Unit 1

Periodic Properties and Catalysis (12 Marks)

Periodic properties :-Effective nuclear charge, penetration
of orbitals, electronic configurations, Periodic trends of
atomic and ionic sizes, ionization energies, electron
affinity, electro negativity
Catalysis: Basic Concepts, Homo and
Heterogenous ,Industrial Significance of Catalyst in the
preparation of PF resin and Bio diesel

Periodic Table-Introduction
In 1859 two physicists Robert Willhem Bunsen and Gustav Robert Kirchoff
discovered spectroscopy which allowed for discovery of number of new
elements. It was noticed that there is a pattern among known elements, in
1869, Russian chemistry professor Dmitri Mendeleev and German chemist
Julius Meyer independently made efforts to develop a systematic method to
classify the elements. Mendeleev’s approach, based upon atomic weight
wise arrangement of elements, was ultimately adopted at the time for
several reasons; one of them was that, he left gaps for elements that had yet
to be discovered.
With Consideration of Mendeleev’s periodic table Alfred Werner proposed
the framework of modern periodic table.Modern periodic table also known
as long form of periodic table, organizes the known elements in several
ways; it lists them in order of patterns of atomic number, electron
configuration, reactivity and electronegativity. It is an effective manner of
organizing and presenting the known elements that it has been used to
successfully predict the existence of certain elements. It organizes elements
according to similar properties in such a way that one can tell the
characteristics of an element just by looking at its location on the table.
It helps to predict the types of chemical reactions that an element is likely to
participate in. Rather than memorizing facts and figures for each element.

Structural features of the long form of the periodic table:

• In this table, the elements are arranged in the order of increasing
atomic numbers in such a way that elements with similar properties
fall in the same vertical column.
 • These vertical columns are referred to as 'Groups'. There are eight
groups, which are further sub-divided into eighteen sub-groups.
• There are 7 horizontal rows in the periodic table. These are called the
periods.
• Noble (inert) gases are placed in the 18 or VIII A, which is at the
extreme right of the table.
• Halogens are placed in group 17 or VII A, just ahead of the noble gas
elements.
• The alkali metals (Na, K, etc.) are placed in group 1 or I A and the alkaline
• earth metals (Ca, Ba, etc.) are placed in 2 or II A which is at the
extreme left of the table.
• Transition elements such as copper, iron, etc., are placed in the 3 to
12 groups, which occur at the middle of the table.
• The inner transition elements, lanthanides and actinides are placed
in two separate series at the bottom of the main body of the periodic
table.

Periodicity / Periodic properties

The recurrence of similar properties of the elements when they are
arranged in the order of increasing atomic number, after certain regular
intervals, is called periodicity.
 The properties which are directly or indirectly related to their electronic
configuration and show gradual change when we move from left to right in a
period or from top to bottom in a group are called periodic properties. Such
properties show a variation with change in atomic number.
Periodic Properties of the Elements
 Atomic and Ionic Radius (Atomic and Ionic sizes)
 Ionization Energy (ionization potential)
 Electron Affinity.
 Electronegativity.
 Polarizability
 Metallic Character
 Electronics configuration
 Effective nuclear charge
 Penetration of orbital

Atomic and Ionic Radius (Atomic and Ionic sizes)

The term ionic radius is generally used for distance between the nucleus
and the outermost shell of electrons of the atomic or ionic particle.
As it is impossible to isolate an individual atom or an ion, it is not possible
to measure the atomic or ionic radius. These quantities are, however,
generally derived in anindirect manner from the measured distance bet
ween the nuclei of two bonded atoms in a gaseous molecule or between the
nuclei of two ions in crystals (or solids).
In the first case, these distances are called internuclear distances (or bond
lengths or bond distances) and in the second case these are called interionic
distances.
The internuclear distances (in covalent substances) and inter-ionic distances
(in ionic substances) are generally determined by X-ray diffraction, electron
diffraction, NMR spectroscopy techniques etc.
Periodic variations of atomic and ionic radii-
Atomic or ionic radius is a periodic function of the atomic number, i.e. it
changes with the change of atomic number in the periodic table as shown
below:
(a) In a period-
Atomic and ionic radii both decreases from left to right across a period in
the periodic table when we consider only normal elements, e.g. in the
elements of 2nd period the covalent radii decrease as we move from Li to F
as shown below:
Elements of 2nd period: Li Be B C N O
F Covalent radii (Ao) 1.23 0.90
0.82 0.77 0.75 0.73 0.72
Values decreasing →
Thus, in any period the alkali metals (that are present at the extreme left of
the periodic table) have the largest size while the halogens (that are present
at the extreme right, excluding the zero group elements) have the smallest
size.
As we proceed from left to right in a period the electrons are added to the
orbitals of the same main energy level. Addition of differentiating electrons
to the same main energy level puts the electrons on the average, no farther
from the nucleus and hence cannot add to the size. But with the addition of
each electron, the nuclear charge (i.e. atomic number) increases by one.The
increased nuclear charge attracts the electrons more strongly close to the
nucleus and thus decreases the size of the atoms.
(b) In a group-
On moving down, a group of regular elements both atomic and ionic radii
increase with increasing atomic number.
Ex. In the elements of IIA Group both covalent and ionic radii of M 2+ ions
increase when we pass from Be to Ba.
Elements of IIA Group: Be Mg Ca Sr Ba
Covalent radii (Ao): 0.90 1.36 1.74 1.91 1.98
Ionic radii of M+ cations 0:31 0.65 0.99 1.13 1.35
(Ao)
Values increasing →
When we proceed from top to bottom in a group, the following two opposite
forces act simultaneously.
On proceeding downwards in a group the electrons are added to higher
main energy levels which are, on the average, farther from the nucleus. This
effect decreases the electrostatic attraction between the nucleus and the
valence-shell electrons and this decreased electrostatic attraction increases
the atomic and ionic radii.
The nuclear charge (i.e. atomic number) increases as we proceed from top
to bottom. This increase in nuclear charge decreases the atomic and ionic
radii.

