Periodic Table & Periodicity

Section (A) : Development of Periodic Table & Modern Periodic Table

Need to classify Elements:
 At present 118 elements are known. Of them the recently discovered elements are man-made.
 With such a large no. of elements it is very difficult to study individually the chemistry of all these
elements and their innumerable compounds individually.
 To ease out this problem, scientists searched for a systematic way to organize their knowledge by
classifying the elements.
 It would rationalize known chemical facts about elements, but even predict new ones for undertaking
further study.
Development of Modern Periodic Table:
(a) Dobereiner’s Triads: He arranged similar elements in the groups of three elements called as triads,
in which the atomic mass of the central element was merely the arithmetic mean of atomic masses of
other two elements or all the three elements possessed nearly the same atomic masses.
Li Na K
7  39
7 23 39 = 23
2
Fe Co Ni
55.85 58.93 58.71 nearly same atomic masses
It was restricted to few elements, therefore discarded.
(b) Newland’s Law of Octave: He was the first to correlate the chemical properties of the elements
with their atomic masses.
According to him if the elements are arranged in the order of their increasing atomic masses the eighth
element starting from given one is similar in properties to the first one.
This arrangement of elements is called as Newland’s Octave.
Li Be B C N O F
Na Mg Al Si P S Cl
K Ca
This classification worked quite well for the lighter elements but it failed in case of heavier elements and
therefore, discarded
(c) Lother Meyer’s Classification: He determined the atomic volumes by dividing atomic masses with
their densities in solid states.
He plotted a graph between atomic masses against their respective atomic volumes for a number of
elements. He found the following observations.
 Elements with similar properties occupied similar positions on the curve.
 Alkali metals having larger atomic volumes occupied the crests.
 Transitions elements occupied the troughs.
 The halogens occupied the ascending portions of the curve before the inert gases.
 Alkaline earth metals occupied the positions at about the mid points of the descending portions of the
curve.
On the basis of these observations he concluded that the atomic volumes (a physical property) of the
elements are the periodic functions of their atomic masses.
It was discarded as it lacks practical utility.
(d) Mendeleev’s Periodic Table:
Mendeleev’s Periodic’s Law
According to him the physical and chemical properties of the elements are the periodic functions of their
atomic masses.
He arranged then known elements in order of their increasing atomic masses considering the facts that
elements with similar properties should fall in the same vertical columns and leaving out blank spaces
where necessary.
Periodic Table & Periodicity
This table was divided into nine vertical columns called groups and seven horizontal rows called
periods.
The groups were numbered as I, II, III, IV, V, VI, VII, VIII and Zero group
Merits of Mendeleev Periodic table:
 It has simplified and systematised the study of elements and their compounds.
 It has helped in predicting the discovery of new elements on the basis of the blank spaces given in its
periodic table.
Mendeleev predicted the properties of those missing elements from the known properties of the other
elements in the same group. Eka-aluminium and Eka-silicon names were given for gallium and
germanium (not discovered at the time of Mendeleev). Later on it was found that properties predicted
by Mendeleev for these elements and those found experimentally were almost similar.
Table-1

eka-aluminium Gallium eka-silicon Germanium

Proeprty
(predicted) (found) (predicted) (found)

Atomic Mass 68 70 72 72.6

Density / (g/cm 3) 5.9 5.94 5.5 5.36

Melting point (K) Low 30.2 High 1231

Formula of oxide E2O3 Ga2O3 EO2 GeO2

Formula of chloride ECl3 GaCl3 ECl4 GeCl4

 Atomic weights of elements were corrected. Atomic weight of Be was calculated to be 3 × 4.5 = 13.5 by
considering its valency 3, was correctly calculated considering its valency 2 (2 × 4.5 = 9)
Demerits in Mendeleev’s Periodic Table :
 Position of hydrogen is uncertain. It has been placed in lA and VIIA groups because of its resemblance
with both the groups.
 No separate positions were given to isotopes.
 Anomalous positions of lanthanides and actinides in periodic table.
 Order of increasing atomic weights is not strictly followed in the arrangement of elements in the periodic
table. For example Ar(39.94) is placed before K(39.08) and Te (127.6) is placed before  (126.9).
 Similar elements were placed in different groups e.g. Cu in IB and Hg in IIB and similarly the elements
with different properties were placed in same groups e.g. alkali metals in IA and coinage metals in IB.
 It didn’t explained the cause of periodicity.
(e) Long form of the Periodic Table or Moseley’s Periodic Table or Modern Periodic Table :
S.No. Introduction DISCRIPTION
1. Proposed by Moseley
(i) In the long form of periodic table there is contribution of Ramsey, Werner,
Bohr and Bury.
(ii)This table is also referred to as Bohr's table since it follows Bohr's scheme
2. Contribution
of the arrangements of elements into four types based on electronic
configuration of elements The modern periodic table consits of horizontal rows
(periods) and vertical column (groups).
3. Based on Atomic number
(i) Moseley did an experiment in which he bombarded high speed electrons on
different Metal surfaces and obtained X-rays(electromagnetic rays).
He observed regularities in the characteristic X-ray spectra of the elements
4. Experiment and found that plot  vs. Z (atomic number) is straight line while  vs. A
(atomic weight) is not, and  = a(Z – b), where a and b are constants that
are same for all elements and  is frequency of X-rays. Thus he concluded
that atomic number is more fundamental property than atomic weight.
Periodic Table & Periodicity

(ii) Moseley concluded that the physical and chemical properties of the
elements are periodic function of their atomic number.
The physical and chemical properties of elements are periodic function of their
Modern Periodic
5. atomic number. So the elements are arranged in order of increasing atomic
Law
number, the elements with similar properties comes after regular intervals.
The repetition of the properties of elements after regular intervals when the
elements are arranged in the order of increasing atomic number is called
periodicity.
6. Periodicity (a) In a period, the ultimate orbit remain same, but the number of electrons
gradually increases.
(b) In a group, the number of electrons in the ultimate orbit remains same, but
the values of n increases.
The periodic repetition of the properties of the elements is due to the
recurrence of similar valence shell electronic configuration after certain regular
Cause of intervals. For example, alkail metals have same electronic configuration ns1,
7.
Periodicty therefore, have similar properties.
In the periodic table, elements with similar properties occur at intervals of 2, 8,
8, 18, 18 and 32. These numbers are called as magic numbers.
The modern periodic table consists of horizontal rows (periods) and vertical column (groups).
Periods :
There are seven periods numbered as 1, 2, 3, 4, 5, 6 and 7.
 Each period consists of a series of elements having same valence shell.
 Each period corresponds to a particular principal quantum number of the valence shell present in it.
 Each period starts with an alkali metal having outermost electronic configuration as ns1.
 Each period ends with a noble gas with outermost electronic configuration ns2np6 except helium having
outermost electronic configuration as 1s2.
 Each period starts with the filling of new shell.
 The number of elements in each period is twice the number of atomic orbitals available in shell that is
being filled. For illustration–
 st period shortest period having only two elements. Filling of electrons takes place in the first
shell, for which, n = 1,  = 0 (s-subshell) and m = 0.
Only one orbital (1s) is available and thus it contains only two elements.
 3rd period (short period) having only eight elements. Filling of electrons takes place in the third
shell. For which,
n = 3,  = 0, 1, 2 and number of orbitals 1 3 5
(3s) (3p) (3d)
––––––––––––––––
Total number of orbitals 9
––––––––––––––––
But the energy of 3d orbitals are higher than 4s orbitals. Therefore, four orbitals (one 3s and
three 3p orbitals) corresponding to n = 3 are filled before filling in 4s orbital (next energy level).
Hence 3rd period contains eight elements not eighteen elements.
 Periodic Table & Periodicity
Groups :
There are eighteen groups numbered as 1, 2, 3, 4, 5, ........... 13, 14, 15, 16, 17, 18.
Group consists of a series of elements having similar valence shell electronic configuration.
Table-2
Periods Number of elements Called as
st
(1) n = 1 2 Very short period
(2)nd n = 2 8 Short period
rd
(3) n = 3 8 Short period
th
(4) n = 4 18 Long period
th
(5) n = 5 18 Long period
th
(6) n = 6 32 Very long period
th
(7) n = 7 32 Very long period

