance without causing precipitation.
5. Prediction of minimum concentration of a substance that has to be present in order to
initiate precipitation.
6. Prediction of the order of solubility (ex: Given a list of compounds, arrange in the
order of increasing or decreasing solubility).
7. Prediction of order of precipitation (ex: Given a list of substances, arrange beginning
with the substance with the highest tendency to precipitate).

Influence of a common ion on solubility

The effect of common ion upon a precipitate in equilibrium with its ions is the
decrease in the solubility of the solid phase, thus more precipitate is formed.

Fractional precipitation
Fractional precipitation – the process of precipitating one at a time several ions present in
one solution by the gradual addition of the same precipitating agent. This is possible only
if the Ksp of the ions precipitated have wide difference in their K sp values. Ex: H2S
precipitates both group 2 and group 3 cations based upon a careful control of the
concentration of the sulfide ion.

Increasing solubility in water

 We can do this by merely looking at K sp values provided the salts have the same
stoichiometry (or same subscript).
  In cases where we are comparing salts of different stoichiometry, we have solved
their individual solubilities in g/L as the basis of comparison.
 The solubility is the same when there is no common ion.
Fractional Precipitation
Ex: H2S as a precipitating agent for both group II cations (or acid sulfide group) and
group III cations (or basic sulfide group)

 Fractional precipitation is effective only when the ratio of the K sp of the cations
separated is one million is to one.
 Now look at the ratios of Ksp of the sulfides of Group II and III (p. 170) cations
and make a conclusion whether their separation by H 2S is effective or complete.
How do you go about the separation? What do you control?
- by controlling the addition of H2S.
 HYDROLYSIS

Hydrolysis is a chemical reaction or process, in which a molecule is split into two parts
by reacting with a molecule of water, which has the chemical formula H2O. One of the
parts gets an OH- from the water molecule and the other part gets an H+ from the water.

Case 1: Hydrolysis of anions that are bases (or salts of SB and WA).
Case II: Hydrolysis of cations that are acids (or salts of WB and SA).
Case III: Hydrolysis of salts whose cations are acids and whose anions are bases (or
salts of WB and WA).
Case IV: Hydrolysis of salts whose ions are aprotic (or salts of SB and SA).
 No hydrolysis takes place between the ions of this type of salt and water.
 QUANTITATIVE CHEMISTRY

Analytical Chemistry

Qualitative Chemistry Quantitative Chemistry

The nature of the constituents of a given material is determined by the methods

of QUALITATIVE ANALYSIS; the proportions in which these constituents are present
are determined by the methods of QUANTITATIVE ANALYSIS.

Divisions of Quantitative Analyses

Volumetric Analyses Gravimetric Analyses Other methods

The principle of volumetric analysis differs from that of gravimetric analysis in that,
instead of isolating and weighing the desired substance, the volume of a reagent required
to bring about a reaction with that substance is measured. From the volume of the reagent
and its concentration, the weight of the desired substance is calculated.

Volumetric Analysis is more commonly known as titration.

Titration - the determination of the concentration of a solution by the gradual addition to

it of a standard solution
Standard solution – a solution whose concentration is accurately known; it is used as the
titrating solution in volumetric analyses.
Analyte – the term used to refer to substance being titrated in volumetric analyses
Equivalence point – the point in titration in which a chemical reaction is completed
End point – the point in titration in which the indicator changes color; it coincides with
the equivalence point
Indicator – a substance which changes in color on the passage from acidity to alkalinity,
or the reverse
Standardization – the process of knowing the exact concentration of a solution by using
it as a titrant against a known weight of a primary standard
Primary Standard – a solid substance whose percent purity is known
Requirements for a primary standard:
1. Its purity should be known to accuracy well within that required in the analyses in
which the standardization solution is to be used. A standard that is at least 99.9% pure is
desirable.
2. It must be of definite, known composition, and it must react quantitatively and in a
known way with the solution to be standardized.
3. Its composition should not be affected by drying or by changes in humidity.
4. It should be relatively soluble in water, and the salts formed by its neutralization
should also be soluble.
5. It is desirable that its equivalent weight be fairly high so that a relatively large weight
of it can be taken without requiring for titration more than one buretful of the solution to
be standardized.