Ionization Potential or Ionization Energy-

The electrons are raised to higher energy levels by absorption of energy
from an external source. If this process is continued, a stage comes when
the electron goes completely out of the influence of the nucleus and a
positive ion is produced.
The amount of energy required to remove the most loosely bound electron
(i.e., the outermost electron) from an isolated gaseous atom of an element in
its lowest energy state (i.e., ground state) to produce a cation is known as
ionization potential or ionization energy of that element. It is generally
represented as I or IP and is measured in electron volts (eV) or Kilo calories
(K. calories) per gm atom. Thus, ionization potential can be defined by the
process.
M(g) + Energy supplied (Ionization energy, I) → M+(g)
+ e- isolated gaseous atom
The process by which the element loses an electron (i.e., ionizes) to convert
itself into a cation is called is Ionization.

Ionization potentials (in eV) of s-and p-block

elements. S-block p-block Elements

Elements
IA II A III A IV A VA VI A VII A Zer
o
H
He
13.5 24.
5
Li Be Be C N O F Ne
5.4 9.3 8:3 11.2 14.5 13.6 17.4 21
6
Na Mg Al Si P S Cl Ar
5.1 7.6 6.0 8.1 11.0 10.4 13.0 15.
8
K Ca Ga Ge As Se Br Kr
4.3 6.1 6-0 7:8 9.8 9.8 11.8 14.
0
Rb Sr In Sn Sb Te I Xe
4.2 5.7 5.7 7.3 8.6 9.0 10.4 12.
1
Cs Ba Ti Pb Bi Po At Rn
3.9 5.2 6.1 7.4 7.2 8.4 ---- 10.
7

Electron Affinity or Affinity Energy-

In ionization potential, we express the energy supplied to the atom to
remove successively one, two or more electrons, and thereby produce
cations. In the concept of electron affinity, we refer to a reverse process.
Thus, we have an energy associated with the addition of an electron (or even
more electrons in succession) to a neutral atom.
The amount of energy released when an electron is added to an isolated
neutral gaseous atom in its lowest energy state (i.e. ground state) to
produce an anion is called its electron affinity or affinity energy. It is
generally represented as EA or E and is measured in electron volts (eV) or
Kilocalories. (Kcal) per gm atom. Thus, electron affinity can be defined by
the equation:
A(g) + e- (g) → A- (g) + Energy released (Electron
affinity E) Neutral atom Anion
The above process by which the neutral gaseous atom adds an electron is an
exo-thermic process, since energy is released in it. Since electron affinity
represents the energy released, it is represented with a negative sign placed
before it. Electron affinity just defined is first electron affinity (E1). Since it
corresponds to the addition of one electron only. In the process of adding an
electron to an anion, A- (g) against the electrostatic repulsion between the
electron being added and the negative charge on A - (g) ion, energy instead
of being released is supplied to A- (g) to form A2-(g).
A(g) + e- (g) → A (g)+ Energy
released (E) A-(g) + e- (g) + Energy supplied → A2-
(g)
Energy supplied in the process to convert A-(g) to A2-(g) is called second
electron affinity. Since E2 is the energy absorbed, it is given a positive sign.
Factors influencing the magnitude of electron affinity are –
i) Atomic size, ii) Effective nuclear charge, iii) Screening effect of inner electrons

Periodic Variations-

a) In a group

In moving down in a group electron affinity values generally decrease, e.g.

ECl> EBr> EI. This is due to the steady increase in the atomic radius of the
elements.

There are, however, some exceptions to this general rule as is evident from the
following examples:

i) Although the elements of second period of the periodic table are

relatively smaller in size than those of the third period, yet E values
of elements of second period are smaller than the E values of third
period elements. This unexpected behavior is explained by saying
that the much smaller sizes of the second period elements give a
very much higher value of charge densities for the respective
negative ions.
ii ) The lower value of E for F is probably due to the electron-electron
repulsion in relatively compact 2p-orbital of F atom.

b) In a period

Electron affinity values generally increase on moving from left to right in a

period in the periodic table. There are however some exceptions also to this
general rule;
e.g. i) Be and Mg have their E values equal to zero. Since Be and Mg have
filled s- orbitals (Be →2S2, Mg→ 3S2), theadditional electron will be entering
the 2p-orbital in case of Be and 3p-orbital in case of Mg which are of
considerably higher energy than the 2s-orbitals respectively. Similarly, in
case of inert gases in which the ns-and np-orbitals are filled (ns2 p6
configuration) the incoming electron must go into an electron shell having a
larger value for the principal quantum number, n. Thus, inert gases also
have their E values equal to zero.

ii) Nitrogen and phosphorus have unexpected lower values ofelectron

affinities. This 1s because of the presence of half-filled 2porbitals which are
relatively more stable and hence to which it isdifficult to add an additional
electron.