p–Block Elements
S–Block Elements

1 18
IA VIII A

1 2
H
2 d –Block Elements 13 14 15 16 17
He
II A III A IV A VA VI A VII A
1.007 4.002
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
6.941 9.012 10.811 12.011 14.006 15.999 18.998 20.179
11 12 13 14 15 16 17 18
3 4 5 6 7 8 9 10 11 12
Na Mg Al Si P S Cl Ar
III B IV B VB VI B VII B VIII VIII VIII IB II B
22.98 24.30 26.981 28.085 30.973 32.006 35.452 39.948
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.08 40.078 44.959 47.88 50.9415 51.996 54.938 55.84 55.933 58.693 63.546 65.39 69.723 72.61 74.921 78.96 79.904 83.80
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.46 87.62 88.905 91.224 92.906 95.94 98 101.07 102.905 106.42 107.868 112.411 114.82 118.710 121.757 127.60 126.904 132.29
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La* Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.90 137.27 138.905 178.49 180.947 183.85 186.207 190.2 192.22 195.08 196.666 200.59 204.383 207.2 207.980 209 210 222
87 88 89 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118
Fr Ra Ac** Rf Ha Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo
223 226 227 261.11 262.114 263.118 262.12 265 266 269 272 285 284 289 288 292 294

Inner - Transition Metals (f-Block elements)

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
*Lanthanides 140.115 140.907 144.24 145 150.36 151.965 157.25 158.925 162.50 164.930 167.26 168.934 173.04 174.967
90 91 92 93 94 95 96 97 98 99 100 101 102 103
**Actinides Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
232.038 231 238.028 237 244 243 247 247 251 252 257 258 259 260

Classification of the Elements :

It is based on the type of orbitals which receives the differentiating electron (i.e., last electron).
(a) s-block elements
When shells upto (n – 1) are completely filled and the last electron enters the s-orbital of the outermost
(nth) shell, the elements of this class are called s-block elements.
 Group 1 & 2 elements constitute the s-block.
 General electronic configuration is [inert gas] ns1-2
 s-block elements lie on the extreme left of the periodic table.
 This block includes metals.
Periodic Table & Periodicity
(b) p-block elements
When shells upto (n – 1) are completely filled and differentiating electron enters the p-orbital of the nth
orbit, elements of this class are called p-block elements.
 Group 13 to 18 elements constitute the p-block.
 General electronic configuration is [inert gas] ns2 np1-6
 p-block elements lie on the extreme right of the periodic table.
 This block includes some metals, all nonmetals and metalloids.
(c) d-Block elements
When outermost (nth) and penultimate shells (n – 1)th shells are incompletely filled and differentiating
electron enters the (n – 1) d orbitals (i.e., d-orbital of penultimate shell) then elements of this class are
called d-block elements.
 Group 3 to 12 elements constitute the d-block.
 General electronic configuration is [inert gas] (n – 1)d1-10ns1-2 (except, palladium which has valence
shell electron configuration 4d105s0).
 All the transition elements are metals and most of them form coloured complexes or ions.
 d-block elements are classified into four series as given below.
(1) Ist transition series i.e. 3d series contains 10 elements and starts from 21Sc–30Zn. Filling of
electrons takes place in 3d sub-shell.
(2) IInd transition series i.e. 4d series contains 10 elements and starts from 39Y–48Cd. Filling of
electrons takes place in 4d sub-shell.
(3) IIIrd transition series i.e. 5d series contains 10 elements and starts from 57La, 72Hf–80Hg. Filling
of electrons takes place in 5d sub-shell.
(4) IVth transition series i.e. 6d series contains 10 elements and starts from 89Ac, 104Rf–112Uub.

Filling of electrons takes place in 6d sub-shell (incomplete series).

 Those elements which have partially filled d-orbitals in neutral state or in any stable oxidation state are
called transition elements. (Zn, Cd, Hg, Uub are not transition elements)
(d) f-Block elements
When n, (n – 1) and (n – 2) shells are incompletely filled and last electron enters into f-orbital of
antepenultimate i.e., (n – 2)th shell, elements of this class are called f-block elements. General
electronic configuration is (n – 2)f 1-14(n – 1)d0-1ns2
 All f-block elements belong to 3rd group.
 They are metals
 Within each series, the properties of the elements are quite similar.
 The elements coming after uranium are called transuranium elements.
 They are also called as inner-transition elements as they contain three outer most shell
incomplete and were also referred to as rare earth elements since their oxides were rare in earlier days.
The elements of f-blocks have been classified into two series.
1.  st inner transition or 4 f-series, contains 14 elements 58Ce to 71Lu. Filling of electrons takes
place in 4f subshell.
2. IInd inner transition or 5 f-series, contains 14 elements 90Th to 103Lr. Filling of electrons takes
place in 5f subshell.
 The actinides and lanthanides have been placed at the bottom of the periodic table to avoid the
undue expansion of the periodic table.
 Periodic Table & Periodicity

Ex-1 Elements A, B, C, D and E have the following electronic configurations :

A : 1s2 2s2 2p1 B : 1s2 2s2 2p6 3s2 3p1 C : 1s2 2s2 2p6 3s2 3p3
2 2 6 2 5 2 2 6 2 6 2
D : 1s 2s 2p 3s 3p E : 1s 2s 2p 3s 3p 4s
Which among these will belong to the same group in the periodic table ?
Sol. Out of these, elements A and B will belong to the same group of the periodic table because they have
same outer electronic configuration, ns2 np1.
Prediction of period, group and block:
  Period of an element corresponds to the principal quantum number of the valence shell.
  The block of an element corresponds to the type of subshell which receives the last electron.
  The group is predicted from the number of electrons in the valence shell or/and penultimate
shell as follows.
(a) For s-block elements, Group number = the number of valence electrons
(b) For p-block elements, Group number = 10 + number of valence electrons
(c) For d-block elements, Group number = number of electrons in (n – 1) d sub shell + number of
electrons in valence shell.
(58-71) 4f 
(d) For f block element –  - All f block elements are belongs to group number 3.
(92-103) 5f 
Two exceptions to this categorization:
Strictly, helium belongs to the s-block but its positioning in the p-block along with other group 18
elements in justified because it has a completely filled valence shell (1s2) and as a result, exhibits
properties & characteristics of other noble gases.
Hydrogen has only one s-electron and hence can be placed in group 1 (alkali metals). It can also gain
an electron to achieve a noble gas arrangement and hence it can behave similar to a group 17 (halogen
family) elements. Because it is a special case, we shell place hydrogen separately at the top of the
periodic table.
 Periodic Table & Periodicity
Isotopes in modern periodic table:
As isotopes of a elements have same atomic number and in modern periodic table the elements have
been allotted places based on their atomic number. All the isotopes an elements have been assigned
the same position in the modern periodic table.

