PART-C : PERIODIC PROPERTIES

PERIODICITY :
(a) The regular gradation in properties from top to bottom in a group and from left to right in a
period is called periodicity in properties.
(b) In a period, the ultimate shell remain same, but the number of electron gradually increases.
(c) In a group, the number of electron in the ultimate shell remains same, but the values of n increases.
Cause of periodicity
(a) The cause of periodicity in properties is due to the same outermost shell electronic configuration
coming at regular intervals.
(b) In the periodic table, elements with similar properties occur at intervals of 2, 8, 8, 18, 18 and
32. These numbers are called magic numbers.
SCREENING EFFECT (s) AND EFFECTIVE NUCLEAR CHARGE (Zeff)
(a) Valence shell electron suffer force of attraction due to nucleus and force of repulsion due to
inner shell electrons.
(b) The decrease in force of attraction on valence electron due to inner shell electron is called
screening effect or shielding effect.(i.e. total repulsive force is called shielding effect.)
(c) Due to screening effect, valence shell electron experiences less force of attraction by nucleus.
(d) Due to screening effect, net attractive force felt by the electron is measured by effective nuclear
charge, Zeff
(e) If nuclear charge = Z, then effective nuclear charge = Z – s (Where s 'sigma' is called screening
constant/sheilding constant)
So, Zeff = Z – s

CALCULATION OF s (using slater’s rule)

To calculate the shielding constant (s) :
(a) Write the electronic configuration of the element in the following order and groupings :
(1s), (2s, 2p), (3s, 3p), (3d), (4s, 4p), (4d), (4f), (5s, 5p), etc.
For s and p electrons :
(b) Electrons in any group to the right of the (ns, np) group contribute nothing to the shielding
constant.
(n-shell no. of the electron for which s is calculated)
(c) All of the other electrons in the (ns, np) group, shield the concern electron to an extent of
0.35 each. (Except for the 1s orbital for which value is 0.30).
(d) All electrons in the (n – 1) shell shield to an extent of 0.85 each.
(e) All electrons (n – 2) or lower group shield completely ; that is, their contribution is 1.00 each.
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 For d and f electrons :
(f) Electrons in any group to the right of the nd or nf group contribute nothing to the shielding
constant.
(g) All the other electrons in the nd or nf group, shield the valence electron to an extent of 0.35
each.
(h) All electrons in groups lying to the left of the nd or nf group contribute 1.00.
(Effective Nuclear charge of elements of second period)
Element Electronic Z s of ns & np s (n–1) Total Effective
Configaration electron orbital Screeing nuclear
Constant charge#
(a) (b) (a + b) Z*=Z – s
2 1
3Li 1s 2s 3 – 0.85× 2=1.70 1.70 1.30
2 2
4Be 1s , 2s 4 1× 0.35=0.35 0.85× 2=1.70 2.05 1.95
2 2 1
5B 1s ,2s ,2p 5 2× 0.35=0.70 0.85× 2=1.70 2.40 2.60
2 2 1
6C 1s ,2s ,2p 6 3× 0.35=1.05 0.85× 2=1.70 2.75 3.25
2 2 3
7N 1s ,2s ,2p 7 4× 0.35=1.40 0.85× 2=1.70 3.10 3.90
2 2 4
8O 1s ,2s ,2p 8 5× 0.35=1.75 0.85× 2=1.70 3.45 4.55
2 2 5
9F 1s ,2s ,2p 9 6× 0.35=2.10 0.85× 2=1.70 3.80 5.20
# Calculated for valence electron.
Key Points :
(a) From left to right in a period Zeff increases
(i) For s and p-block elements, Zeff in a period increases by 0.65 where atomic number increases
by 1, and hence atomic size decreases considerably.
(ii) In transition series Z increase by + 1 but screening constant increases by 0.85 So Zeff is increased
by 0.15
(1– 0.85 = 0.15) [Because e– enters in (n – 1) orbit which has value of s = 0.85]
(b) From top to bottom in a group Zeff remain constant for s-block elements, after Li and Be.
Element Li Na K Rb Cs Fr
Zeff 1.30 2.20 2.20 2.20 2.20 2.20
Example-7 :
What is the effective nuclear charge at the periphery of nitrogen atom when an extra electron is
added during the formation of an anion. Also find the value of Zeff when the atom is ionized to N +.
Ans. Ground state electron configuration of N(Z = 7) = 1s2 2s2 2p3
Electron configuration of N– = (1s2) (2s2 2p4)
Shielding constant for the last 2p electron,
s = [(2 × 0.85) + (5 × 0.35)] = 3.45
So Zeff = Z – s = 7 – 3.45 = 3.55
Electron configuration of N+ = (1s2) (2s2 2p2)
Shielding constant for the last 2p electron,
s = [(2 × 0.85) + (3 × 0.35)] = 2.75
So Zeff for last electron on N+ = 7 – 2.75 = 4.25

