Classification of

Elements and
Periodicity in Properties
We know by now that the elements are the basic units of all types of
matter. In 1800, only 31 elements were known. By 1865, the number of
identified elements had more than doubled to 63. At present 114 elements
are known. Of them, the recently discovered elements are man-made.
Efforts to synthesize new elements are continuing. With such a large
number 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 organise
their knowledge by classifying the elements. Not only that it would
rationalize known chemical facts about elements, but even predict new
ones for undertaking further study. Earlier altempts of classifications .

included Dobereiner’s triads, Newland octaves and Lothar Meyer’s atomic

volume curves, etc.
The periodic table displays all chemical elements systematically in order
of increasing atomic number i.e. the number of protons in the nucleus.
Mendeleev’s periodic Mendeleev arranged the elements on the basis of law which stated, the
Table physical and chemical properties of elements are periodic functions of
their atomic weights. If the elements are arranged in the order of their
increasing atomic weights, after a regular interval elements with similar
properties are repeated. The table is divided into nine vertical columns
‘

called groups and seven horizontal rows called periods.

Characteristics of periods
(a) First period iscalled shortest period and contains only two elements.
Second and third periods are called short periods containing eight
elements each. Fourth and fifth periods are long periods containing
eighteen elements each. Sixth period is longest period with thirty-two
elements. Seventh period is an incomplete period containing nineteen
elements. Numbers 2, 8, 8, 18, 18, 32 are called magic numbers.
8

(b) Lanthanide and actinide series containing 14 elements each are placed
separately under the main periodic table. These are related to sixth
and seventh periods of IIIrd group respectively.
(0) Elements of third period from sodium (Na) to chlorine (Cl) are called
representative or typical elements.
((1) Valency of an element in a period increases from 1 to 7 with respect
to oxygen.
N320 Mgo A1203 Si02 P205 SO3 01207
1 2 3 4 5 6 7
(e) From left to right in a period generally
(i) Atomic weight, effective nuclear charge, ionisation potential,
electronegativity and electron affinity of an element increase.
(ii) Atomic radius, electropositive character and metallic character of
an element decrease.

90
 (f) Diagonal relationship : Elements of second period Li, Be and B resemble
closely with the elements Mg, Al and Si of third period in the next
higher group.

(g)
Second period
Third period
LiN BeNB
Na Mg Al\ C
Si _

Elements-of second period are called bridge elements.

Characteristic of groups
(a) Mendeleev’s periodic table contains nine groups. These are represented
by Roman numerals I, II, III, IV, V, VI, VII, VIII and zero. Groups
I to VII are divided into subgroups A and B, group VIII consists of
three sets, each one containing three elements.
(b) Inert gases are present in zero group. These were not discovered till
that time.
(c) The valency of an element in a group is equal to the group number.
((1) There is no resemblance in the elements of sub-groups A and B of
same group, except valency.
(e) The elements ofthe groups which resemble with typical elements are
called normal elements. For example - IA, IIA, IIIA, IVA, VA, VIA,
VIIA group elements are normal elements.
(f) Those elements of the groups which do not resemble with typical
elements are called transition elements. For example— IB, IIB, IIIB,
IVB, VB, VIB, VIIB and VIII group elements are transition elements.
(g) Hydrogen is placed in both IA and VIIA groups.
(h) In a group, from top to bottom in general,
(i) Atomic weight, atomic size, electropositive character and metallic
character of an element increase.
(ii) Ionisation potential, electron affinity and electronegativity of an
element decrease.
Moseley’s periodic table Moseley (1909) studied the frequency of X-rays produced by the
bombardment of a strong beam of electrons on a metal target. He found
that the square root of the frequency of X-rays (‘11)) is directlyproportional
to the number of nuclear charge (Z) of metal. «10 = a (Z — b) where a and
b are constants. Nuclear charge of metal is equal to the atomic number.
So Moseley related the properties of elements with their atomic number
and gave the new periodic law.
According to him, physical and chemical properties of elements are the
periodic functions of their atomic number. If the elements are arranged
in order of their increasing atomic number, after a regular interval, element
with similar properties are repeated.
Bohr’s periodic table With better understanding of the role of electrons in the properties of
elements and the development of the nature of the electrons in atoms,
a better understanding of the periodic properties of elements or the periodic
table was possible. The long form of periodic table is also known as Bohr’s
periodic table.
The long form of periodic table offers the following advantages over the
Mendeleev’s classification.
(i) Sub-group A and sub-group B elements are placed separately. There
is clear demarcation between metals and non-metals.