Ex-2 An element X with Z = 112 has been recently discovered. What is the electronic configuration of the
element ? To which group and period will it belong ?
Sol. (a) The electronic configuration of element X is [Rn]86 5f 14 6d107s2
(b) It belongs to d-block as last electron enters in d subshell.
(c) As number of electrons in (n – 1)d subshell and valence shell is equal to twelve i.e. 10 + 2. So it
belongs to group 12.
(d) It belongs to period 7 of the periodic table as principal quantum number of valence shell is 7 (i.e.,
7s2).

Metals and nonmetals :

 The metals are characterised by their nature of readily giving up the electron(s) and from shining lustre.
Metals comprises more than 78% of all known elements and appear on the left hand side of the
periodic table. Metals are usually solids at room temperature (except mercury, gallium). They have high
melting and boiling points and are good conductors of heat and electricity. Oxides of metals are
generally basic in nature (some metals in their higher oxidation state form acid oxides e.g. CrO 3).
 Nonmetals do not lose electrons but take up electrons to form corresponding anions. Nonmetals are
located at the top right hand side of the periodic table. Nonmetals are usually solids, liquids or gases at
room temperature with low melting and boiling points. They are poor conductors of heat and electricity.
Oxides of nonmetals are generally acidic in nature.
Metalloids (Semi metals) :
 It can be understood from the periodic table that nonmetallic character increases as we move from left
to right across a row. It has been found that some elements which lie at the border of metallic and
nonmetallic behavior, possess the properties that are characteristic of both metals and nonmetals.
These elements are called semi metals or metalloids.
 The metalloids comprise of the elements Si, Ge, As, Sb, Se and Te.
 Oxides of metalloids are generally amphoteric in nature.
Diagonal relationship :
Some elements of certain groups of 2nd period resemble much in properties with the elements of third
period of next group i.e. elements of second and third period are diagonally related in properties. This
phenomenon is known as diagonal relationship. For example, the similarity between lithium (the first
member of group 1) and magnesium (the second element in group 2) is called a diagonal relationship.
Diagonal relationship also exist between other pairs of elements Be and Al, B and Si as shown in figure;
2nd period Li Be B C

3rd period Na Mg Al Si
Diagonal relationship arises because of ;
 (i) on descending a group, the atoms and ions increase in size. On moving from left to right in the
periodic table, the size decreases. Thus on moving diagonally, the size remains nearly the
same. (Li = 1.23 Å & Mg = 1.36 Å; Li+ = 0.76 Å & Mg2+ = 0.72 Å)
 (ii) it is sometimes suggested that the diagonal relationship arises because of diagonal similarity in
electronegativity values. (Li = 1.0 & Mg = 1.2; Be = 1.5 & Al = 1.5; B = 2.0 & Si = 1.8)
 (iii) Be and Al also show a diagonal relationship. In this case sizes are not so close (Be2+ = 0.45 Å
and Al3+ = 0.535 Å) but the charge / ionic radius ratio is nearly similar because the charges are
2+ and 3+ respectively.
(Ionic charge)
Charge /Ionic radius ratio =
(Ionic radius)
 Periodic Table & Periodicity
Section (B) : Shielding Effect and Zeff
The periodicity of atomic properties :
(1) Effective nuclear charge (Zeff):
The outer electron experiences
two opposing force : -
(i) Force of attraction from
nucleus.
(ii) Force of repulsion from inner
electrons.
Suppose inner electrons are not
present there then force of
attraction experience by test
electron must be greater than it
actually experienced because
electronic repulsion weakens the
force of attraction. This reduced
nuclear charge or nuclear
actually experienced by an electron is termed as effective nuclear charge.
Zeff = Z  
Zeff = Effective nuclear charge
Z = Atomic number
 = Screening constant or shielding constant or slater constant
Effective nuclear charge is not same for all the electrons present in an atom and it varies with distance
between electron and nucleus.
This effect in which inner electrons shield valence electron from the attraction due to nucleus is called
shielding effect.
It is also known as screening effect as inner electron create a protective screen between nucleus and
valence electrons.
Due to shielding effect valence electron experiences less attraction from the side of nucleus as if inner
electrons are absent.
s-orbitals have the largest screening effect for a given n value since s electrons are closer to the
nucleus.
Screening effect decreases as s-orbital > p-orbital > d-orbital > f-orbital.
th
n shell (valence shell )
th
(n–1) shell
th
(n–2) shell
e Electronic
Repulsion

Z Force of
Attraction

Electronic
e
Test electron

e Repulsion

Section (C) : Oxidation states & Inert pair effect

(2) Oxidation States:
Definition: The oxidation states (O.S) of an atom in a molecule or in an ion is the (imaginary) charge
the atom would have if the electron in each bond were located on the more electronegative atom.
Rule for determining the oxidation state
Fundamental Rule: Sum of oxidation no. of all the atoms of a species is equal to the charge on that
species.
e.g. For SO42– ion ; (O.N. of S atom) + (O.N. of O atom) × 4 = –2
 Periodic Table & Periodicity
For C60 molecule ; (O.N. of C atom) × 60 = 0
For NO2+ ion ; (O.N. of N atom) + (O.N. of O atom) × 2 = +1
Corollary 1: All atoms have oxidation state zero in their elemental state
Eg. Phosphorus atoms in P4, C atoms in graphite or diamond or fullerenes, O atoms in nascent oxygen
[O], diatomic O2.
Remember: Oxidation state of uncombined element is zero.
Corollary 2: Charge on any monoatomic ion is equal to its oxidation state.
Note : Oxidation state is often imagined as charge on the atom. In an ionic species this idea work very well. In
a covalent molecule, the electrons involved in bonding are considered to belong entirely to the more
electronegative species (i.e. it is assumed to be entirely ionic).
Caution: This is just an imagination, not the real picture.
Other Rules: In species when the following are combined with dissimilar atom(s) their O.No. is
(i) F atom: –1 ; alkali metals : +1 ; alkaline earth metals : +2; Al, Ga : +3 No exception.
(ii) H is mostly: +1, Exception: Hydrides of metals mentioned in (i) Where it's O.N is –1.
(iii) O is mostly: –2, exceptions, (a) in peroxides (b) when in conflict with rules (i) and (ii) e.g. in
peroxides like BaO2 , Ba is fixed as + 2. If we assume O as –2, Ba will have to assume a charge of +4
which is not permissible [Since Rule (i) has more weightage than rule (ii) or (iii)]. Hence, Ba must have
a charge of +2. Accordingly, we must adjust oxygen. Naturally we have O 22–, this is immediately
identified as our familiar peroxide ion. Naturally oxidation number of each atom is –1 in this case.
Similarly O atom is +1 or +2 with fluorine in O2F2 and OF2.
(iv) N is mostly: –3 e.g. in ammonia or ammonium ion e.g. in CN–, we can simply assume N as –3 and
move a head. Accordingly, C will be +2 (Check it for yourself by fundamental rule). Exceptions : When
in conflict with rule (i) (iii) eq. N +3 in NF3 (since F must be –1) and +5 in NO3– (since O must be –2).
(v) Cl, Br and I are usually –1 e.g. in halides.
Exceptions: When is conflict with rules (i)-(iv). Amongst halogens, the reactivity order is Cl > Br > I e.g.
in ICl, Cl is regarded as –1. Naturally, I must adjust itself as +1. BrCl 3 Br is + 3 since Cl must be –1.
However, is Cl2O, Cl must adjust to +1 state. Since O should preferably be –2.
Interestingly, in a case like POCl3, both O and Cl can have their desirable state of –2 and –1
respectively. In this case, P must adjust as per the convenience of O and Cl atoms (which have higher
priority i.e. higher electonegativity).
(vi) S is –2 in sulphides. If however, can have higher oxidation state, highest being equal to the group
no. (i.e. 6)
(vii) Metal usually do not exhibit negative oxidation states. Exceptions: Gold is sometimes found in –1.
Remember: Non-stoichiometric compounds always have metal cation in at least two different oxidation
state.
Average oxidation number: A given element may be present in more than one oxidation states within
a given molecule if more than one atoms of the element are present.
e.g. NH4NO2 contain N atom in NH4+ ion as well as NO2– ion. Try finding their oxidation state separately.
In NH4+ ion, N is present in –3 oxidation state and in NO2– ion N is present in +3 oxidation state. Else,
even if you consider the average state of N atom in the compound, it comes out to be [{(+3) + (–3)}/2]
that is 0.
(3) Inert Pair Effect :
The outer shell ‘s’ electrons (ns2) penetrate to (n–1)d electrons and thus become closer to nucleus and
are more effectively pulled towards the nucleus. This results in less availability of ns2 electron pair for
bonding or ns2 electron pair becomes inert. This is called Inert Pair Effect. The inert pair effect begins
after n > 4 and increases with increasing value of n. This can be thought as a reason for two different
oxidation states, normal and (normal – 2), among elements of Boron, Carbon and Nitrogen family.
In these families, the stability of higher oxidation state decreases while that of lower oxidation state
increases on moving down the group.
Eg. Ga3+ > In3+ > Tl3+ ; Ga+ < In+ < Tl+
Ge4+ > Sn4+ > Pb4+ ; Ge2+ < Sn2+ < Pb2+
As5+ > Sb5+ > Bi5+ ; As3+ < Sb3+ < Bi3+
Thats why, Pb4+ and Bi5+ compounds are strong oxidising agents. However the last elements of the
group do form compounds in oxidation state, but only with highly electronegative higher elements like F
and O.
So compounds like TlF3, Tl2O3, PbF4, PbCl4, BiF5, NaBiO3 exist in nature while compounds like PbI4,
PbBr4, BiI5, BiBr5, BiCl5 etc do not exist. TlI3 exists exceptionally as Tl+(I3)–.
 Periodic Table & Periodicity
Table-3
List of common oxidation sate of an element in Periodic Table
1 18
1 2
H He
+1
–1