Requirements of Volumetric Analysis:

1. Accurate balance with which to weigh the material for analysis
Ex: analytical balance, digital balance
2. Graduated instruments in which to measure the volumes of the solutions used
Ex: buret
3. Standard solution
4. Indicator that will show the endpoint

Principle in Volumetric Analysis

If the reaction at equivalence point is:
A+B→C+D where: A is the Analyte
B is the titrating solution
C and D are the products, then
At equivalence point: eqv A = eqv B = eqv C = eqv D
meq A = meq B = meq C = meq D

eqv substance = (Normality X Volume in liters)substance = wt of substance

# of eqv substance

meq substance = (Normality x Volume in ml)substance = wt of substance

# of meq of substance

Where: # of eqv substance = mol. Wt. of substance

Factor of substance

# of meq of substance = mol. Wt. of substance

Factor of substance x 1000

Classification of Volumetric Analysis:

1. Neutralization method - the reactants are acid and base: the acid is titrated with a
standard solution of an alkali (acidimetry) or a basic substance is titrated with a standard
solution of an acid (alkalimetry)

2. Redox method – the reactants are reducing and oxidizing agents; a reducing substance
is titrated with a standard solution of an oxidizing agent or vice versa.
3. Precipitation or Saturation method
4. Complex formation method

Neutralization - the reaction between an acid and a base to form water and salt
Ex: NaOH + HCl → HOH + NaCl

2 Divisions of Neutralization Volumetric Analysis:

1. Acidimetry – an acidic substance (Analyte) is being titrated with a standard solution

(titrant) of an alkali
2. Alkalimetry – a basic substance (Analyte) is being titrated with a standard solution
(titrant) of an acid
 REDOX TITRATION
Redox titration is a division of volumetric analysis where the reactants are oxidizing and
reducing agents.
Oxidation is a reaction in which a substance increases in its oxidation number due to
losing electrons.
Reduction is a reaction in which a substance reduces in its oxidation number in a redox
reaction.
Oxidizing agent is a substance which reduces its oxidation number in a redox reaction.
Reducing agent is a substance which increases its oxidation number in a redox reaction.

How to determine the factor of a reducing/ oxidizing agent:

f = (absolute difference in the change in oxidation number) x (number of molecules
present in the left side)

Exercises:
Division of redox titration:
1. Permanganate Process - the oxidizing agent is a permanganate solution like KMnO4
2. Dichromate Process – the oxidizing agent is a dichromate solution like K2Cr2O7
3. Ceric Process – the oxidizing agent is a ceric solution like Ce(SO4)2
4. Iodimetry Process – the oxidizing agent is I2

Solutions used in Redox Titration:

A. Oxidizing Agents B. Reducing Agents
1. K2Cr2O7 1. Ferrous solutions like FeSO4 and
FeSO4•(NH4)SO4•6H2O
2. KMnO4 2.Oxalic acid
3. K3Fe(CN)6 3. Sodium oxalate
4. I2 4. Sodium thiosulfate, Na2S2O3
5. Ceric Sulfate, Ce(SO4)2 5. Stannous chloride, SnCl2
6. KIO3 6. Sodium arsenite, Na3AsO3
7. KBrO3 7.H2SO3
8. Zn

Important Combinations of Oxidizing Agent and Reducing Agent in Redox

Titrations:

1. K2Cr2O7 and ferrous solutions

2. KMnO4 and ferrous solutions
3. KMnO4 and Na2C2O4
4. I2 and sodium thiosulfate, Na2S2O3
5. Hypochlorites (Ex: HClO4) and arsenous acid
 PERMANGANATE PROCESS
This is a division of redox titration where the OA used is KMnO 4 solution. There is no
auxiliary indicator used in the permanganate titration because the potassium
permanganate serves as the indicator itself. In such titration, when carried out in the
presence of an acid, the permanganate ion is reduced to manganous ion (Mn ++), which in
dilute solution appears colorless. One drop of excess permanganate colors the solution a
very definite shade of pink (this is the end point color in the permanganate process being
carried out in the acidic medium).

Advantages of the Permanganate Process over the Redox Titration:

 No auxiliary indicator is needed. The KMnO4 itself serves as the indicator.
 KMnO4 is a very powerful oxidizing agent and has intense coloring power.

Disadvantages of the Permanganate Process:

 Permanganate ion tends to decompose even in neutral medium
(4MnO4- + 2H2O → 4MnO2 + 3O2 + 4OH-)
 Permanganate ion is even less stable in acidic medium than in neutral medium.