91
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92
 .(ii)The nine elements of group VIII have been placed in separate groups
corresponding to d“, d7 and d 8 configurations.
(iii)Fourteen lanthanides are not placed together, but are assigned a
separate group for each lanthanon in the f—block of elements.
(iv) The uniform trivalent state of the lanthanides can be explained due
to the availability of only three electrons in the outer, high energy
levels, the differentiating electrons going, to the inner chemically inert
orbitals.
(v) Uniform bivalence for the transition elements is due to the presence
of outer ns2 electrons, which makes them electropositive in nature.
(vi) The change from a highly electronegative to electropositive character
through inert gas structure has been explained on the basis of the
long form of periodic table.
Nomenclature of Enrico fermi and coworkers (1934), first prepared the elements beyond
Elements with Atomic uranium. They irradiated uranium with slow neutrons and found several
number more than 100 radioactive products. These were called transuranic or transuranium
elements. The elements with, Z = 104 — 112, 114 and 116 have been
reported recently and are called transactinides or superheavy elements.
These are synthetic, i.e., man-made elements. Recently out of competitive
spirit dispute have arisen over the names of these newly discovered
elements. To overcome this problem, scientists proposed a systematic
nomenclature based on the atomic number ofthe element. After wards in
1997, IUPAC gave the approved official names for elements with atomic
numbers 104 to 109. A systematic nomenclature based on the atomic
number of the element having atomic numbers > 100 is given as follows:
0 The names are derived by using the numerical roots for three digits in
the atomic number of the element and adding the ending ium. The
roots for the numbers are
Digit Name Abbreviation
0 nil n
1 un u
2 bi b
3 tri t
4 quad q
5 pent p
6 hex h
7 sept s
8 oct o
9 cm e
o In few cases the names are shortened. e.g, ‘biium’ and ‘triium’ are
shortened to ‘bium’ and ‘trium’.
o The symbol for the element is made up from the first letters from the
roots which make up the names. The mixture of latin and Greek roots
has been chosen to ensure that the symbols are all different.
Illustration - 1 : What would be the IUPAC name and symbol of the element with atomic number
120?
Soln.: The roots for 1, 2 and 0 are un, bi and nil respectively.
Name of element : Unbinilium
Symbol : Ubn

93
Illustration - 2 : The elements Z = 107 and Zhave been made recently; element Z
= 109 = 108 has not
yet been made. Indicate the group in which you will place the above elements.
Soln.: The electronic configurations of these elements are :
Z = 107 [Rnl5f14 6d5 732
Z = 108 [Rnl5f14 6d6 732
Z = 109 [Rn]5f14 6d 7 782
These elements will be placed in d-block in groups 7th, 8th and 9th respectively.
Illustration - 3 : .

(a) Elements A, B, C and D have atomic numbers 12, 19, 29 and 36 respectively. On the basis of electronic
configuration, write to which group of the periodic table each element belongs.
(b) Predict the blocks to which these elements can be classified. Also predict their periods and groups.
'

(0) Which of these are representative elements?

Soln.: (a)
Element At. No. Electronic Group
configuration
A 12 152 282 2p6 332 2
B 19 Is2 232 2p6 332 3p6 4s1 1
C 29 152 2s2 2p6 332 3p6 3d10 431 11
D 36 1:52 232 2p6 332 3P6 3d10 482 4p6 18

[According to old system, these elements belong to groups :'IIA (A), IA (B), IB (C), VIIA or zero (D)]
(b) Prediction of blocks
(i) A receives the last electron in 3s-subshell, therefore, it belongs to s-block.
Period = 3rd
Group = No. of valence electrons = 2
(ii) B receives the last electron in 4s-orbital, therefore, it belongs to s-block.
Period = 4th
Group = No. of valence electrons = 1.
'

(iii)C receives the last electron in 3d-orbital, therefore, it belongs to d-block.

Period = 4th .

Group = N0. of electrons in ns and (n — 1) d subshells = 11

(iv)D receives the last electron in the 4p-orbital, therefore, it belongs to p-block.
Period = 4th
Group = 10 + valence electrons = 10 + 8 = 18
(c) The elements A and B are representative elements.

LONG FORM OF THE The table is based on the modern periodic law. It is an improved form of
PERIODIC TABLE the Mendeleev’s periodic table. This table has the following features:
o All the elementshave been arranged in the increasing order of atomic
'

numbers.
0 Elementswith similar electronic configurations have similar properties
and hence have been placed together at one place. Elements with
different electronic configurationshave different properties and hence
have been placed at different places in the periodic table. The periodic
table consists of
> Seven horizontal rows called periods.
> Eighteen vertical columns called groups or families.
Four blocks.
'

>

94
Periods There are seven horizontal rows called periods. The 112 known elements
have been accommodated in these periods according to the following scheme:
1st period : The first main energy shell (K—shell) is completed. As the
maximum capacity of K—shell is of 2 electrons, it consists of only two
elements, hydrogen (131) and helium (132).
2nd period: The second main energy shell is completed, i.e., 23 and
2p are completed. It includes eight elements from Li (231) to Ne
(2s2 2p6).
In third period corresponding to n = 3, there are nine orbitals: one
3s, three 3p and five 3d. However, we know from energy level diagram
for multielectron atoms that 3d-orbitals are higher in energy than 43-
orbitals. Consequently, 3d-orbitals are filled after filling
4s— orbital.Hence, this period involves the filling of only four orbitals
(33 and 3p) and contains eight elements from sodium (Z: 11) to argon
(Z: 18)
The fourth period corresponding to n = 4 involves the filling of one
4s-and three 4p-orbitals (4d and 4f orbitals are higher in energy than
5s-orbita1s and are filled later). In between 4s-and 4p-orbitals, five 3d-
orbitals are filled which have energies in betweenthese orbitals. Thus,
in all nine orbitals are to be filled and, therefore, there are eighteen
elements in fourth period from potassium (Z = 19) to krypton
(Z = 36).
The fifth period, like the fourth period also consists of 18 elements.
It begins with rubidium (Z = 37) with filling of 5s-orbital and ends at
xenon (Z = 54) with the filling up of the 5p-orbitals.
The sixth period contains 32 elements (Z = 55 to 86) and successive
electrons enter into 63, 4f, 5d- and 6p-orbitals, in that order. It starts
with cesium (Z = 55) and ends at radon (Z = 86).
The seventh period,9§hough expected to have 32 elements is,
incomplete and contains only 19 elements at present. This also provides
a theoretical justification for periodicity occurring at regular intervals
of 2, 8, 8, 18, 18 and 32. These numbers i.e., 2, 8, 18 and 32 are also
called magic numbers.
The first three periods containing 2, 8 and 8 elements respectivelyare
called short periods, the next three periods containing 18, 18 and 32
elements respectively are called long periods.
Groups Vertical columns in the periodic table starting from top to bottom are
called groups or families. There are 18 groups in the periodice table
which are numbered from 1—18.
On the basis of electronic configuration, the elements may be divided
into four groups:
(i) s-blockelements
(a) These are present in the left part of the periodic table.
(b) These are 1 and 2 group elements.
(0) These are metals.
(d) In these elements last electron fills in the s-orbital.
(e) Electronic configuration of valence shell is nsl‘z (n = 1 to 7).
(ii) p-block elements
(a) These are present in right part of the periodic table.