2 13 14 15 16 17
3 3 5 6 7 8 9 10
Li Be B C N O F Ne
+1 +2 +3 +4 +5 +2 –1
–
–3 +2 +4
1/2
–4 +3 –1
etc. +1 –2
–3
0
etc.
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
+1 +2 +3 +4 +5 +6 +7 0
–4 +3 +4 +5
+1 +2 +3
–3 –2 +1
0
3 4 5 6 7 8 9 10 11 12 –1
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
+1 +2 +2 +2 +2 +2 +2 +2 +2 +2 +1 +2 +3 +4 +5 +6 +7 +4
+3 +3 +3 +3 +3 +3 +3 +3 +2 –4 +3 +4 +5 +2
+4 +4 +4 +4 +4 +4 +4 –3 –2 +3 0
+5 +5 +5 +5 +5 +1
+6 +6 +6 –1
+7
37 38 49 50 51 52 53 54
Rb Sr In Sn Sb Te I Xe
+1 +2 +3 +4 +5 +6 +7 +8
+1 +2 +3 +4 +5 +6
–3 –2 +3 +4
+1 +2
0 0
–1
55 56 81 82 83 84 85 86
Cs Ba Tl Pb Bi Po At Rn
+1 +2 +3 +4 +5
+1 +2 +3
* Bold mark oxidation number are general stable oxidation number of an element in
compound state.
 Periodic Table & Periodicity
Section (D) : Atomic and Ionic radius
(4) Atomic radius :
It is distance between outermost electron and nucleus.

X-ray diffraction, electron diffraction method and nuclear magnetic resonance (NMR) spectrum methods
are used to determine internuclear distance or bond length.
Atomic radius depends on the type of chemical bond between atoms in a molecule. These are :
1. Covalent radius 2. Ionic radius 3. Metallic radius 4. Vander waal’s radius
Type of
S.No. DISCRIPTION
radius

Covalent
radius
SBCR(Single
1.
Bonded
Covalent
Radius)
Covalent radius is calculated in covalent compounds.
Covalent compound’s form covalent bonds.
Covalent bonds are formed by overlapping of atomic orbitals.
Type of Covalent radius.
d(X−X) / pm d(X−X) / pm
Halogen Molecule Structure Model
(gas phase) (solid phase)

F—F
Fluorine F2 143 149
143pm

Cl — Cl
Chlorine Cl2 199 198
199pm

Br — Br
Bromine Br2 228 227
228pm

I—I
Iodine I2 266 272
266pm
Periodic Table & Periodicity
Covalent radius is the one-half of the internuclear distance between two singly
bonded two nuclei (of like atoms).
Internuclear distance of A–A(A2) molecule is (dA–A) and covalent radius is rA then
dA–A = rA + rA dA–A = 2rA
(i) In Homo d AA
atomic rA 
2
Molecules
1.98
e.g. – In Cl2 molecule, internuclear distance is 1.98 Å so rCl = = 0.99 Å
2
SBCR of O, N and C etc. elements can be determined by taking H2O2, N2H4,
C2H6 respectively.
(a) For Hetero atomic molecule with not E.N. difference.
dA–B = rA + rB
Example : For A–B molecule Electronegativities of A and B are approximately
(ii) Hetero equal e.g. C–I E.N. of C and I are approx equal (2.5) internuclear distance of C–I
atomic is 2.13Å and rC is 0.77Å.
molecule
Solution : dC–I = rC + rI  rI = 2.13 – 0.77 = 1.36Å
(b) Heteroatomic molecule withE.N. difference more
If in a diatomic molecule electronegativities of A–B have more difference. Then
actual bond length will be reduced.
2. Ionic Radius
When an neutral gaseous atom loses electron it converts into cation.
Radius = Atomic radius > Cationic radius
Reason: After loosing electron number of electron reduces, but number of
protons remains same, due to this Zeff increases, hence electrons pulls towards
nucleus and atomic radius decreases, moreover after losing all the electrons from
the outer most shell, penultimate shell becomes ultimate shell which is nearer to
(i) Cationic nucleus so size decreases.
radius 1
Size of cation 
Magnitude of +ve charge or z eff

Example
Size of cation = Fe > Fe+2 > Fe+3
Size of cation = Pb+2 > Pb+4
Size of cation = Mn > Mn+2 > Mn+3 > Mn+4 > Mn+5 > Mn+6 > Mn+7
When neutral gaseous atom gains electron it converts into anion.
Radius = Anionic radius > Atomic radius
Reason: In an anion electron are more than protons so effective nuclear charge
reduces, and inter electronic repulsion increases, which also increases screening
effect. So distance between electron and nucleus increases and size of anion
(ii) Anionic also increases.
Size of anion  Magnitudeof  ve charge

Example : Size of F– > F why ?