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 ATOMIC RADIUS :
Problem in calculating actual size of atom and hence distance between nuclei is calculated giving rise to
three type of radii for atoms.

d
(a) Covalent radius : Cr =
2

[Used for H2, Cl2 and such molecules]

d
d
(b) Metallic Radius : Mr =
2

[Used for metals]

(c) VanderWaal's Radius or Collision radius

Two adjacent
I2 molecules
Two
adjacent
iodine atoms

I I I I

Cr Vr

1
VanderWaal's radius = × Internuclear distance between nuclei of two neighbouring atoms
2
belonging to nearest molecules.
VanderWaal's radius > Metallic radius > Covalent radius
The VanderWaal's radius and covalent radius of chlorine atom are 1.80 Å and 0.99 Å respectively
Ionic Radius
A neutral atom changes to a cation by the loss of one or more electrons and to an anion by the gain
of one or more electrons. The magnitude of charge on cation and anion is equal to the number of
electrons lost or gained respectively. The ionic radii of the ions present in an ionic crystal may be
calculated from the internuclear distance between the two ions.
(a) Radius of Cation
Radius of cation is smaller than that of corresponding atom. Since due to removal of electron(s),
Zeff increases.
(b) Radius of an Anion
Radius of an anion is invariably larger than that of the corresponding atom, since due to addition
of electron(s) Zeff decreases.
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 Factors affecting atomic radius:
(a) Zeff increases, atomic radius decreases Li > Be > B > C > N > O > F
(b) Number of shell(n) increases, atomic radius increases Li < Na < K < Rb < Cs
(c) Screening effect increases, atomic radius increases.
(d) Magnitude of –ve charge increases, atomic radius increases O < O– < O–2
(e) Magnitude of +ve charge increases, atomic radius decreases Mn > Mn+2 > Mn+3 > Mn+4
(f) Bond order increases, atomic radius decreases N — N > —N N— >N N
Periodic Trend :
(a) For normal elements:
(i) Across a period : It decreases from left to right in a period as Zeff. increases.
Ex. Li > Be > B > C > N > O > F
(ii) In a group : It increases from top to bottom in a group as number of shells increases.
Ex. Li < Na < K < Rb < Cs
Note : In III A group size of Al and Ga is nearly same or Ga slightly smaller than Al (transition contraction)
(b) For inert gases:
In respective period generally, the atomic radius of inert gas is largest, because for inert gas
VanderWaal's radius is defined. The VanderWaal's radius of inert gases also increases on moving
from top to bottom in the group.
(c) For transition elements:
From left to right in a period:
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radius (Å) 1.44 1.32 1.22 1.77 1.17 1.17 1.16 1.15 1.17 1.25
Radius/Å