95
 (b) These constitute 13 to 18 groups of the periodic table.
(c) Most 0" these elements are metalloids and nonmetals but some of
them are metals also.
(d) The last electron fills in p-orbital of valency shell.
'
(e) The electronic configuration of valence shell is ns2np1 6 (n = 2 to 7).
(f) 7232an is stable noble gas configuration. The electronic configuration
of He is 132.

(iii) d-block elements

(a) These are present in the middle part of the periodic table (between
3 and p block element).
1

(b) These constitute 3 to 12 groups of the periodic table.

(0) All are metals.
(d) The last electron fills in (n — 1)d orbital.
(e) The outermost electronic configuration is (n — 1)d1 ‘ 1° ns1 ‘ 2
(n = 4 to 7 ).
(f) There are three series of d-block elements:
3d series - Sc (21) to Zn (30)
4d series - Y (39) to Cd (48) '

5d series - La (57), Hf (72) to Hg (80)

(iv) f-block elements
(a) These are placed separately below the main periodic table.
(b) These are mainly related to group 3 of the periodic table.
(c) There are two series of f—block elements:
4f series - Lanthanides - 14 elements - Ce (58) to Lu (71)
5f series - Actinides - 14 elements - Th (90) to Lr (103)
(d) The last electron fills in (n — 2) f-orbital.
(e) Their outermost electronic configuration is (n — 2)f1 ‘ 14 (n — 1)s2
(n — 1)p6 (n - 1)d°‘ 1ns2 (n = 6 and 7).

BOHR’S On the basis of electronic configuration of the incomplete shells, the

CLASSIFICATION OF elements are classified into five main categories-
ELEMENTS Inert gases
1.
2. Representative elements
3. Transition elements
4. Inner transition elements
5. Transuranium elements.
Although this classification is convenient for understanding of chemical
properties of the elements, it overlooks the specific properties of the
individual elements.
1. Inert gases
(a) s and p-orbitals of the outer most shell of these elements are completely
filled. The outermost electronic configuration is ns2 np6.
(b) He is also inert gas but its electronic configuration is 132.
2. Representativeor normal elements
(a) Outermost shell of these elements is incomplete. The number of
electrons in the outermost shell is less than eight.
(b) Inner shells are complete.
(0) s- and p-block elements except inert gases are called normal or
representative elements.
96
 Transition elements
(a) Last two shells ofthese elements namely outermost and penultimate
shells are incomplete.
(b) The last shell contains one or two electrons and the penultimate shell
may contain more than eight up to eighteen electrons.
(e) Their outermost electronic configurationis similar to d-block elements
i.e. (n 1)d1 ‘ 1° ns1 ‘ 2.
-—

(d) According to latest definition of transition elements those elements

which have partially filled d-orbitals in neutral state or in any stable
oxidation state are called transition elements. According to this
definition, Zn, Cd and Hg (IIB group) are d-block elements but not
transition elements because these elements have d10 configuration in
neutral as well as in stable +2 oxidation state.
Inner transition elements
(a) In these elements last three shells i.e. last, penultimate and
prepenultimate shells are incomplete.
(b) The last shell contains two electrons. Penultimate shell may contain
eight or nine electrons and prepenultimate shell contains more than
18 upto 32 electrons.
(c) Their outermost electronic configuration1s similar to f- block elements
i e. (n — 2)f 1‘ 14(n — 1)32(n — 1)p6(n - 1)d 0‘ 1n
5. Transuranium elements
Elements of the seventh period after atomic number 93 (i.e. actinides) are
synthetic elements and are called transuranium elements.
In 1934, an Italian Physicist Enrico Fermi had observed that when
an element is bombarded with slow neutrons, the element is transformed
into a new element havingnext higher atomic number. First transuranic
element, having atomic number 93 was identified by American Physicist
Edwin Mcmilan and Philip H. Abelson. In the next year, element
number 94 was discovered in uranium fission products by American
Chemist Glenn T. Seaborg and coworkers. The elements 93 and 94
were named Neptunium (Np) and Plutonium (Pu) respectively for
Neptune and Pluto, the planets discovered after Uranus.
92U238 + on1 —) 9211239 + y-rays
92U239_) 93Np239 + _1e°
93Np239 _) 94Pu239 + 490'

PERIODICITY IN The term periodicity in properties in the classification of elements

PROPERTIES means that same properties of the elements reappear at definite
intervals when the elements are arranged in order of their increasing
atomic numbers. In modern periodic table, these intervals are 2, 8,
8, 18, 18 and 32, i.e., similar properties are observed with elements
belonging to the same subgroup which have been arranged in subgroups
after the difference of either 2 or 8 or 18 or 32 in atomic numbers
as similar valency-shell electronic configuration recur after certain
regular intervals of atomic number. This is the cause of periodicity
in properties.