Electronegativity
The tendency of an atom in a molecule to attract the shared pair of electrons
towards itself is known as electronegativity.
Consider the formation of a covalent bond between two similar atoms of a
molecule like
H. In this molecule, the electron pair participating in the formation of
covalent bond is shared equally by both hydrogen atoms i.e. the electron
pair lies exactly in the center of the molecule.
On the other hand, consider the formation of a covalent bond between two
dissimilar atoms of a molecule like HCI. In this molecule, the electron pair
participating in the formation of covalent bond is not shared equally by the
two atoms viz. H and Cl, i.e. the electron pair lies near to Cl atom than to H
atom. The reason for this unequal sharing of electron pair is given by saying
that Cl atom has a greater tendency than H atom to attract the electron pair
shared between them towards itself. In other words, CI atom has greater
electronegativity than H atom. Thus, the electronegativity of bonded atom is
defined as its relative tendency (or ability) to attract the shared electron
pair towards itself.
Electronegativity of an atom A is generally represented as XA.

Electronegativity generally increases across a period from left to right (say

from lithium to fluorine) and decrease down a group (say from fluorine to
astatine) in the periodic table.
Electronegativity values of s and p-block elements as determined by Pauling
(Scale F=4.0)
S block elements p-block elements
IA IIA IIIA IVA VA VIA VIIA
H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Ge Ga As Se Br
0.8 1.0 1.6 1.8 2.0 2.4 2.8

Polarizability
Electric polarizability is the relative tendency of a charge distribution, like
the electron cloud of an atom or molecule, to be distorted from its normal
shape by an external electric field.
The polarizability α in isotropic media is defined as the ratio of the induced
dipole moment P of an atom to the electric field E that produces this dipole
moment.

α = P/ E
Polarizability allows us to better understand the interactions between
nonpolar atoms and molecules and other electrically charged species, such
as ions or polar molecules with dipole moments.
Neutral nonpolar species have spherically symmetric arrangements of
electrons in their electron clouds. When in the presence of an electric field,
their electron clouds can be distorted. The ease of this distortion is defined
as the polarizability of the atom or molecule. The created distortion of the
electron cloud causes the originally nonpolar molecule or atom to acquire a
dipole moment. This induced dipole moment is related to the polarizability
of the molecule or atom and the strength of the electric field by the
following equation:

μind=αE
where E denotes the strength of the electric field and αis the polarizability
of the atom or molecule with units of C m2V-1.

Factors Influencing Polarizability

The relationship between polarizability and the factors of electron density,
atomic radii, and molecular orientation is as follows:
The greater the number of electrons, the less control the nuclear charge has
on charge distribution, and thus the increased polarizability of the atom.
The greater the distance of electrons from nuclear charge, the less control
the nuclear charge has on the charge distribution, and thus the increased
polarizability of the atom.
Molecular orientation with respect to an electric field can affect
polarizability (labeled Orientation-dependent), except for molecules that are:
tetrahedral, octahedral or icosahedral (labeled Orientation-independent).
This factor is more important for unsaturated molecules that contain areas
of electron-dense regions, such as 2,4- hexadiene. Greatest polarizability in
these molecules is achieved when the electric field is applied parallel to the
molecule rather than perpendicular to the molecule.
Polarizability Influences Dispersion Forces
The dispersion force is the weakest intermolecular force. It is an attractive
force that arises from surrounding temporary dipole moments in nonpolar
molecules or species. These temporary dipole moments arise when there are
instantaneous deviations in the electron clouds of the nonpolar species.
Surrounding molecules are influenced by these temporary dipole moments
and a sort of chain reaction results in which subsequent weak, dipole-
induced dipole interactions are created. These cumulative dipole- induced
dipole interactions create attractive dispersion forces. Dispersion forces are
the forces that make nonpolar substances condense to liquids and freeze
into solids when the temperature is low enough.
Polarizability affects dispersion forces in the following ways:
As polarizability increases, the dispersion forces also become stronger.
Thus, molecules attract one another more strongly and melting and boiling
points of covalent substances increase with larger molecular mass.
Polarizability also affects dispersion forces through the molecular shape of
the affected molecules. Elongated molecules have electrons that are easily
moved increasing their polarizability and thus strengthening the dispersion
forces. In contrast, small, compact, symmetrical molecules are less
polarizable resulting in weaker dispersion forces.
Effective Nuclear Charge-
The periodic table having number of elements, out of that if we consider
hydrogen atom, it has only one electron, the energy determined by level of
which is determined by its principal quantum number n. All the orbitals
inside this shell have the same energy and the only force experienced by the
electron is the attractive force towards the positively charged nucleus. In
case of poly electron atoms force experienced by the electron is the
attractive force towards the nucleus along with repulsive force with
themselves. The effective nuclear charge is the net positive charge
experienced by an electron in a polyelectronic atom.
The term "effective" is used because the shielding effect of negatively
charged electrons prevent higher orbital electrons from experiencing the
full nuclear charge of the nucleus due to the repelling effect of inner layer
electrons. The repulsion of outer-shell electrons by the inner-shell electrons
is very important, because the outer shell electrons are pushed away from
the nucleus due to repulsion of the inner-shell electrons. Therefore, only a
part of the nuclear charge is effective on the electrons of the outermost
orbit. Thus, the inner electrons protect or shield the nucleus and thereby
decrease the effect of nuclear charge towards the electrons of the outermost
orbit. Thus, the nuclear charge felt by the outer-shell electrons is less than
what it would have been ifthere were no inner electrons. This net charge felt
by the valence electrons is called as Effective nuclear charge. It is
represented by Zeff.or Z*