Sol.
radius F F–
Proton 9 9
electron 9 10
Z 9 9
=1 = 0.9
 9 10
e
As Zeff of F– is less than F so size of F– > F
Periodic Table & Periodicity

(iii) Size of
iso
electronic
species

H– He
Li +
Be +2
N 3–
O 2–
F– Ne
Na+ Mg+2 Al+3 S2– Cl– Ar
K+ Ca+2 Sc+3 Se2– Br– Kr
Rb+ Sr+2 Y+3 Te2– I– Xe
Cs+ Ba+2 La+3

Those species having same number of electron but different nuclear charge
forms isoelectronic series.
For isoelectronic species the atomic radius increases with decrease in nuclear
charge.
Ions K+ Ca2+ S2– Cl –
Atomic number 19 20 16 17
electron 18 18 18 18
Example
Order of radius = S2– > Cl– > K+ > Ca2+
Order of radius = P3– > S2– > Cl–
Order of radius = N3– > O2– > F– > Na+ > Mg2+ > Al3+
Order of radius = Au+  Hg2+  Tl3+  Pb4+

It is one-half of the nuclear distance between two adjacent metallic atoms in

Metallic
crystalline lattice structure.
radius
so metallic radius > Covalent radius.
3. 1
Metallic radius 
Metallic bond strength
More metallic radius  loose crystal packing  less bond strength (body
centered packing)
Less metallic radius tight crystal packing FCC  High bond strength
(Hexagonal close packing)
Periodic Table & Periodicity
Those atoms (like noble gases) which are not bonded with each other,
experiences a weak attractive force to come nearer.
The half of the distance between the nuclei of adjacently placed atoms in solid
state of a noble gas is Vander Waal’s radius.
Vander Waal radius > Covalent radius.
Inert gas have only Vander Waal radius
In molecules of nonmetals both covalent and Vander Waal radius exists.

Van der
4. Waal’s
radius

Radius = Vander Waal radius > Metallic Radius > Covalent Radius
Van der waal force of attraction  Molecular weight OR atomic weight (in inert gases)

In a period from left to right Vander Waal radius decreses.

In a group from top to bottom its values increases.
Factors
affecting
atomic size

(i) Effective 1
Atomic radius 
nuclear Effective nuclear charge Example Li > Be > B > C > N > O > F
charge

(ii) Number Atomic radius  No. of shells Example Li < Na < K < Rb < Cs
of shells

5. (iii)
screening Atomic radius  Screening effect
effect
(iv) 1
Atomic radius 
Magnitude of Magnitudeof  vecharge Example Mn > Mn+2 > Mn+3 > Mn+4
+ve charge
(v)
Magnitude of Atomic radius  Magnitudeof  ve charge Example O < O– < O–2
-ve charge

(vi) Bond 1
Atomic radius  Example N–N > N=N > NN
order Bond order
 Periodic Table & Periodicity
Table-4
Variation in a Period (left to right) : Variation in a Group (top to bottom) :

Nuclear charge (Z) increases by one unit Nuclear charge (Z) increases by more than one unit

Effective nuclear charge (Zeff) almost remains

Effective nuclear charge (Zeff) also increases constant because of increased screening effect of
inner shells electrons.

But number of orbitals (n) remains constant But number of orbitals (n) increases.

As a result, the electrons are pulled closer to the

nucleus by the increased Zeff.
The effect of increased number of atomic shells
1
rn  overweighs the effect of increased nuclear charge.
Z* As a result of this the size of atom increases from top
Hence atomic radii decrease with increase in to bottom in a given group.
atomic number in a period from left to right.

Irregularties
 In the transition series (e.g. in first transition series), the covalent radii of the elements decrease from
left to right across a row until near the end when the size increases slightly. On passing from left to
right, extra protons are placed in the nucleus and the extra electrons are added. The orbital electrons
shield the nuclear charge incompletely. Thus the nuclear charge attracts all the electrons more strongly,
hence a contraction in size occurs. The radii of the elements from Cr to Cu, are very close to one
another because the successive addition of d-electrons screen the outer electrons (4s) from the inward
pull of the nucleus. As a result of this, the size of the atom does not change much in moving from Cr to
Cu.
Table-5
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radius (pm) 144 132 122 117 117 117 116 115 117 125
 The elements of group 3 belonging to d-block show the expected increase in size as that found in case
of s-block and p-block elements. However, in the subsequent groups that is 4th onwards (upto 12th
group), there is increase in size between the first and second member, but hardly any increase between
the second and third elements of the given group. There are 14 lanthanide elements between
lanthanum and hafnium, in which the antepenultimate 4f shell of electrons (exert very poor shielding
effect) is filled. There is a gradual decrease in size of the 14 lanthanide elements from cerium to
lutetium. This is called lanthanide contraction. This lanthanide contraction cancels out the normal size
increase on descending a group in case of transition elements.

Ex-3 Atomic radius of Li is 1.23 Å and ionic radius of Li + is 0.76 Å. Calculate the percentage of volume
occupied by single valence electron in Li.
4
Sol. Volume of Li = × 3.14 × (1.23)3 = 7.79 Å3 (–Li = 1s22s1)
3
4
Volume of Li+ = × 3.14 × (0.76)3 = 1.84 Å3 (–Li+ = 1s2)
3
 Volume occupied by 2s subshell = 7.79 – 1.84 = 5.95 Å3.
5.95
 % Volume occupied by single valence electron i.e., 2s electron = ×100 = 76.4%
7.79
Ex-4 Select from each group the species which has the smallest radius stating appropriate reason.
(a) O, O–, O2– (b) P3+, P4+, P5+
Sol. (a) O is having smallest radius. Anion is larger than its parent atom. Also the anion of the same
atom with higher negative charge is bigger in size as compared to anion with smaller negative charge
as proton to electron ratio decreases thus attraction between valence shell electrons and nucleus
decreases. Hence electron cloud expands.
 Periodic Table & Periodicity
(b) The ionic radius decreases as more electrons are ionized off that is as the valency increases. So the
correct order is P5+ < P4+ < P3+.
Ex-5 Mg2+ is smaller than O2– in size, though both have same electronic configuration. Explain ?
Sol. Mg2+ and O2– both are isoelectronic i.e., have same number of electrons. But Mg2+ having 12 protons in
its nucleus exerts higher effective nuclear charge than O2– having 8 protons and thus valence shell as
well as inner shells electrons are more strongly attracted by the nucleus in Mg 2+ resulting smaller size
than O2–.
Section (E) : Ionisation energy
(5) Ionisation Energy :
Ionisation energy (IE) is defined as the amount of energy required to remove the most loosely bound
electron from an isolated gaseous atom to form a cation.
(IE )
M(g) 
1
 M+(g) + e– ; M+ (g) + IE2  M2+ (g) + e–
M2+ (g) + IE3   M+3 (g) + e–
IE1, IE2 & IE3 are the Ist, IInd & IIIrd ionization energies to remove electron from a neutral atom,
monovalent and divalent cations respectively.
In general, (IE)1 < (IE)2 < (IE)3 < .............. because, as the number of electrons decreases, the
attraction between the nucleus and the remaining electrons increases considerably and hence
subsequent ionization energies increase.
 Ionization energies are determined from spectra and are measured in kJ mol–1, k Cal mol–1, eV
(electron volt).
 Factors Influencing Ionisation energy
Variation in ionization energies in a period and group may or not be regular and can be influenced by
the following factors.
(A) Size of the Atom : Ionisation energy decreases with increase in atomic size.
As the distance between the outer most electrons and the nucleus increases, the force of attraction
between the valence shell electrons and the nucleus decreases. As a result, outer most electrons are
held less firmly and lesser amount of energy is required to knock them out.
For example, ionisation energy decreases continuously in a group from top to bottom with increase in
atomic size. But in 13th & 14th group the ionisation energy does not decrease continuously and order is
as follows:
For 13th group: B > Tl > Ga > Al > In
For 14th group: C > Si > Ge > Pb > Sn
(B) Nuclear Charge : The ionisation energy increases with increase in the nuclear charge.
This is due to the fact that with increase in the nuclear charge, the electrons of the outer most shell are
more firmly held by the nucleus and thus greater amount of energy is required to pull out an electron
from the atom.
For example, ionisation energy increases as we move from left to right along a period due to increase in
nuclear charge.
(C) Shielding or screening effect : The electrons in the inner shells act as a screen or shield between
the nucleus and the electrons in the outer most shell. This is called shielding effect. The larger the
number of electrons in the inner shells, greater is the screening effect and smaller the force of attraction
and thus ionization energy (IE) decreases.

