STRUCTURE OF ATOM

& PERIODIC PROPERTIES OF

ELEMENTS

Textbook:
Essentials of Physical Chemistry.
By: B.S. Bahl, G.D.Tuli
CHAPTER: 01 - 02 &
Inorganic Chemistry
by Madan
CHAPTER: 01- 04 1
1
 Slater’s rules
Slater’s rules:
:
Zeff = Z – S ;

Where Z = nuclear charge, Zeff = effective

nuclear charge, S= shielding constant

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The effective nuclear charge is a measure of
the pull exerted on the electrons by the
Calculation of S and Zeff by Slater's Rules.
nucleus.

According to these rules the value of a for a given electron is

estimated as follows:

(1)Write down the complete electronic configuration of the

element and divide the electrons into the following orbital groups
starting from the inside of the atom. (1s); (2s, 2p); (3s, 3p); (3d);
(4s, 4p); (4d); (4fl; (5s, 5p); (6s, 6p) etc.

(2) Now select the electron for which the value of S is to be

calculated. For this calculation add up the contributions to S for the
other electrons according to the following rules:
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Values of S may be estimated as follows:
A particular electron in a ns or np orbital

All electrons in groups outside the electron chosen 0

For other electrons in (ns, np) S = 0.35

For electrons in (n-1) S = 0.85

For electrons in (n-2) or lower shells S = 1.00

A particular electron in a nd or nf orbital

All electrons in groups outside the electron chosen 0
For other electrons in the (nd, nf) S = 0.35
For electrons in a lower group S = 1.00

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Question: Confirm that the experimentally observed electronic

configuration of K, 1s22s22p63s23p64s1 is energetically more stable

than the configuration 1s22s22p63s23p63d1.
For K, Z = 19:
For 1s22s22p63s23p64s1 is: Zeff = Z – S
= 19 – [(8 × 0.85) + (10 × 1.00)]
= 2.2
For 1s22s22p63s23p63d1 is: Zeff = Z – S
= 19 – (18 × 1.00)
=1
Thus, an electron in the 4s (rather than the 3d) is under the
influence of a greater effective nuclear charge. So, the electronic

• configuration of K, 1s 2
2s 2
2p6
3s 2
3p6
4s 1
, is energetically more stable
than the configuration 1s22s22p63s23p63d1. 5
Applications of Effective Nuclear Charge
(I) 4s orbital is filled before 3dorbitals.

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 DO
1. Show that Slater’s rules give a value of Zeff = 5.20 for a 2p
electron of F (9) .

2. Use Slater’s rules to estimate values of Zeff for

(a) a 4s and (b) a 3d electron in a V(23) atom.

3. Using Slater’s rules, confirm that Zeff of Ar (18) > Zeff of Cl (17)

4. Using Slater’s rules, confirm that the experimentally observed

electronic configuration of Ca (20)=1s2 2s2 2p6 3s2 3p6 4s2 is energetically
more stable than the configuration 1s2 2s2 2p6 3s2 3p6 3d2.
5. Using Slater’s rules, confirm that the experimentally observed
electronic configuration of Sc (21)=1s2 2s2 2p6 3s2 3p6 4s2 3d1 is
energetically more stable than the configuration 1s2 2s2 2p6 3s2 3p6 3d3 .
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 Approaching Slater’s rules on
Notable periodic properties
1. Atomic radius 2. Ionic radius
3. Ionizational Energy 4. Electron affinity
5. Electronegativity 6. Hydration of ions
7. Reducing and oxidising power
Elements Li Be B C N O F
Atomic 0.123 0.089 0.08 0.077 0.074 0.073 0.072
Radius
(nm)

decreases

Increases
We know Zeff = Z – S. Here shielding electrons in
same orbital are equal for Li, Be , B and so on. In
this trend, S increases by 0.35 whereas Z increases
by +1. So Zeff increases. Consequently electrons
in the outermost shell feel greater attraction by
nucleus. As a result, atomic radius decreases.
It is seen that the same net charge is equal and Zeff is also same

when we descend a group. But The valence electrons enter into a

new shell. So shell increases. As a result, atomic radius increases.

 Ionic radius
Atom / Ion Radius(nm)

Na 0.157

Na+ 0.097

Atom/ Ion Radius(nm)

F 0.072

F- 0.133
 Why Na>Na+?
We know Zeff = Z – S. No. of electrons from
outermost and intervening/ intermediate shell
decreases if we remove electrons one after one.
So shielding electrons decreases. So Zeff
increases.(i.e. the remaining electrons feel
greater attraction by nucleus)
Why F<F-?
The addition of one or more electrons will
increase repulsion among electrons. So Zeff
decreases.
 Ionizational Energy
The ionization energy (IE) of an
element is defined as the energy M(g ) + I E 1 ⎯⎯→ M+
( g ) + e−
needed to remove a single M (g ) + I E2 ⎯⎯→ M ( g ) + e−
+ 2+

electron from an atom of the M2+(g ) + I E3 ⎯⎯→ M3+( g ) + e−

element in the gaseous state.