Zeff. =Z- shielding

constant or

Z* = Z – S
where,
Z* =Effective nuclear charge
S = shielding constant or screening constant / the number of non-
valence electrons. Z- nuclear charge
Thus, the part of the nuclear charge that works against outer electrons, is
known as Effective Nuclear Charge.
Slaters Rule-
To calculate Effective Nuclear Charge by Slaters Rule steps are
given bellow- Step 1- Write down the electronic configuration.
Step 2- Group the electron in the following way-

(s) (2s, 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f) (5s, 5p) (5d)…………….
Step 3- Electron on the right of the one under consideration has no shielding
contribution (zero)

Step 4- For each electron in the same group the shielding contribution by
each electron will be 0.35 unless it is the 1s orbital the shielding
contribution by each electron will be 0.30.

Step 5- If the electron under consideration belongs to an s or p orbital then

shielding contribution by the electrons having principal quantum number
less by one would be
0.85 each and all electrons further left would contribute an amount of 1.0 each.

Step 6- If the electron under consideration belongs to d or f orbital then the

shielding contribution by the electrons on the left would be 1.0 each.

Numericals
1.
Calculate Effective Nuclear Charge

for K19 Solution-

Electronic configuration

of K19 1s2, 2s2, 2p6, 3s2,

3p6, 4s1
Grouping the configuration according to
Slater's rule (1 s2) (2s2,2p6) (3s2, 3p6)
4s1
n-3 n-2 n-1 n
Since we must calculate effective charge on 4s 1, and there is only one
electron in this energy shell, single electron in this orbital should not be
considered. The screening constant of the electrons as per the above table is
used and the values are substituted as follows
(2 x 1) + (8 x 1) + (8 x 0.85) = 16.83
S= 16.8
Z* = 19- 16.8 = 2.2

2.
What is the value of Zeff for N7?

Solution: Electronic configuration- 1s2,

2s2, 2p4 Group the configuration per

Slater's rule-

(1s2) (2s2,2p4)

n-1 n

Since nth shell has s & p orbitals containing total 5 electrons. Excluding 1
electron, remaining 4 electrons in nth shell will have shielding effect equal
to 0.35. Hence S will be calculated according the rule is as follows

(2 x 0.85) +(4 x .35) = 3.1

Z* = 7- 3.1 = 1 3.9

3. What is the effective nuclear charge for each? A neutral neon atom (Ne),
a sodium cation (Na+), and a fluorine anion (F–).

Solution:

Start by figuring out the number of non-valence electrons, which can be

determined from the electron configuration.

Ne has 10 electrons. The electron configuration is 1s 22s2 2p6. The valence

shell is shell 2 and contains 8 valence electrons. Thus, the number of
nonvalenced electrons is 2 (10 total electrons – 8 valence). The atomic
number for neon is 10, therefore:

Zeff(Ne) = 10 – 2 = 8

Flourine has 9 electrons but F – has gained an electron and thus has 10. The
electron configuration is the same as for neon and the number of nonvalence
electrons is 2. The atomic number for F– is 9, therefore:

Zeff(F–) = 9 – 2 = 7
Sodium has 11 electrons but the Na+ ion has lost an electron and thus has 10.
Once again, the electron configuration is the same as in the previous
examples and the number of nonvalence electrons is 2 (by losing one
electron, the valence shell becomes the n=2 shell). The atomic number for
Na+ is 11, therefore:

Zeff(Na+) = 11 – 2 = 9

In each of the above examples (Ne, F–, Na+) an atom has 10 electrons but
the effective nuclear charge varies because each has a different atomic
number. The sodium cation has the largest effective nuclear charge, which
results in electrons being held the tightest, and therefore Na+ has the
smallest atomic radius.