(D) Penetration effect of the electron : The ionization energy also depends on the type of electron
which is removed. s, p, d and f electrons have orbitals with different shapes. An s electron penetrates
closer to the nucleus, and is therefore more tightly held than a p electron. Similarly p-orbital electron is
more tightly held than a d-orbital electron and a d-orbital electron is more tightly held than an f-orbital
electron. If other factors being equal, ionisation energies are in the order s > p > d > f.
For example, ionisation energy of aluminium is comparatively less than magnesium because outer most
electron is to be removed from 3p-orbital (having lesser penetration effect) in aluminium where as in
magnesium it will be removed from 3s-orbital (having larger penetration effect) of same energy level.
 Periodic Table & Periodicity
(E) Electronic Configuration:
If an atom has exactly half-filled or completely filled orbitals, then such an arrangement has extra
stability.
The removal of an electron from such an atom requires more energy then expected. For example, first
ionisation energy of beryllium is greater than boron because beryllium has extra stable outer most
completely filled outer most 2s orbital while boron has partially filled less stable outer most 2p-orbital.
Be (Z = 4) 1s2, 2s2 B (Z = 5) 1s2, 2s2, 2p1
Similarly noble gases have completely filled electronic configurations and hence they have highest
ionisation energies in their respective periods.
 Metallic or electropositive character of elements increases as the value of ionisation energy decreases.
 The relative reactivity of the metals in gaseous phase increases with the decrease in ionisation energy.
 The reducing power of elements in gaseous phase increases as the value of ionisation energy
decreases. Amongst alkali metals, the lithium is strongest reducing agent in aqueous solution.

Ex-6 From each set, choose the atom which has the largest ionization enthalpy and explain your answer with
suitable reasons. (a) F, O, N (b) Mg, P, Ar
Sol. (a) Fluorine (F) has the largest ionization enthalpy because in moving from left to right in a period,
atomic size decreases and electrons are held more tightly. Since F has the smallest size and maximum
nuclear charge. It has the largest ionization enthalpy among these elements.
(b) Argon (Ar) has the largest ionization enthalpy as argon has extra stable fully filled configuration.
Ex-7 First and second ionisation energies of magnesium are 7.646 eV and 15.035 eV respectively. The
amount of energy in kJ needed to convert all the atoms of magnesium into Mg2+ ions present in 12 mg
of magnesium vapour will be ? [Given 1 eV = 96.5 kJ ml –1].
Sol. Total energy needed to convert one Mg atom into Mg2+ gas ion,
= IEI + IEII = 22.681 eV = 2188.6 kJ mol–1.
  12 mg of Mg = 0.5 × 10–3 mole.
 Total energy = 0.5 × 10–3 × 2188.6 = 1.0943 kJ Ans.
Ex-8 Following graph shows variation of ionization energies with atomic number in second period (Li–Ne).
Value of ionization energies of Na(11) will be :

(A) above Ne (B) below Ne but above O.

(C) below Li (D) between N and O.
Sol. Na is 3rd period element and is bigger than Li. The distance between the nucleus and outer most
electron is more as compared to Li. Thus the outer most electron is loosely bound with nucleus and
removal of electron is easier. So option (C) is correct.
Ex-9 M(g)  M+ (g) + e– ; H = 100 eV.
M(g)  M2+ (g) + 2e– ; H = 250 eV.
Which is/are correct statement(s) ?
(A) IE1 of M(g) is 100 eV (B) IE1 of M+ (g) is 150 eV.
(C) IE2 of M(g) is 250 eV. (D) IE2 of M(g) is 150 eV.
Sol. M(g)  M+(g) + e– IE1 of M
M  M + e
+ 2+ –
IE2 of M but IE1 of M+
M M2+ + 2e– (IE1 + IE2). Ans. (A,B,D)
 Periodic Table & Periodicity
Section (F) : Electron gain enthalpy
(6) Electron Affinity:
Electron affinity is conventionally defined as the energy released when an electron is added to the
valence shell of an isolated gaseous atom.
F + e–  F– Ea = 328 kJ mol–1
A positive electron affinity indicates that the ion X– has a lower, more negative energy than the neutral
atom X. The second electron gain enthalpy, the enthalpy change for the addition of a second electron to
an initially neutral atom, invariably positive because the electron repulsion out weighs the nuclear
attraction.
O(g) + e–(g) 
Exothermic
 O– (g) ; Ea = 140.9 kJ mol–1 ; egH = – 140.9 kJ mol–1
O–(g) + e–(g) 
Endothermic
 O2– (g) ;Ea = – 744 kJ mol–1 ; egH = 744 kJ mol–1
An element has a high electron affinity if the additional electron can enter a shell where it experiences a
strong effective nuclear charge.
The electron gain enthalpy egH, is the change in standard molar enthalpy when a neutral gaseous
atom gains an electron to form an anion.
X (g) + e– (g)  X– (g)
Now a days both electron affinity and electron gain enthalpy terms are used.
Both are same in magnitude but opposite in sign.
E.A. = +ve (Exothermic):– egH < 0.
E.A. = –ve (Endothermic):– egH > 0.
The units of EA and Electron gain enthalpy are ev/atom or Kcal / mole or KJ / Mole.
Electron gain enthalpy provides a measure of the ease with which an atom adds an electron to form
anion. Electron gain may be either exothermic or endothermic depending on the elements.
When an electron is added to the atom and the energy is released, the electron gain enthalpy is
negative and when energy is needed to add an electron to the atom, the electron gain enthalpy is
positive.
Although the electron gain enthalpy is the thermodynamically appropriate term, much of inorganic
chemistry is discussed in terms of a closely related property, the electron affinity, E a of an element
which is the difference in energy between the gaseous atoms and the gaseous ions.
Ea = E (X, g) – E (X–, g)
 Group 17 elements (halogens) have very high negative electron gain enthalpies (i.e. high electron
affinity) because they can attain stable noble gas electronic configuration by picking up an electron.
 Across a period, with increase in atomic number, electron gain enthalpy becomes more negative
because left to right across a period effective nuclear charge increases and consequently it will be
easier to add an electron to a small atom.
 As we move in a group from top to bottom, electron gain enthalpy becomes less negative because the
size of the atom increases and the added electron would be at larger distance from the nucleus.

In general the electron gain enthalpies for some third period element (e.g. P, S, Cl) are more negative
than the corresponding second period members (e.g. N, O, F). This is due to the smaller size of the
atoms of the second period elements which would produced larger electron-electron repulsions for the
additional electron.

Group 1  e.g. H Group 16  e.g. H Group 17  e.g. H Group 0  e.g. H

H –73 He +48
Li –60 O –141 F –328 Ne +116
Na –53 S –200 Cl –349 Ar +96
K –48 Se –195 Br –325 Kr +96
Rb –47 Te –190 I –295 Xe +77
Cs –46 Po –174 At –270 Rn +68
 Noble gases have large positive electron gain enthalpies because the electron has to enter the next
higher energy level leading to a very unstable electronic configuration.
 Periodic Table & Periodicity
 Negative electron gain enthalpy of O or F is less than S or Cl. This is due to the fact that when an
electron is added to O or F, the added electron goes to the smaller n = 2 energy level and experiences
significant repulsion from the other electrons present in this level. In S or Cl, the electron goes to the
larger n = 3 energy level and consequently occupies a larger region of space leading to much less
electron-electron repulsion.
 Electron gain enthalpies of alkaline earth metals are very less or positive because the extra electron is
to be added to completely filled s-orbitals in their valence shells.
 Nitrogen has very low electron affinity because there is high electron repulsion when the incoming
electron enters an orbital that is already half filled.
1
 (i) Electron affinity 
Atomic size
(ii) Electron affinity  Effective nuclear charge (zeff)
1
(iii) Electron affinity 
Screening effect
(iv) Stability of half filled and completely filled orbitals of a subshell is comparatively more and the
addition of an extra electron to such an system is difficult and hence the electron affinity value
decreases.