Sc Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
La Hf Ta W Re Os Ir Pt Au Hg
Trends in atomic radii of
transition elements
In a group :
(i) The atomic radius of elements increases on moving down the first transition series (3d) to second transition
series (4d). This is due to the increases in number of shells with the increase in atomic number.
(ii) The atomic radii of second (4d) and third (5d) transition series in a group is almost same except
Y(39) and La(57)
(d) For inner transition elements:
As we move along the lanthanide series, there is a decrease in atomic as well as ionic radius. The
decrease in size is regular in ions but not so regular in atoms. This is called lanthanide contraction*.
Exceptions :
(1) Noble gases have largest atomic sizes as compared to corresponding halogen [Vander waal radii]. However,
their covalent radii are smaller e.g. Xe.
(2) Size of Ga and Al are same, or Ga slightly smaller than Al [Zeff increasing]
(3) Size of Hf & Zr are same (lanthanide contraction)
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 Graphical representation of atomic radius :
ALKALI METALS ALKALINE EARTH METALS GROUP III-A
2.5 1.8
Cs, 2.35 2.5
Rb, 2.16 1.6 Tl, 1.55
2 K, 2.03 Ba, 1.98 In, 1.5
Sr, 1.91 1.4
2 Ca, 1.74
Na, 1.57 1.2 Al, 1.24 Ga, 1.24
1.5 Mg, 1.36

(in Å)
1.5
in Å

Li, 1.23 1
1 0.8 B, 0.8
1
Be, 0.89 0.6
0.5 0.5 0.4
0.2
0 0 0
Li Na K Rb Cs Be Mg Ca Sr Ba
B Al Ga In Tl

CARBON FAMILY NITROGEN FAMILY (PNICOGENS)

1.6
1.6
Bi, 1.52
Sn, 1.41 Pb, 1.44 1.4 Sb, 1.41
1.4
1.2 Ge, 1.22 1.2 As, 1.21
Si, 1.17 P, 1.1
1 1
(in Å)

(in Å)
0.8 C, 0.77 0.8
N, 0.74
0.6 0.6
0.4 0.4
0.2 0.2
0 0
C Si Ge Sn Pb N P As Sb Bi
CHALCOGENS HALOGENS
1.6
1.4
1.4 I, 1.33
Te, (1.37) 1.2
1.2 Br, 1.14
Se, (1.14) 1 Cl, 0.99
1
S, (1.04)
(in Å)

(in Å)

0.8
0.8 F, 0.64
O, (0.66) 0.6
0.6
0.4
0.4
0.2
0.2
0
0 F Cl Br I
O S Se Te
[ what can you predict or say about the increment in size along a group and decrement along a period]
ISOELECTRONIC MONOATOMIC SPECIES [Size a 1/Z] :
(i) S 2 - , Cl - , K + , Ca 2 + , Sc 3 + (ii) H - , He , Li +
radius of cation Z of Anion
(iii) O–2 , F¯ , Na+ , Mg+2, Al+3 (iv) = eff
radius of anion Zeff of Cation
IONISATION ENERGY :
Amount of energy required to remove the most loosely bounded electron from an isolated gaseous atom form
its ground state electronic configuration.
Units : kJ mol–1, k cal mol–1, eV per atom.
Ionisation is endothermic (endoergic) i.e. requires energy. Hence DHionsation is +ve.
M + Energy (IE1) ¾® M + e + –

M ¾® M+ + e– DH = IE1
M+ ¾® M+2 + e– DH = IE2 ù
ú Successive ionisation energy
M+2 ¾® M+3 + e– DH = IE3 û
IE3 > IE2 > IE1 (always)
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 FACTORS AFFECTING IONISATION ENERGY :
(1) Atomic size : Varies inversely
(2) Screening effect : varies inversely
(3) Nuclear charge (Z) : varies directly
(4) Special electronic configuration of outermost electron (half filled / fully filled)
(5) Type of orbital involved in Ionisation :s > p > d > f.
Note : Half fillness and full fillness of inner orbitals, affects d block and f block trends.
General Trend: Along period I.E. increases [with some exception] [Zeff ­]
Along a group I.E. decrease [Zeff constant, n ­ ]