Electronic Configurations of Elements and the Periodic Table

We know that an electron in an atom is characterized by a set of four
quantum numbers, and the principal quantum number (n) defines the main
energy level known as shell. We have also studied about the filling of
electrons into different subshells, also referred to as orbitals (s, p, d, f) in an
atom. The distribution of electrons into orbitals of an atom is called its
electronic configuration. An element’s location in the Periodic Table
reflects the quantum numbersof the last orbital filled.
(a) Electronic Configurations in Periods-
The period indicates the value of n for the outermost or valence shell. In
other words, successive period in the Periodic Table is associated with the
filling of the next higher principal energy level (n = 1, n = 2, etc.). It can be
readily seen that the number of elements in each period is twice the number
of atomic orbitals available in the energy level that is being filled.
1. The first period (n = 1) starts withthe filling of the lowest level (1s)
and therefore has two elements — hydrogen (1s1) and helium (1s2)
when the first shell (K) is completed.
2. The second period (n = 2) starts with lithium and the third electron
enters the 2s orbital. The next element, beryllium has four electrons
and has the electronic configuration 1s22s2. Starting from the next
element boron, the 2p orbitals are filled with electrons when the L
shell is completed at neon (2s22p6). Thus there are 8 elements in the
second period.
3. The third period (n = 3) begins at sodium, and the added electron
enters a 3s orbital. Successive filling of 3s and 3p orbitals gives rise to
the third period of 8 elements from sodium to argon. The fourth period
(n = 4) starts at potassium, and the added electrons fill up the 4s
orbital. Now you may note that before the 4p orbital is filled, filling
up of 3d orbitals becomes energetically favorable and we come across
the so called 3d transition series of elements. This starts from
scandium (Z = 21) which has the electronic configuration 3d14s2. The
3d orbitals are filled at zinc (Z=30) with electronic configuration
3d104s2 .
4. The fourth period ends at krypton with the filling up of the 4p orbitals.
Altogether we have 18 elements in this fourth period.
 5. The fifth period (n = 5) beginning with rubidium is similar to the
fourth period and contains the 4d transition series starting at yttrium
(Z = 39). This period ends at xenon with the filling up of the 5p
orbitals.
6. The sixth period (n = 6) contains 32 elements and successive electrons
enter 6s, 4f, 5d and 6p orbitals, in the order — filling up of the 4f
orbitals begins with cerium (Z = 58) and ends at lutetium (Z = 71) to
give the 4f-inner transition series which is called the lanthanoid series.
7. The seventh period (n = 7) is similar to the sixth period with the
successive filling up of the 7s, 5f, 6d and 7p orbitals and includes
most of the man-made radioactive elements. This period will end at the
element with atomic number 118 which would belong to the noble gas
family. Filling up of the 5f orbitals after actinium (Z = 89) gives the
5f-inner transition series known as the actinoid series. The 4fand 5f-
inner transition series of elements are placed separately in the Periodic
Table to maintain its structure and to preserve the principle of
classification by keeping elements with similar properties in a single
column.
(b) Group wise Electronic Configurations
Elements in the same vertical column or group have similar valence shell
electronic configurations, the same number of electrons in the outer
orbitals, and similar properties. For example, the Group 1 elements (alkali
metals) all have ns1 valence shell electronic configuration as shown below.
Atomic number Symbol Electronic
configuration 3 Li 1s22s1(or) [He]2s1
11 Na 1s22s22p63s1(or) [Ne]3s1
19 K 1s22s22p63s23p64s1(or) [Ar]4s1
37 Rb 1s22s22p63s23p63d104s24p65s1(or) [Kr]5s1
55 Cs 1s 2s 2p63s23p63d104s24p64d105s25p66s1(or)[Xe]6s1
2 2

Thus it can be seen that the properties of an element have periodic

dependence upon its atomic number and not on relative atomic mass.

Electronic Configurations and Types of Elements: s-, p-, d-, f- blocks

The Aufbau (build up) principle and the electronic configuration of atoms
provide a theoretical foundation for the periodic classification. The
elements in a vertical column of the Periodic Table constitute a group or
family and exhibit similar chemical behavior. This similarity arises because
these elements have the same number and same distribution of electrons in
their outermost orbitals. We can classify the elements into four blocks viz.,
s-block, p-block, d-block and f-block depending on the type of atomic orbitals
that are being filled with electrons.
Filling of Orbitals in Atom
The filling of electrons into the orbitals of different atoms takes place
according to the Aufbau principle which is based on the Pauli’s exclusion
principle, the Hund’s rule of maximum multiplicity and the relative energies
of the orbitals.
Aufbau Principle
The word ‘Aufbau’ in German means ‘building up’. The building up of
orbitals means the filling up of orbitals with electrons.
Statement: In the ground state of the atoms, the orbitals are filled in order
of their increasing energies. In other words, electrons first occupy the
lowest energy orbital available to them and enter into higher energy orbitals
only after the lower energy orbitals are filled.
Energy of a given orbital depends upon effective nuclear charge and
different type of orbitals are affected to different extent. Thus, there is no
single ordering of energies of orbitals which will be universally correct for
all atoms. However, following order of energies of the orbitals is extremely
useful:
1s, 2s, 2p, 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 4f, 5d, 6p, 7s...
The order may be remembered by using the method given in Fig. 2.17.
Starting from the top, the direction of the arrows gives the order of filling of
orbitals, that is starting fromright top to bottom left. With respect to
placement of outermost valence electrons, it isremarkably accurate for all
atoms. For example, valence electron in potassium mustchoose between 3d
and 4s orbitals and as predicted by this sequence, it is found in 4sorbital.
The above order should be assumed to be a rough guide to the filling of
energy levels. In many cases, the orbitals are similar in energy and small
changes in atomic structure may bring about a change in the order of
filling. Even then, the above series is a useful guide to the building of the
electronic structure of an atom provided that it is remembered that
exceptions may occur.