97
 Electronic configurations of alkali metals
Element At. No. Electronic configuration
Li 3 132 281
Na 11 132 232 2p6 35‘
K 19 Is2 232 2p6 3s2 3p6 481
R1) 37 132 282 2p6 332 3})6 3d1° 432 4p6 531
Cs 55 152 282 2p6 382 3p6 3d10 4s2 4p6 4d10 532 5p6 631
Fr _87 182 282 2p6 352 3p6 3d10 4s2 4p6 4d10 532 5p6
682 4f 14 5d10 6p6 781

Thus, the cause of periodicity of the properties of elements is the

repetition of similar electronic configuration of their atoms in the outermost
energy shell (or valence shell) after certain regular intervals.
Atomic 'Radii > It is usually defined as the distance between the nucleus and
outermost shell where electrons are present. Three types of radii
are commonly used, i.e., (a) covalent radii (b) crystal radii (c) van
der Waals’ radii.
o Covalent radius
> It is defined as half of the distance between the two nuclei of two like
atoms bonded together by a single covalent bond.
> Consideringa homonuclear diatomic molecule A2, bonded together by
a single covalent bond, it is assumed that electron clouds of each atom
touch each other. Let the bond length be dA _ A.
ThendA_A=rA+rA=2rA
So iii-.4.
rA =
2
> In a heteronuclear diatomic AB molecule if both atoms are linked by
a single covalent bond and have nearly same electronegativity, the
bond length dA_B is equal to sum of covalent radii of the two atoms.
dA—B = rA +
r3
> If the covalent bond is formed between two elements of different
electronegativity then we use the following relation:
dA—B = rA+ TB — 0.09 (XA— X3)

where XA and X3 are electronegativity of A and B respectively. This

relation was given by Stevenson in 1941.
0 Crystal radii : It is defined as one half of the distance between the
, nuclei of two adjacent metal atoms in the metallic closed packed crystal
lattice in which metal exhibits a coordination number of 12.
o _van der Waals’ radii : It is half of the distance between the nuclei
of two nonbonded neighbouring atoms of two adjacent molecules.
rcovalent < rcrystal < I'van der Waals
Atomic radius in the nth orbit is given by
12240
-
n "‘
Z*
where n is principal quantum number (i.e., number of shell), a0, the
Bohr’s radius of H-atom (= 0.529A) and Z*, the effective nuclear charge.
The screening effect or In a multielectron atom, the electrons of the valence shell (outermost
shielding effect shell) are attracted towards the nucleus and repelled by the electrons
present in the inner shells. On account of this, the combined effect of the
attractive and repulsive force acting on the valence electron is that the
valence electron experiences less attraction from the nucleus. This

98
 decreased force ofattraction exerted by the nucleus on the valence electrons
due to the presence of electrons in the inner shells, is called screening
effect or shielding effect.
Effective atomic number Due to screening effect the valence electron experiences less attraction
towards nucleus. This results in decrease in the nuclear charge (Z) actually
present on the nucleus. The reduced nuclear charge is termed effective
nuclear charge and is represented by Z*. It is related to actual nuclear
charge (Z) by the following formula :
Z* = (Z o) where 0' is screening constant.
—-

The magnitude of ‘o’ is determined by the Slater’srules. The contribution

of inner electrons to the magnitude of ‘o’ is calculated in the following
ways:
Slater's rule for Estimating Effective Nuclear Charges, Z*
(1) Write down the electronic configurationof the elementin the following
order and grouping: ‘

(Is), (2s, 2p), (3s, 3p), (3d), (4s, 4p), (4d), (41‘), (5s, 5p) etc.
(2) Electrons in any group higher in the sequence show that the electron
under considerationcontribute nothing to the shielding o.
(3) Then for an electron in an us or np orbital
(a) all other electrons in (ns, np) group contribute o = 0.35 each
(b) all electrons in the (n — 1) shell contribute 0' = 0.85 each
(c) all electrons in the (n — 2) or lower shell contribute
a = 1.00 each
(4) For electron in an nd or nf orbital, all electrons in the same group
contribute a = 0.35 each; those in group lying lower in the sequence
than the (nd) or (nf) group contribute o = 1.00 each.
a Radius is also dependent on the extent of force of attraction which
pulls outer shell inward.
Variation in Period
Li Be B C N O F Ne
Z 3 4 5 6 7 8 9 10
a 1.7 2.05 2.40 2.75 3.10 3.45 3.80 4.15
Z* 1.30 1.95 ,
2.60 3.25 3.90 4.55 5.20 5.85
n 2 2 2 2 2 2 2 2
r, 123 90 80 77 75 74 72 160
(pm)

In a period, left to right :

0 Z (atomic no.) increases (by one unit)
0 Z* also increases (but by 0.65 unit)
a n (number of shells) remains constant
Thus rn oc 1/Z*
In case of Noble gases (as in Ne) there is no covalent bond formation,
hence only van der Waal’s radius is considered. Thus there is high jump
in the value of radius from F (72 pm) to Ne (160 pm).
Variation in a Group
Element Z a Z* n Radius (pm)
Li 3 1.7 1.3 2 123
Na 11 8.8 2.2 3 157
K 19 16.8 2.2 4 203
Rb 37 34.8 2.2 5 216
Cs 55 52.8 2.2 6 235
Fr 87 84.8 2.2 7 —
99
 In a group, top to bottom :
0 Z increases
0 Z* almost remains constant
0 n increases
Thus, rn oc n2
Hence atomic radius in a group is dependent on the value of n.