Common Primary Standards for the Standardization:

1. Sodium Oxalate (Na2C2O4)
2. Arsenious Oxide (As2O3)
3. And others seen in p. 216 by Hamilton and Simpson

The Reduction of the Permanganate ion in Different Media:

1. In acidic medium, permanganate ion is reduced to Mn ++, therefore, the factor of each
permanganate ion is equal to (7-2) x 1 = 5 (see p.212 by Hamilton and Simpson)
a. With Ferrous salts
MnO4- + 5Fe+2 + 8H+ → Mn+2 +5Fe+3 + 4H2O
b. With Oxalate radical (oxalate is oxidized to CO2)
2MnO4- + 5C2O4-2 +16H+ → 2Mn+2 + 10CO2 + 8H2O
c. With arsenic (III)
2MnO4- + 5As+3 + 12H2O → 5H3AsO4 + 2Mn+2 + 9H+

2. In neutral or slightly alkaline medium, permanganate ion is reduced to MnO 2,

therefore, the factor of each permanganate is (7-4) x 1 =3 (see p. 212 by Hamilton and
Simpson).

a. Volhard method which is used for determining Mn in steel

3Mn+2 + 2MnO4- + 4OH- → MnO2 + 2H2O
b. Determination of Formic Acid (HCOOH)
 3COOH- + 2MnO4- + 2H2O → 3CO2

Common applications of the permanganate process aside from those mentioned

above:
1. Analysis of OA (requires the indirect titration method)
 The analyte can’t be directly titrated with KMnO 4 (an OA). So a measured
amount of an RA is added to the analyte OA and the excess RA is titrated with
KMnO4.
 Meq analyte = meq RA- meq KMnO4

Examples of applications in this method are:

a. Determination of Mn or MnO2 in Pyrolusite [OA] (an ore whose
composition is MnO2), see p. 232
b. Determination of dichromate ion, see p.211
c. Determination of other OA
2. Analysis of RA (uses the direct titration method)
i. The KMnO4 is directly used to the titrated, the analyte is an RA.
ii. meq analyte = meq KMnO4 – meq solution back titration
What is the difference between direct and indirect titration? {See p. 178}

 KMnO4 has 2 factors depending upon the medium:

a. In an acid environment, it is reduced to Mn+2, thus its factor is
equal to 5.
b. in a neutral/basic environment, it is reduced to MnO2-2, thus its factor
is equal to 3.
 DICHROMATE AND CERIC PROCESSES

 Redox titrations where the OA used are K 2Cr2O7 and Ce(SO4)2, respectively.
The most common RA used in this process is ferrous solutions.

Advantages of Dichromate and Ceric Process over Permanganate Process

1. Potassium dichromate and ceric sulfate are stable, at higher temperatures unlike
permanganate which easily decomposes.

Disadvantages of Dichromate and Ceric Process over Permanganate process

1. Special indicator (known as redox indicator) is used in each case whereas
permanganate serves as its own indicator.

 The sodium salt of diphenylamine sulfonate is the most commonly used redox
indicator whose change is from colorless to purple.

Reactions
K2Cr2O7 → Cr+3 factor of K2Cr2O7 = (6-3) x 2 = 6
Ce(SO4) → Ce+3 factor of Ce(SO4) = (4-3) x 1 = 1

Applications of Dichromate/Ceric Process

1. Determination of Fe in limonite in solutions containing Fe like FeCl3 solution
2. Determination of Cr in Chromite (an ore whose composition is Fe(CrO2)2 )
 IODIMETRY
 The redox titration of iodine (as the OA) against sodium thiosulfate, with starch
as the indicator. The endpoint color is deep blue.

Reactions

I2 + 2Na2SO3→ 2NaI + Na2S4O6

Where:
Na2S2O3 is Sodium Thiosulfate
Na2S4O6 is Sodium Tetrathionate

The factor if I2 = [0-(-1)] x 2 = 2

The factor of Na2S2O3 = [2.5 - 2] x 2 = 1

Analysis of Iodimetry
1. Analysis of Reducing Agents (such as H2S, sulfites, arsenites, stannous salts)
 The RA is directly titrated with I2
 Principle: meq I2 = meq RA

2. Analysis of Oxidizing Agents (such as permanganate chromate, H2O2)

 The method makes use of the idea that all OA oxidize iodide in dilute acid
solution to free iodine (as I2), which in turn can be titrated with standard sodium
thiosulfate.

OA + Excess KI → Free Iodine in the form of I2 which in turn is titrated with

Na2S2O3

Principle: meq OA = meq I2 = meq Na2S2O3

 Gravimetric Methods

The constituent to be determined is isolated, either as an element or as a compound of

definite (or known) composition. This element or compound is weighed, and from its
weight and its known formula, the amount of the desired constituent is determined.

 Steps Involved in Gravimetric Analysis:

a. Weighing the sample

b. Dissolving the sample
c. Separation of some substance from solution containing, or bearing a definite
relation to, the constituent to be measured, under conditions which render
this separation as complete as possible.
d. The isolation of that substance, commonly by filtration.
e. Determination of its weight or that of some derivative formed from it on
ignition.

 Volumetric Method vs., Gravimetric Method

 VOLUMETRIC methods are generally more rapid, require less apparatus,
and are frequently capable of greater accuracy than GRAVIMETRIC
methods. They are particularly useful when many determinations of the
same sort are required.