Pauli Exclusion Principle

The number of electrons to be filled in various orbitals is restricted by the
exclusion principle, given by the Austrian scientist Wolfgang Pauli (1926).
According to this principle, No twoelectrons in an atom can have the sameset
of four quantum numbers.
Statement :“Onlytwo electrons may exist in the same orbitaland these
electrons must have oppositespin.”
This means that the two electrons can have the same value of three
quantum numbers n, l and ml, but must have the opposite spin quantum
number. The restriction imposed by Pauli’s exclusion principle on the
number of electrons in an orbital helps in calculating the capacity of
electrons to be present in any subshell. For example, subshell 1s comprises
one orbital and thus the maximum number of electrons present in 1s
subshell can be two, in p and d subshells, the maximum number of electrons
can be 6 and 10 and so on. This can be says as the maximum numberof
electrons in the shell with principal quantum number n is equal to 2n2.

Hund’s Rule of Maximum Multiplicity

This rule deals with the filling of electrons into the orbitals belonging to the
same subshell Order of filling of orbitals (that is, orbitals of equal energy,
called degenerate orbitals).
Statement:Pairing ofelectrons in the orbitals belonging to thesame subshell
(p, d or f) does not take placeuntil each orbital belonging to thatsubshell has
got one electron each i.e., itis singly occupied.Since there are three p, five d
and seven forbitals, therefore, the pairing of electrons will start in the p, d
and f orbitals with the entry of 4th, 6th and 8th electron, respectively. It has
been observed that half-filled and fully filled degenerate set of orbitals
acquire extra stability due to their symmetry.
Shielding effect

Electrons in an atom can shield each other from the pull of the nucleus. This
effect, called the shielding effect, describes the decrease in attraction
between an electron and the nucleus in any atom with more than one
electron shell. The more electron shells there are, the greater the shielding
effect experienced by the outermost electrons.

In hydrogen-like atoms, which have just one electron, the net force on the
electron is as large as the electric attraction from the nucleus. However,
when more electrons are involved, each electron (in the n-shell) feels not
only the electromagnetic attraction from the positive nucleus but also
repulsion forces from other electrons in shells from 1 to n-1. This causes the
net electrostatic force on electrons in outer shells to be significantly smaller
in magnitude. Therefore, these electrons are not as strongly bound as
electrons closer to the nucleus.

The shielding effect explains why valence shell electrons are more easily
removed from the atom. The nucleus can pull the valence shell in tighter
when the attraction is strong and less tight when the attraction is weakened.
The more shielding that occurs, the further the valence shell can spread out.
Thus, atoms will be larger.

The repulsion experienced by the outer electrons due to the inner electrons
is known as the shielding effect. It is called so because the inner electrons
shield/screen the outer electrons from experiencing the actual nuclear
charge. Electrons in the inner shells are called intervening electrons. It
should be notedthat only inner electrons cause the shielding of nucleus from
outer electrons and outer electrons do not produce any shielding effect on
any of the inner electrons. The shielding constant is greater than zero and
less than Z and is a measure of the degree to which the intervening
electrons shield the outer shell electronsfrom the nuclear pull. Shielding
effect caused by inner electrons depends uponthe type of sub-shells in which
these electrons are present. Shielding effectshows variation as s > p> d> f.
Hence, s-electrons cause maximum shielding and f- electrons cause
minimum shielding effect.
An atom (assuming its atomic number is greater than 2) has core electrons
that are extremely attracted to the nucleus in the middle of the atom.
However, the numbers of protons in the nucleus are never equal to the
number of core electrons adjacent to the nucleus. The number of protons by
one across the periodic table, but the number of core electrons change by
periods. The first period has no core electrons, the second has 2, the third
has 10, and etc, this number is not equal to the number of protons. So, that
means that the core electrons feel a stronger pull towards the nucleus than
any other electron within the system. The valence electrons are farther from
the nucleus, so they experience a smaller force of attraction. Shielding
refers to the core electrons repelling the outer rings and thus lowering the
1:1 ratio. The nucleus has "less grip" on the outer electrons and are shielded
from them.
Penetration of orbitals

Penetration and shielding determines the physical and chemical properties

ofelements. Trends in basic properties of elements can be predicted by
usingshielding and penetration of orbitals.

Introduction

Electrons are close to each other, which mean that they can repel eachother.
The repulsion an electron feels is shielding and the attraction it feels tothe
nucleus is penetration.In an ideal setting (for atoms at least), every electron
should feel the sameamount of "pull" from the nucleus. This means that the
negative to positivecharge ratio should be 1:1. However, that is not the case
when observing atomicbehavior. When considering the core electrons (or
the electrons closest to thenucleus), the ratio is 1:1, or at least close to it. As
you proceed from the coreelectrons to the outer valence rings of electrons,
the negative to positive chargeratio falls below 1:1. This is because of
shielding, or simply the electronsrepelling each other, but these same core
electrons penetrate and feel more ofthe nucleus than the other electrons.

Orbital Penetration

Penetration describes the proximity of electrons in an orbital to the

nucleus.Electrons which experience greater penetration experience less
shielding andtherefore experience a larger Effective Nuclear Charge (Ze)
but shield otherelectrons more effectively. Electrons in different orbitals
have different wave- functions and therefore different distributions around
the nucleus. However, contrary to what many think, penetration is not the
outer electrons penetrating through the shield of the core electrons. It is
just how well the electronsfeel the nucleus. This is like the idea of outer
electrons penetrating, butnot the same. They are not the same because
the core electrons have more penetration than the outer electrons since
they (the core electrons) feel thestrongest pull.