Illustration - 4 : Calculate the screening constant in zinc (a) for a 4s-electron (b) for a 3d-electron.
Soln.: (a) The electronic configuration of zinc (30) is, (ls)2 (23 2p)8 (3s 3p)8 (3d)10 (4s)2
a = 10 x 1.0 + 18 x 0.85 + 1 x 0.35 = 25.65
(b) For 3d-electron, a = 18 x 1.0 + 9 x 0.35 = 21.15
It is clear that the magnitude of screening constant in the case of s- and p-block elements increases
in a period as well as in a group as the atomic number increases.
Ionic Radii It is defined as the distance between the nucleus and outermost shell of
an ion or it is the distance between the nucleus and the point where the
nucleus exerts its influence on the electron cloud.
Metal ions are smaller than the atoms from which they are formed.
When a positive ion is formed, the number of positive charges on the
nucleus exceeds the number oforbital electrons, and the effective nuclear
charge (which is the number of charges on the nucleus to the number
of electrons) is increased. This results in the remaining electrons being
more strongly attracted by the nucleus. These electrons are pulled in
further reducing the size.
A positive ion is thus always smaller than the corresponding atom, and
the more the electrons are removed, the smaller the ion becomes.
Thus Mg > Mg” > Mg2+
Fe > Fe2+ > Fe3+
The negative ion is always larger than that of the corresponding atom.
0 Negative ion is formed by gain of one or more electrons in the neutral
atom and thus number of electrons increasesbut magnitude of nuclear
charge remains the same.
0 Due to decrease in nuclear charge per electron, there is an expansion
of outer shell. Thus size of anion is increased.
02‘ > 0' > O,
I— > I > I+

Nuclear
charge
These can be explained on the basis of Z/ e ratio ( J' en
No. of electrons
Z / e ratio increases, the size decreases and when Z / e ratio decreases, the
size increases.
Na Na+ C1 Cl—

me
11 ll 17 17
«—=1.0;
11
——=l.1;
10
—=1.0; —=0.95;
17 18
So Na" < Na 01‘ > C1
For isoelectronic species the size decreases with an increase of atomic
number. This is illustrated in the following table:
Atom Atomic No. of Z / e ratio Size in
or Ion Number (Z) electrons (e) A
02‘ 8 '
10 0.8 1.40
F‘ *

9 10 0.9 1.30
Ne 10 10 1.0 1.12
Na+ 11 10 1.1 0.95
Mg2+ 12 10 1.2
‘

0.65

100
 H+ and Cs+ are the smallest and largest cations respectively.
H‘ and I‘ are the smallest and largest anions respectively.
Illustration- 5: Arrange the following inns in the order ofIncreasing size.
Be2+, Cl‘, 82‘, Na, Mg2+, Br‘
Soln.: Be2+ < Mg2+ < Na+ < Cl‘ < S2“ < Br‘
Illustration - 6 :Which of the following species will have the largest and the smallest size?
Mg, Mg2+ A1 A13+
Soln.: Atomic radii decrease across a period. So, Mg will have larger size than Al. Cations are smaller
is
than their parent atoms. So size . Mg2+ < Mg and Al3+ < Al. Now, among isoelectronic ions, the
ion with the larger positive nuclear charge will have a smaller radius i.e., size is : Al3+ < Al.
Hence, the largest species is Mg and the smallest species is A13".
Illustration - 7 : Which of the following atoms and ions are isoelectronic?
(i) (ii) F (iii) Cl‘ (iv) 02' (v) Na
A13+_ (vi) Mg2+
7
Arrange the isoelectronic ions in the decreasing order of their size.
Soln.: The number of electrons in these atoms or ions are :
Ion or atom Al3+ F Cl— 02‘ Na Mg2+
No. of electrons 10 9 18 10 11 10
Thus A132 02‘ and Mg2+ are isoelectronic ions because all the three ions have ten electrons. Now
_

nuclear charge in Al3+ is +13, in O?" is +8 and in Mg2+ is +12. With increase in nuclear charge (electrons
remain same), size will decrease. Consequently, the size follows the order:
02— > Mg2+ > A13+

Illustration - 8 : Give the formula of a species that will be isoelectronic with the following atoms or
ions?
(i) Ar (ii) F‘ (iii) K” (iv) Sr2+
Soln.: Isoelectronic species are those which have same number of electrons
(i) Ar has 18 electrons Therefore, the species P3’, 82' ,C,1‘ K”, Ca2+, etc., are isoelectronic to Ar.
(ii) F— has 10 electrons. Therefore, the species N3‘, 02‘, Ne, Na”, Mg2+, etc are isoelectronic to F“.
(iii) K+ has 18 electrons. Therefore, the species P3", SZ‘C,1‘, Ar, Ca2+, etc., are isoelectronic to K”.
(iv) Sr2+h as 36 electrons. Therefore, the species Br‘, Kr, Rb, etc, are isoelectronic to Srz“.