2500
2500 He
Ne
Ne
2000 (2080)
2000
–1 F
Ar I.E 1/kJ mol
–1

(1681)
I.E1/kJ mol

1500 Kr
1500 N
Xe (1402)
1000 O
Be (1314)
1000 C
(899)
500 (1086)
Li Na Li B
K Rb Cs (520) (801)
0 500
0 10 20 30 40 50 60 0 2 4 6 8 10
Atomic number(Z) Atomic number(Z)
Variation of first ionization energy (I.E1)
First ionization energy (I.E1) of elements of the
with atomic number for elements with Z = 1 to 60
second period as a funciton of atomic number(Z)

Exception :
(1) Along a period, half filled and fully filled configurations have higher I.E.
e.g. Be > B and N > O.
(2) along a group, Ga > Al
PROPERTIES AFFECTED BY IONISATION ENERGY :
(1) Metallic character
(2) Reducing power
(3) Tendency to stay in which state A+1. A+2 or A+3
Note :
(a) Helium (He) has the highest ionisation energy (IE1) among all the elements and Caesium (Cs)
has the least (IE1) value.
(b) Ionisation potential of inert gases is very high due to most stable s2p6 electronic configuration.
Element He Ne Ar Kr Xe Rn
IE1(eV) 24.5 21.6 15.8 14.0 12.1 10.7
(c) For isoelectronic species I.P. increases with positive charge and decreases with negative charge.
e.g. Al+3 > Mg +2 > Na+ > F– > O–2 > N–3

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 Graphical representation of ionisation energy :
ALKALI METALS ALKALINE EARTH METALS GROUP III A

6 10 900
Li, 5.4 9 Be, 9.32 800 B, 801
5 Na, 5.1
8 Mg, 7.64 700
K, 4.3 Rb, 4.2 7
4 600 Tl, 589

(in kJ/mol)
Cs, 3.9 Al, 577 Ga, 579 In, 558
6 Ca, 6.11
(in eV)

(in eV)
Sr, 5.7 500
3 5 Ba, 5.2
400
4
2 3 300
2 200
1
1 100
0 0 0
Li Na K Rb Cs Be Mg Ca Sr Ba B Al Ga In Tl

CARBON FAMILY NITROGEN FAMILY (PNICOGENS)

4 00
12
C , 11.2 3 50 N , 3 36
10
3 00
8 Si, 8.1 Ge, 7.8 (in kcal/mol)
Sn, 7.3 Pb, 7.4 2 50 A s, 2 31
(in eV)

P , 25 3
6 2 00 S b , 19 9
Bi, 1 8 4.9
4 1 50
1 00
2
50
0
0
C Si Ge Sn Pb
N P As Sb Bi

CHALCOGENS HALOGENS
16 20
18 F, 17.4
14 O, 13.6 16
12 14
S, 10.4 Cl, 13
10 Se, 9.75 12 B r, 11.8
(in eV)
(in eV)

Te, 9.01 Po, 8.43 I, 10.4

8 10
8
6
6
4 4
2 2
0 0
O S Se Te Po F Cl Br I

Ionisation energy of d-block elements :

1st, 2nd, 3rd IE's are increasing from left to right for 1st Transition series, but not regularly.
For 2nd IE Cr > Fe > Mn and Cu > Zn
For 3rd IE Mn > Cr > Fe and Zn has highest.

Atomic number 21 22 23 24 25 26 27 28 29 30
Electronic configuration
2 2 3 2 5 1 5 2 6 2 7 2 10 2 10 1 10 2
M 3d14s2 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s 3d 4s
2 3 4 8 9
M2+ 3d 1 3d 3d 3d 3d 5 3d 6 3d 7 3d 3d 3d10
3+ 1 2 3 4 5 6 7
M [Ar] 3d 3d 3d 3d 3d 3d 3d – –
Enthalpy of atomisation, DaH!/kJ mol–1
326 473 515 397 281 416 425 430 339 126
Ionisation Enthalpy, D1H!/kJ mol–1
!
D1H I 631 656 650 653 717 762 758 736 745 906
II 1235 1309 1414 1592 1509 1561 1644 1752 1958 1734
III 2393 2657 2833 2990 3260 2962 3243 3402 3556 3829

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