To relate the idea of penetration, we can use the idea of 2ef or the effective
nuclear charge. It is essentially the number of protons' charge minus
thenumber of electrons shielding- basically how effective the nucleus is
atattracting the electrons. Since core
electrons do not shield themselves, they penetrate the most and are exposed
to the most (effective) nuclear charge. Different orbitals have greater
nuclear penetration than others. Penetration refers to how effectively
electrons can get close to the nucleus. The electron probability density for s-
orbitals is highest in the center of the orbital, or at the nucleus. If we
imagine a dartboard that represents the circular shape of the s- orbital
and if the darts landed in correlation to the probability to where and
electron would be found, the greatest dart density would be at the 50 points
regions but most of the darts would be at the 30-point region. When
considering the 1s-orbital, the spherical shell of 53 pm is represented by
the 30-point ring.

In a multi-electron system, the penetration of the nucleus by an electron is

measured by the relative electron density near the nucleus of an atom for
each shell and subshell of an electron. For example, we see that since a 2s
electron has more electron density near the nucleus than a 2p electron, it is
penetrating the nucleus of the atom more than the 2p electron. The
penetration power of anelectron, in a multi-electron atom, is dependent on
the values of both the shelland subshell of an electron in an atom.Therefore,
for the same shell value (n) the penetrating power of an electronfollows this
trend in subshells:S>p>d>f And for different values of shell (n) and subshell
(1), penetrating power of an electron follows this trend:

1s>2s>2p>3s>3p>4s>3d>4p>5s>4d>5p>6s>4f..

and the energy of an electron for each shell and subshell goes as follows...

1s<2s<2p<3s<3p<4s<3d<4p.

Because the order of electron penetration from greatest to least is s, p, d, f;

the rder of the amount of shielding done is also in the order s, p, d, f.Since
the 2s electron has more density near the nucleus of an atom than a 2p
electron, it is said to shield the 2p electron from the full effective charge of
the nucleus. Therefore, the 2p electron feels a lesser effect of the
positively charged

Electrons are negatively charged and are pulled close to each other by their
attraction to the positive charge of a nucleus. The electrons are attracted to
the nucleus at the same time as electrons repel each other. The balance
between attractive and repulsive forces results in shielding. The orbital (n)
and subshell (ml) define how close an electron can approach the nucleus.
The ability of an electron to get close to the nucleus is penetration.

These electrons that are shielded from the full charge of the nucleus are
said to experience an effective nuclear charge (ZeffZeff)of the nucleus,
which is some degree less than the full nuclear charge an electron would
feel in a hydrogen atom or hydrogenlike ions. The effective nuclear charge
of an atom is given by the equation:

Zeff=Z−S(4)(4)Zeff=Z−S
where.
ZZ is the atomic number (number of protons in

nucleus) and SS is the shielding constant

We can see from this equation that the effective nuclear charge of an atom
increases as the number of protons in an atom increases. Therefore as we go
from left to right on the periodic table the effective nuclear charge of an
atom increases in strength and holds the outer electrons closer and tighter
to the nucleus. This phenomena can explain the decrease in atomic radii we
see as we go across the periodic table as electrons are held closer to the
nucleus due to increase in number of protons and increase in effective
nuclear charge.

Catalysis

It is the process of increasing the rate of a chemical reaction by adding a

substance known as a catalyst. Catalysts are not consumed in the reaction
which remain unchanged after the reaction. Catalysts generally react with
one or more reactants to form intermediates that subsequently give the final
reaction product& in the processe catalyst get regenerated.

Catalysis may be classified as

1. Homogeneous, whose components are dispersed in the same phase as the reactant.
2. Heterogeneous, whose components are not in the same phase.
3. Enzymes and other bio catalysts.
1. Homogeneous Catalyst
In chemistry, homogeneous catalysis is which is soluble in the solution. Homogeneous catalysis
refers to reactions where the catalyst is in the same phase as the reactants.
Examples-
A) Acid catalysis- .
The proton is a homogeneous catalyst. because water is the most common solvent. Water forms
protons by the process of self-ionization of water.
CH3CO2CH3 + H2O ⇌ CH3COOH + CH3OH
B) Carbonylations-
Hydroformilation a one of the form of carbonylation, which, involves the addition of H and
"C(O)H" across a double bond. This process is almost exclusively conducted with soluble
rhodium and cobaltcontaining complexes. A related carbonylation is the conversion of alcohols
to carboxylic acids. CH3OH and CO react in the presence of homogeneous catalysts to give
acetic acid.
Advantages of Homogeneous catalyst-
1. Homogeneous catalysts are generally more selective than heterogeneous catalysts.
2. For exothermic processes, homogeneous catalysts dump heat into the solvent.
3. Homogeneous catalysts are easier to characterize, so their reaction mechanisms are
amenable to rational manipulation.
Disadvantages of Homogeneous catalyst-
1. The separation of homogeneous catalysts from products can be challenging. In some cases
involving high activity catalysts, the catalyst is not removed from the product.
2. Homogeneous catalyst have limited thermal stability compared to heterogeneous catalysts.