Ionisation Potential or The minimum amount of energy required to remove the most loosely
Ionisation Energy bound electron from an isolated atom in the gaseous state is known as
ionisation potential or ionisation energy or first ionisation potential (11)
of the element.
M———)°““gy111* + e
The energy required to remove the second electron from the monovalent
cation is called second ionisation potential (12).
M+ + I2 —-> M2+ + e
Similarly, we have third, fourth . ,. . ionisation potentials.
M2+ + I3 —) M3+e
M3+ + 14 -> M4+ + e

It is observed that I2is higher than

i.e., < < I3 <
11 12
I3 higher than I2 and so on,
11, 1s
Theincrease in the values of successive ionisation
I4.
potentials can be explained on the basis that effective nuclear charge
increases from Me) to M”+ (g), i..,e force of attraction of the outermost
electron towards nucleusincreases.

101
 Factors affecting the value of ionisation potential
Properties Efl'ect
1. Atomic Size Larger the atomic size, smaller is the value of
ionisation potential.
.
'

2. Screening Effect Higher the screening effect, the lesser is the

value of ionisation potential.
3. Nuclear charge Ionisation potential increases with the increase
in nuclear charge.
4. Penetration effect Values of ionisation potential
or shape of orbtial s, p, d and f electrons are as : s > p > d > f.
If an atom has fully filled or half-filled orbitals, its IE is higher than
expected normally from its position in the periodic table. e.g.
Li Be B C N O-

F Ne
281 232 2822121 2322p2 2822p3 2322p4 2322p5 2822p6
IE (eV) 5.4 9.3 8.3 11.2 14.5 13.6 17.4 21.6
Be (fully filled 23 orbital) and N (half filled 2p orbital)have higher values
than expected due to stable configurations.
0 Variation of (IE) in a group
Force of attraction between electronsand nucleus decreasesand tendency
to remove the valence electron increases. Hence (IE) decreases on moving
down the group.
a Variation of (IE) in a period
On moving across a period, the atomic size decreases and nuclear charge
increases and therefore the force of attraction exerted by the nucleus on
the electron in outermost shell increases. Hence (IE) increases along a
period from left to right.
0 The energies required to remove subsequent electrons from the atom
in the gaseous state, are known as successive ionisation energies.
o Successive ionisationenergies are higher: The second ionisation
energies are higher than the first ionisation energies. This is mainly due
to the fact that after the removal of the first electron, the atom changes
into monovalentpositive ion. In the ion, the number of electrons decreases
but the nuclear charge remains the same. As a result of this, the remaining
electrons are held more tightly by the nucleus and it becomes difficult to
remove the second electron. Hence, the value of second ionisation energy
(IE2) is greater than that of the first (IE 1).

Illustration - 9 : The ionisation energy of lithium is 520 kJ mol‘l. Calculate the amount of energy
requiredto convert 210 mg of lithium atoms in gaseous state into Li+ ion.
Soln.: Lies.) -—9 Ling), IE = 520 kJ mol‘1
,
Mass of lithium = 210 mg = 210 x 10'3 g = 21 x 10‘2'g.

31:12.: 3 x 10-2 mole

—2

Number of moles of lithium =

Energy required to convert 3 x 10’2 mole atoms of lithium into Li+ ions is
=520x3x 10‘2= l5.60kJ.-'
Illustration - 10 : How much energy in joules must be needed to convert all the atoms of sodium to
sodium ions present in 2.3 mg of sodium vapours? Ionisation enthalpy of sodium is 495 kJ mol—1
(at. maSs of Na = 23).

102
Soln.: According to the definition of ionisation enthalpy,
Nag) + IE —> Naflg) + e13) ; IE = 495 kJ mol"1
The amount of energy needed to ionise 1 mole of sodium vapours = 495 kJ mol‘1
2.3 x 10‘3
Moles of sodium vapours present in given sample = = 1 x 10‘4 mole
23
Amount of energy needed to ionise 1 x 10“4 mol of sodium vapours
= 495 x 1 x 10‘4 = 0.0495 kJ or 49.5 J.

Electron Affinity or o The amount of energy releasedwhen an electron is added to an isolated

Electron Gain Enthalpy gaseous atom to produce a monovalentanion is called electron affinity
or first electron affinity.
A + e———> A‘ + energy
a Most elements have a negative electron affinity. This means they do
not require energy to gain an electron; instead, they release energy.
Atoms more attracted to extra electrons have a more negative electron
affinity. Chlorine most strongly attracts extra electrons; radon most
weakly attracts an extra electron.
0 Electron gain enthalpy is expressed in terms of enthalpy change when
an electron is added to an isolated gaseous atom. Larger the energy
released in this process, more negative the value of electron gain
enthalpy or more positive the value ofelectron affinity.
Although electron affinities vary in an irregular manner across the table,
some patterns emerge. Generally,nonmetals have more negative electron
affinities than metals. However, the noble gases are an exception: they
have positive electron affinities.
Factors affecting the value of electron affinity
Properties Effects
1. Nuclear charge ‘
Electron affinity increases with the
increase in nuclear charge.
2. Atomic size With the increase in atomic size, electron
afl'inity decreases.
3. Electronic configuration Electron affinities are low or almost zero
in cases of stable configurations i.e. half
filled or full-filled valence shell.
Li Be B '
C N O F Ne
231 232 .2sz2p1 2s2 2p2 282 2p3 282 2p4 2s22p5 2322p6
eV —0.61 0.0 — 0.30 — 0.20
—1.25 —1.48
—3.6 0.0
‘

Be, N and Ne have low values due to stable configurations.

o The electron affinities increase across a row (since the radius slightly
decreases, because of the increased attraction from the nucleus, and
the number of electrons in the top shell increases, helping the atom
reach maximum stability) in the periodic table and decrease going down
a family (because of a large increase in radius and number of electron
that decrease the stability ofthe atom, repulsing each other).
. Electron affinities are not limited to the elements but also apply to
molecules. For instance the electron affinity for benzene is positive,
that of naphthalene near zero and that of anthracene positive.
0 Successive electron affinities
Like ionisation energies, the second and higher electron affinities are
also possible. However, second electron is added to a negatively charged
ion and the addition is opposed by coulombic repulsions. The energy
has to be supplied to force the second electron into the anion.