Ex-10 Consider the elements N, P, O and S and arrange them in order of increasing negative electron gain
enthalpy.
Sol. Order of increasing negative electron gain enthalpy is N < P < O < S. For detail refer text.
Ex-11 Why do halogens have high electron gain enthalpies (i.e. –egH) ?
Sol. The valence shell electronic configuration of halogens is ns2np5 and thus they require one electron to
acquire the stable noble gas configuration ns2np6. Because of this they have strong tendency to accept
an additional electron and hence have high electron gain enthalpies.
Ex-12 Which will have the maximum value of electron affinity O x ,Oy, Oz [x, y and z respectively are 0, –1 and
–2] ?
(A) Ox (B) Oy (C) Oz (D) All have equal.
Sol. Being neutral atom oxygen will have higher electron affinity as there is electrostatic repulsion between
additional electron and negative ion in case of O– and O2–. So option (A) is correct.
Ex-13 The amount of energy when million atoms of iodine are completely converted into I – ions in the vapour
state according to the equation, I (g) + e– (g)  I– (g) is 5.0 × 10–13 J.
Calculate the electron gain enthalpy of iodine in terms of kJ mol –1 and eV per atom.
Sol. The electron gain enthalpy of iodine is equal to the energy released when 1 mole of iodine atoms in
vapour state are converted into I– ions.
5.0  10 –13  6.023  1023
=– = – 30.1 × 104 J = – 301 kJ.
106
–301
Electron gain enthalpy of iodine in eV per atom = = –3.12.
96.5
Ex-14 Account for the large decrease in electron affinity between Li and Be despite the increase in nuclear
charge.
Sol. The electron configurations of Li and Be are [He]2s1 and [He]2s2, respectively. The additional electron
enters the 2s orbital of Li but the 2p orbital of Be and hence is much less tightly bound. In fact, the
nuclear charge is so well shielded in Be that electron gain is endothermic.
 Periodic Table & Periodicity
Section (G) : Electronegativity
(7) Electronegativity:
Electronegativity is a measure of the tendency of an element to attract shared electrons towards itself in
a covalently bonded molecules.
The magnitude of electronegativity of an element depends upon its ionisation potential & electron
affinity. Higher ionisation potential & electron affinity values indicate higher electronegativity value.
 With increase in atomic size the distance between nucleus and valence shell electrons increases,
therefore, the force of attraction between the nucleus and the valence shell electrons decreases and
hence the electronegativity values also decrease.
 With increase in nuclear charge force of attraction between nucleus and the valence shell electrons
increases and, therefore, electronegativity value increases
 In higher oxidation state, the element has higher magnitude of positive charge.
Thus, due to more positive charge on element, it has higher polarising power.
Hence with increase in the oxidation state of element, its electronegativity also increases.
Charge on cation  electronegativity of the atom.
 The electronegativity also increases as the s-character in the hybrid orbitals increases.
Hybrid orbital sp3 sp2 sp
s-character 25% 33% 50%

Electronegativity increases
Electronegativity of some elements according to pauling scale.
Elements H Li Be B C N O F Ne P S Cl Br I
Electronegativity 2.1 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0.9 2.1 2.5 3.0 2.8 2.5

Table-6
Variation of electronegativity in a group Variation of electronegativity in a period

On moving down the groups, Z increases but Zeff almost

While moving across a period left to right, Z,
remains constant, number of shells (n) increases, rn
Zeff increases & rn decreases. Therefore,
(atomic radius) increases. Therefore, electronegativity
electronegativity increases along a period.
decreases moving down the groups.