2. Heterogeneous Catalyst-
In chemistry, heterogeneous catalysis is catalysis where the phase of catalysts differs from that of
the reactants or products. Heterogeneous catalysis typically involves solid phase catalysts and
gas phase reactants. In this case, there is a cycle of molecular adsorption, reaction, and
desorption occurring at the catalyst surface. Heterogeneous catalysis is very important because it
enables faster, large-scale production and the selective product formation
Adsorption-
Adsorption is an essential step in heterogeneous catalysis. Adsorption is the process by which a
gas phase molecule binds to solid or liquid surface atoms. There are two types of adsorptions-
A) Physisorption, weakly bound adsorption
B) Chemisorption, strongly bound adsorption
Desorption-
The reverse of adsorption is desorption, the adsorbate splitting from adsorbent. In a reaction
facilitated by heterogeneous catalysis, the catalyst is the adsorbent and the reactants are the
adsorbate.

3. Enzymes-

Enzymes are homogeneous catalysts that are essential for life but are also harnessed for
industrial processes. A well-studied example is carbonic anhydrase, which catalyzes and release
CO2 into the lungs from the bloodstream. Enzymes possess properties of both homogeneous and
heterogeneous catalysts. They are usually regarded as a third, separate category of catalyst.
Water is a common reagent in enzymatic catalysis.
Phenol-Formaldehyde resins-
Phenol-formaldehyde resins are also called phenolic resin. Phenol-formaldehyde resinsare
formed by a step-growth polymerization reaction that can be either acid or base catalyzed.
The initial reaction in all cases involves the formation of a hydroxymethyl phenol:
HOC6H5 + CH2O → HOC6H4CH2OH
The hydroxymethyl group is capable of reacting with either another free ortho or para site, or
with another hydroxymethyl group. The first reaction gives a methylene bridge, and the second
forms an ether bridge:
HOC6H4CH2OH + HOC6H5 → (HOC6H4)2CH2 + H2O
2 HOC6H4CH2OH → (HOC6H4CH2)2O + H2O

Catalyst used in Preparation of PF resins-

To accelerate the curing rate and to lower the curing temperature of PF resin, four types of metal-
mediated catalysts were employed in the synthesis of PF resin. Ex. Barium hydroxide (Ba(OH) 2),
Sodium carbonate (Na2CO3), Lithium hydroxide (LiOH), and Zinc acetate ((CH3COO)2Zn).

Biodiesel
Biodiesel is one of the potential alternative energy sources that can be derived from renewable
and low-grade origin through different processes. One of the processes is alcoholysis or
transesterification in the presence of a suitable catalyst. The catalyst can be either homogeneous
or heterogeneous.
Role of catalyst in Biodiesel-

1. Homogeneous catalysts are generally efficient in converting biodiesel with low free fatty acid
(FFA) and water containing single-origin feedstock.

2. Heterogeneous catalysts, provide superior activity, range of selectivity, good FFA, and water
adaptability.

Different Catalysts used for Biodiesel Production

The catalyst used for Bio-diesel production are either homogeneous or heterogeneous.
Homogeneous Catalysts
The most preferred catalyst used for the production of biodiesel is the homogeneous catalyst, as
they are simple to use and require less time to achieve a complete reaction. Both acidic and basic
catalysts come under this category. Homogeneous catalysts are usually dissolved in a solvent that
is in the same phase with all reactants.
Homogeneous Base Catalyst
Homogeneous base catalysts are an alkaline liquid such as

a) Alkali metal-based hydroxides- Ex. Sodium or potassium hydroxide

b) Aalkali metal-based oxides- Ex. Sodium and potassium methoxides

c) Carbonates
Base catalysts have high activity in transesterification. Metallic hydroxides are frequently used
as catalysts due to lower prices but generally possess lower activity than alkoxides. It was
reported that the rate of base catalyzed reaction is 4,000 times faster than that of the acid-
catalyzed one.

Homogeneous Acid Catalyst

The esterification process is catalyzed by bronsted acids (Ex. sulfonic and sulfuric acids,
hydrochloric acid). These catalysts produce very high yields in alkyl esters. However, the
reactions are slower compared to alkali catalyzed reactions and making the process economically.

Heterogeneous Catalysts

Heterogeneous catalysts are different from the reactants in there phase or state . These are the
type of catalysts that creates active sites with its reactants during a reaction.

Heterogeneous Base Catalyst

These catalysts shows superior catalytic activity under mild conditions.These catalysts have
many advantages as Non-corrosiveness, environmental friendliness, and less problems in
disposal. They are easily separated from the reaction environment and can be designed to give
higher activity, selectivity and longer catalyst lifetime.
Ex. Many metal-based oxides such as alkali metal oxides, alkaline earth metal oxides and
transition metal oxides (Generally used as catalyst for the transesterification process of oils).
Heterogeneous Alkaline earth and alkali metal-based catalyst
Metal-based oxides are the most commonly used as a heterogeneous catalyst for
transesterification. Among the metal-based catalysts, CaO has been the most studied catalyst
material for biodiesel production, It having certain advantages like long catalyst life, relatively
high basic strength, high activity and low solubility in methanol.
Heterogeneous Acid Catalysts

Heterogeneous acid catalysts have a less corrosive and toxic effect and give rise to less
environmental problems compared to homogeneous acid catalysts. These catalysts provide
encouraging results under moderate reaction conditions.They react very slowly compared to
solid base catalysts. To employ this type of catalysts high catalyst loading, high temperature, and
long reaction time are required.