103
Illustration-11 : Which of the following will have the most negative electron gain enthalpy and which
the least negative? P, S, Cl, F. Explain your answer.
Soln.: These elements can be arranged in different periods and groups as :
'
Group No. 15 16 17
2nd period F
3rd period P S Cl
We know that electron gain enthalpy becomes more negative across a period as we move from left
to right. Within the group, electron gain enthalpy becomes less negative as we move down a group.
Therefore, P should have the least negative electron gain enthalpy and F should have the most
negative electron gain enthalpy. However, adding an electron to smaller 2p-orbital leads to greater
inter-electronic repulsions than adding an electron to larger 3p-orbital. Hence, Cl has more negative
electron gain enthalpy than F. Therefore, Cl has the most negative electron gain enthalpy and P
has the least negative electron gain enthalpy.
Illustration» - 12 : Which element will have the greatest negative electron gain enthalpy? Give reasons?
(3) [Ne] 332 3p3 (b) [Ne] 332 3p4 (c) [Nel3s2 3p5 ((1) [Ne] 332 3p6 481 3d5
Soln.: The element corresponding to configuration(c) will have he highest negative electron gain enthalpy.
It corresponds to chlorine (halogen) which has very strong tendency to accept an electron to acquire
noble gas configuration. "

Illustration-13 : Which of the following pairs would have a higher electron gain enthalpy?
(i) N or 0 (ii) F or Cl (iii) Br or I (iv) B or Al
Soln.: Higher negative electron gain enthalpy.
(i) 0 (ii) Cl (iii) Br' (iv) B

Electronegativity o Electronegativityis a measure of the tendency of an element to attract

electrons to itself. In a molecule, tendency of the atom to attract
bonding pair towards itself is its electronegativity.B is said to be more
electronegative than A if it pulls bonding pair towards itself.
5+ 6—

(14) >'<
(15’) -—> (A) — (B)
0 An arbitrary value of 4.0 has been assigned to fluorine (most
electronegativeelement)and the electronegativities of other elements
have been calculated against this standard by application of following
formula:
XA - X3 = 0-203 [EA—B — (EA—,4 X 53—5)U2l“2
where XA and X3 are the electronegativitiesof two atoms A and B and
EA _ 3, EM _ A) and EB _ B are bond energies of molecules A — B, A2
and BZ, respectively .

o Mulliken regarded electronegativity as the average value of ionisation

potential and electron affinity of an atom.
117+ EA
Electronegativity =

On Pauling scale, electronegativity of an atom = [P +

EA
o
5.6
Values of IP and EA are taken in eV

' Electronegativity of an atom =

lP+ EA
2 x 62.5
values of IP and EA are taken in kilo calories per mole
Illustration-14 : Calculatethe electronegativity of fluorine from the following data :

EH_H = 104.2 kcal mol‘l, EF_F = 36.6 kcal mol‘l, EH_F = 134.6 kcal mol—l, X“ = 2.1
Soln.: According to the equation, EA_ B — (EA_ A x 12,343)”2 = A’
A’ = EH_F— (EH_H x EF_F)1/2 = 134.6 — (104.2 x 36.6)"2 = 72.85 kcal

We have, 0.182\/KT = M — x3
XF — xH = 0.182(72.85)1’2 = 1.55
xF = 1.55 + X}, = 1.55 + 2.1 = 3.65

104
Illustration-15 : Calculatethe electronegativity of carbon from the following data :
EH _H = 104.2 kcal mol‘l, EC_C = 83.1 kcal mol‘l, EC_H = 98.8 kcal mol‘l, XH = 2.1
Soln.: According to the equation, EA_ B — (EA_ A x EB_ B)“2 = A’
A’ = EC_H— (EmH x EC_C)1’2 = 98.8 — (104.2 x 83.1)“2 = 5.75 kcal

We have, 0.182JE = M — x3
x0 — xH = 0.182(575)"2 = 0.44
xc = 0.44 + M = 0.44 + 2.1 = 2.54

Valency The electrons present in the outermost shell are calledvalence electrons
and these electrons determine the valency of the atom.
In case of representative elements, the valency is generally equal to either
number ofvalence electrons or equal to eight minus the number ofvalence
electrons. However, the transition elements, exhibit variable valency.
Variation of Valency in the Periodic Table
(a) Variation in a period: The number of valence electrons increases
from 1to 8 on moving across a period, the valency of the elements with
respect to hydrogen and chlorineincreases from 1 to 4 and then decreases
to zero. This may be illustrated by taking the examples of elements of
second and third periods as given below in Table. The number in brackets
represents the valency of the elements in the compound.
Table: Variation of valency of elements of second
and third periods.
Elements of second period
Li Be B C N O F
Valency with respect to H
LiH BeH2 BH3 CH 4 NH3 H20 HF
(1) (2) (3) (4) (3) (2) (1)
Valency with respect to Cl
,

LiCl BeCl2 B013 0014 N013 0120 ClF

(l) (2) (3) (4) (3) (2) (1)
Elements of third period -

Na Mg A1 Si P S Cl
Valency with respect to H
NaH MgH2 AlH3 SiH4 PH3 HZS HCl
(1) (2) (3) (4) (3) (2) (1)

(b) Variation in a group : On moving down a group, the number of

valence electrons remains same and, therefore, all the elements in a
group exhibit same valency. For example, all the elements of group 1
have valency One i.e., are monovalent and those of group 2 have valency
two or divalent.