IONISATION ENERGIES IN KJ mol–1

Fig. Graph showing the variation of first ionisation energies with increase of atomic number.

Why IE increases across a period?

Why IE decreases across a group?
 Electronegativity
The attraction exerted by an atom on the electron pair
bonding it to another atom by a covalent bond.
We know Zeff = Z – S. Here shielding electrons in
same orbital are equal for Li, Be , B and so on. In
this trend, S increases by 0.35 whereas Z increases
by +1. So Zeff increases. Consequently electrons in
the outermost shell feel greater attraction by
nucleus. As a result, atomic radius decreases.
Distance between nucleus and bonding electrons
decreases. So attraction of bonding electrons by
the atom located at shorter distance from bonding
electron pair ( i.e. electronegativity) increases.
Why EN decreases over Group?
 Electron Affinity(EA)
The amount of energy released M(g ) + e− → M- ( g ) + EA1
when an electron is added to a M- (g ) + e− → M2- ( g ) + EA2
gaseous atom to form an anion. M2- (g ) + e− → M3-( g ) + EA3
 EA increases across over period
Li Be B C N O F Ne
-57 ≈0 -15 -121 +31 -142 -333 0

We know Zeff = Z – S. Here shielding electrons in same

orbital are equal for Li, Be , B and so on. In this trend, S
increases by 0.35 whereas Z increases by +1. So Zeff
increases. Consequently electrons in the outermost shell
feel greater attraction by nucleus. As a result, atomic
radius decreases. So attraction between nucleus and
outermost electron increases. So EA increases over
period. 22
 Why EA decreases over group?
F Cl Br I
-333 -348 -324 -295

In a group. On moving down a group both the size of the

atom and the effective nuclear charge increase. The
increase in atomic size tends to decrease the electron
affinity values while the increase in nuclear charge tends
to increase the electron affinity values. The net result is
that the effect produced by the progressive increase of
the atomic size outweighs the effect produced by the
progressive increase in nuclear charge and consequently
the electron affinity goes on decreasing as we move from
top to bottom in a group. 23
 Exception: EA of F(9) < EA of Cl(17)

F(9)= 1s 2 2s 2 2p 5 , Cl (17) = 1s 2
2s 2
2p 6
3 s 2
3 p 5

The lower values for the elements of 2nd period are explained by
saying that, due to the smaller size of the atoms of the elements of
2nd period, the addition of an extra electron to these atoms
produces high electron density round the resulted anions. This high
electron density increases the repulsion between the electrons
(called electron—electron repulsion) already present in the
relatively compact 2p orbital of the 2nd shell of these atoms and
the electron being added. Due to this electron—electron repulsion,
the atoms of the elements of 2nd period show lesser tendency to
attract the extra electron from outside and hence lower values of
electron affinity for these elements.
 Generally 1st EA is exothermic but 2nd EA is
endothermic
e.g. O +e- = O- ; ∆H= -141 KJ/ mole
O- +e- = O2- ; ∆H= +798 KJ/ mole

The negatively charged atom has already higher electron

density(i.e. electron increases in outermost electron). So an

incoming electron faces more repulsion from negatively charged

atom. As a result, it needs more energy to add an electron in

the outermost shell of negatively charged atom. So 2nd EA is

endothermic.
 Hydration of ions, hydrated radii and
hydration energy
The alkali metals are extensively
hydrated.

The smaller the cation, the greater is the degree of its hydration. Thus
the degree of hydration of M+ ions decreases on moving from Li + to
Cs +. As a result of this decrease in hydration degree, the ionic radii of
M ions in water (known as hydrated radii) decrease from Li + to Cs +.

With the decrease of hydrated radii from Li + to Cs +, the ionic

conductance of these hydrated cations increases in the order :
Hydration of ions is an exothermic process. The energy released when one
mole of an ion in the gaseous state is dissolved in water to get it hydrated is
called hydration energy, i.e. it is the energy released in the hydration of M +
(g) ions.

Since the degree of hydration of M ions decreases from Li + to Cs +,

the hydration energy of these ions also decreases in the same order:
Reducing and oxidising power of elements

Reducing power Oxidising power

decreases increases

Increases decreases

Fig: Variation of Reducing and oxidising power of elements

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THANK YOU

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