There is no direct method to measure the value of electronegativity, however, there are some scales to
measure its value.
(a) Pauling’s scale : Linus Pauling developed a method for calculating relative electronegativities
of most elements. According to Pauling
 = XA – XB = 0.208 E.  E E *
A B AA B B
EA-B = Bond enthalpy/ Bond energy of A – B bond.
EA - A = Bond energy of A – A bond
EB –B = Bond energy of B – B bond
(All bond energies are in kcal / mol)
   = XA – XB = 0.1017 E.A B  EA  A  EBB * All bond energies are in kJ / mol.
(b) Mulliken’s scale : Electronegativity  (chi) can be regarded as the average of the ionisation
energy (IE) and the electron affinity (EA) of an atom (both expressed in electron volts).
IE  EA
M =
2
[Paulings’s electronegativity P is related to Mulliken’s electronegativity M as given below.
P = 1.35 (M)1/2 – 1.37
Mulliken’s values were about 2.8 times larger than the Pauling’s values.]*
* Only for reference, student need not memorize it.
 Periodic Table & Periodicity
APPLICATION OF ELECTRONEGATIVITY :
(a) Nomenclature :
Compounds formed from two nonmetals are called binary compounds. Name of more
electronegative element is written at the end and ‘ide’ is suffixed to it. The name of less
electronegative element is written before the name of more electronegative element of the
formula. For example -
Correct formula Name
(a) I+ Cl– Iodine chloride
(b) Cl+ F– Chlorine fluoride
(c) Br+ Cl– Bromine chloride
(d) IBr Iodine bromide
(e) OF2 Oxygen difluoride
(f) Cl2O Dichlorine oxide
(b) Effect on bond length: When the  EN increases between two atoms in a molecule then bond length
between that atoms decreases.
Order of  EN:– HF > HCl > HBr > HI
Order of bond length:– HF < HCl < HBr < HI
 Periodic Table & Periodicity
MISCELLANEOUS SOLVED PROBLEMS
1. A M2+ ion derived from a metal in the first transition metal series has four electrons in 3d subshell. What
element might M be ?
Ans. Chromium
Sol. Electron configuration of M2+ is : [Ar]18 4s0 3d4
 Electron configuration of M is : [Ar]18 4s1 3d5 (and not 4s2 3d4)
So total number of electrons = 24.
Hence, metal M is chromium (Cr).
2. Following are the valence shell electronic configurations of some elements.
(i) 3s2 3p5 (ii) 3d10 4s2 (iii) 2s2 3p6 4s1 (iv) 1s2 2s2
Find out the blocks to which they belong in the periodic table ?
Ans. (i) p-block (ii) d-block (iii) s-block (iv) s-block
Sol. The block of the elements depend on the type of sub-shell which receive the last electron. In case of (i)
it enters in 3p-subshell, (ii) it enters 3d-subshell, (iii) it enters 4s-subshell and (iv) it enters 2s-subshell.
3. Find out the group of the element having the electronic configuration, 1s2 2s2 2p6 3s2 3p6 3d6 4s2.
Ans. As last electron enters in d-subshell, therefore this belongs to d-block. For d-block element the group
number is equal to the number of valence shell electrons + number of electrons in (n-1) d-subshell. So,
group number = 6 + 2 = 8.
4. Arrange the following ions in the increasing order of their size : Be2+, Cl–, S2–, Na+, Mg2+, Br– ?
Ans. Be2+ < Mg2+ < Na+ < Cl– < S2– < Br–
Sol. Be2+ is smaller than Mg2+ as Be2+ has one shell where as Mg2+ has two shells.
Mg2+ and Na+ are isoelectronic species : Ionic radius  1/nuclear charge.
Cl– and S2– are isoelectronic species : Ionic radius  1/nuclear charge.
Cl– is smaller than Br– as Cl– has three shells where as Br– has four shells.
5. The (IE1) and the (IE2) in kJ mol–1 of a few elements designated by Roman numerals are shown below:
I II III
IE1 403 549 1142
IE2 2640 1060 2080
Which of the above elements is likely to be a
(a) non-metal (b) alkali metal (c) alkaline earth metal ?
Ans. (a) non-metal(III) – Due to highest ionisation energy, (IE1) and (IE2).
(b) alkali metal(I) – Due to lowest ionisation energy, (IE1) and there is quite high jump in (IE2) due to
inert gas configuration.
(c) alkaline earth metal (II) – There is little difference in (IE1) and (IE2) and the value of (IE1) is slightly
greater than(I) due to stable configuration(ns2).
6. Ionisation energy and electron affinity of fluorine are respectively 17.42 and 3.45 eV. Calculate
electronegativity of fluorine atom.
Ionisationenergy  Electronaffinity
Sol. According to Mulliken’s electronegativity (M) =
2
17.42  3.45
= = 10.435
2
10.435
Therefore, electronegativity on Pauling’s scale (P) = = 3.726
2.8
Ans. P = 3.726
 Periodic Table & Periodicity
7. Why the electron gain enthalpy values of alkaline earth metals are lower (i.e. less negative) or positive?
Sol. The general valence shell electron configuration of alkaline earth metals is ns2 (stable configuration).
The extra electron must enter np subshell, which is effectively shielding by the two ns electrons and the
inner electrons. Consequently, the alkaline earth metals have little or no tendency to pick up an extra
electron.
8. In Column-I, there are given electronic configurations of some elements. Match these with the correct
metals given in Column-II :
Column-I Column-II
(A) ns2, np5 (p) Chromium
(B) (n – 1) d10, ns1 (q) Copper
(C) (n – 1) d5, ns1 (r) Krypton
(D) (n – 1) d10, ns2, np6 (s) Bromine
Ans. (A)  (s) ; (B)  (q) ; (C) (p) ; (D) (r).
Sol. (A) ns2np5 is general valence shell electron configuration of halogens. So this configuration belongs to
bromine.
(B) (n – 1) d1–10 ns1–2 ; This is electron configuration of d-block elements. As it contains (n – 1) d10ns1
configuration it belongs to copper.
(C) (n – 1) d1–10 ns1–2 ; This is electron configuration of d-block elements. As it contains (n – 1) d5ns1
configuration it belongs to chromium.
(D) Noble gases has valence shell electron configuration ns2 np6, so it belongs to krypton.
9. Match the metals given in Column-II with their type given in Column-I :
Column-I Column-II
(A) Metalloid (p) Sulphur
(B) Radioactive (q) Gold
(C) Transition metal (r) Arsenic
(D) Chalcogen (s) Uranium
Ans. (A)  (r) ; (B)  (s) ; (C) (q) ; (D) (p)
Sol. (A) Arsenic is a metalloid because it behaves as metal (forming cation, As3+ -AsCl3) as well as nonmetal
(forming anion, As3– -AsH3).
(B) Uranium is a radioactive element.
(C) Those elements which in their neutral atoms or in most common oxidation state have partially filled
d-orbitals are called as transition elements. Gold in its +3 oxidation state has electron configuration
[Xe]54, 5d86s0 .
(D) 16th group elements like oxygen and sulphur are ore forming elements and therefore are called as
chalcogens.
10. Match the metals given in Column-II with their type given in Column-I :
Column-I Column-II
(A) Representative element (p) Cerium
(B) Lanthanide (q) Aluminum
(C) Coinage metal (r) Thorium
(D) Actinide (s) Gold
Ans. (A)  (q) ; (B)  (p) ; (C) (s) ; (D) (r)
Sol. (A) s-block and p-block elements are collectively called as representative elements. As in aluminium
last electron enters in p-subshell ([Ne]103s23p1).
(B) Lanthanide series follows lanthanum (atomic number 57) and starts from cerium (atomic number
58) to lutetium (atomic number 71), fourteen 4f- series elements.
(C) Group 11- transition elements copper, silver & gold are known as coinage metals (used for making
the coins).
(D) Actinides series follows actinium (atomic number 89) and starts from thorium (atomic number 90) to
lawrencium (atomic number 103), fourteen 5f- series elements.
 Periodic Table & Periodicity
11. Match the particulars given in Column-I with the process / metal / species given in Column-II.
Column-I Column-II
(A) Isoelectronic species (p) A+(g) + energy  A ++(g) + e– (g)
(B) Half filled orbital (q) Ar, K+, Ca++
(C) Second ionisation energy (r) Lutetium
(D) Inner transition element (s) Antimony
Ans. (A)  (q) ; (B)  (s) ; (C) (p) ; (D) (r)
Sol. (A) Species having same number of electrons but different nuclear charge are called isoelectronic
species. Ar, K+ & Ca++ have same number of electrons i.e. 18 but 18, 19 & 20 number of protons
respectively.
(B) np3, (n–1) d5 and (n–2) f 7 represent half filled orbitals. Antimony has ([Kr]36 4d105s25p3).
(C) The energy required to remove an electron from an univalent cation(g) is called second ionisation
energy.
(D) 4f and 5f- series elements are called inner transition elements because they have three outer most
shells incomplete.
12. Match the type of elements / characteristic of the elements listed in Column-I with the correct element
listed in Column-II.
Column-I Column-II
(A) Highest 1st ionisation energy (p) Technitium
(B) Highest electronegativity (q) Lithium
(C) Synthetic element (r) Helium
(D) Strongest reducing agent (s) Fluorine
Ans. (A)  (r) ; (B)  (s) ; (C) (p) ; (D) (q).
Sol. (A) Helium has highest 1st ionisation energy amongst all the elements of periodic table because of ns2
valence electron configuration and its small size of atom.
(B) Fluorine has highest electronegativity i.e. 4.0 on Pauling scale on account of its small size.
(C) Technitium is a man made element.
(D) Lithium is a strongest reducing agent because of its highest negative value of Eº due to its higher
hydration energy on account of its small size of atom.
13. The Column-I has certain details about the elements of s-, p- and d-block elements. Match those with
the group number of the elements listed in Column-II.
Column-I Column-II
(element / elements) (group number)
(A) An element whose fourth shell contains two p-electrons (p) 8th group
(B) An element whose valence shell contains one unpaired p-electron (q) 12th group
(C) An element which receives last electron in (n – 1) d-subshell (r) 14th group
2 10
(D) An element with the ground-state electron configuration [Ar]4s 3d (s) 17th group
Ans. (A)  (r) ; (B)  (s) ; (C) (p, q) ; (D) (q).
Sol. (A) [Ar]3d104s24p2 : Fourth shell contains two electron in 4p-sub shell i.e., 4p2. Therefore, group number
= 10 + 4 = 14.
(B) Halogens (i.e. group number 17) have valence shell electronic configuration ns2np5 and there is one
unpaired electron in p-subshell i.e.,
(C) The element in which last electron enters in d-subshell belongs to d-block. For d-block elements the
group number = number of electrons in valence shell + number of electrons in (n – 1) d-subshell.
Group number 8. Valence shell electronic configuration is ns2(n – 1)d6. Therefore, group number = 2 +
6 = 8.
Like wise, group 12 is ns2(n – 1)d10. Therefore, group number = 2 + 10 = 12.
So in group 8 and 12 last electron enters in d-subshell.
(D) For electronic configuration. [Ar] 4s23d10 the group number = 2 + 10 = 12.