Illustration-16 : Are the oxidation states andcovalency of Al in [AlCl(H20)5]2+ same?

Soln.: No. The oxidation state of A1 is +3 and the covalency is 6.
Atomic volume Atomic volume increases in a group from top to bottom. The increase
is due to the increase in the number of energy shells.
In a period from left to right, atomic volume varies cyclically, i.e., it
decreases at first for some elements, becomes minimum in the middle
and then increases. The following two factors explain this trend:
(a) Atomic radii decrease due to increase of nuclear charge.

105
 (b) The number of valency electrons increases in a period.
As to accommodate all the valency electrons, the volume increases.
These two factors oppose each other. The effect of first factor is more
on the left hand side and that of the second factor is more on the right
hand side.
Li Be B C N 0 F Ne
g; 13 5 5 5 14 11 15 17 g;

5 Na Mg A1 31 P 3 Cl Ar 5
‘g 24 14 1o 12 17 16 19 24 ‘g
H K Ca ’“
Ga Ge As Se Br Kr
46 26 12 13 16 16 23 33
The maximum value of atomic volume (87) is observed in the case of
francium (last member of alkali group).
Density The density of the elements in solid state varies periodically with their
atomic numbers. At first, the density increases gradually in a period and
becomes maximum somewhere for the central members and then starts
decreasing afterwards gradually.
Li Be B C N O F
0.5 1.8 2.3 2.2 — — -——

Na Mg Al Si P S CI
1.0 1.7 2.7 2.3 1.8 2.1 -—
K Se Br
0.9 4.8 3.1
Rb Te I
1.5 6.2 4.9
Cs
1.9
In solids, osmium has the highest density (22.6) and in liquids, Hg has
the highest density (13.6).
Melting and boiling The melting points of the elements exhibit some periodicity with rise
points of atomic number. It is observed that elements with low values of atomic
volumes have high melting points while elements with high values of
atomic volumes have low melting points. In general, melting points of
elements in any period at first increase and become maximum somewhere
in the centre and thereafter begins to decrease.
The melting points of 2nd and 3rd period elements are as shown in the
table.
.

Elements Li Be B C N O F Ne
M.Pt. (K) 454 1550 2303 4000 63 54 53 24
Elements Na Mg Al Si P S Cl Ar
M.Pt. (K) 370.8 924 933 1693 317 392 172 83.6
Tungsten has the maximum melting point (3410°C) amongst metals and
carbon has the maximum melting point (3727°C) amongst non—metals.
Helium has the minimum melting point (—270°C). The metals Cs, Ga and
Hg are known in liquid state at 30°C.
The boiling points of the elements also show similar trends, however,
the regularities are not so striking as noted in the case of melting points.

106
 Key Notes
0 Importance of electron gain enthalpy
> Certain properties ofthe elements can be predicted on the basis of values of electron gain enthalpies.
(i) The elements havinghigh negative values ofelectron gain enthalpy are capable of accepting electron
easily. They form anions and thus form ionic (electrovalent) compounds. These elements are
electronegativein nature.
(ii) The elements having high negative electron gain enthalpies act as strong oxidising agents, for
example, F, Cl, Br, 0, S, etc.
> On the basis of the general trend of ionisation enthalpy and electron gain enthalpy, the following
properties can be predicted.
(i) Metallic nature decreases in a period while non-metallic nature increases. Metallic nature increases
in a group while non-metallic nature decreases. The arrow (i) represents a group and (-—>) represents
a period.
Metallic Non-metallic

Metallic Decreases ; Non—metallic Increases

(electro +ve) (electro —ve)

Increases Decreases
(ii) Reducing nature decreases in a period while oxidising nature increases. The reducing nature increases
in a group while oxidising nature decreases.
Reducing nature Oxidising nature

Reducing Decreases ; Oxidising Increases

nature nature
Increases Decreases
(iii) Stability of metal increases while activity the
of metal decreasesin a period and in a group stability
decreases while activity increases.
Stability of the metal Activity of the metal

Stability of Increases ; ActiVity 0f Decreases

the metal the metal
Decreases Increases
(iv) The basic nature ofthe oxides decreasesin a period while acidic nature increases. In a group, basic
nature increases while acidic nature decreases.
Basic nature of oxides Acidic nature of oxides

Basic nature Decreases ; Acidic nature Increases

of oxides of oxides
Increases Decreases

107
 Importance of electronegativity
The following predictionscan be made from values of electronegativity.
Nature of the bond between two atoms can be predicted from the electronegativitydifference ofthe two
atoms.
(a) The difference XA —X3 = 0, i.e., X, = X3, the bond is purely covalent. For example, H2, 012, O2 and N2
molecules are purely covalent and non-polar.
(b) The difference XA — X3 is small, i.e., XA > X3, the bond is polar covalent.
(c) The difference XA — X,3 is 1.7, the bond is 50% covalentand 50% ionic.
(d) The difference XA — X3 is very high, the bond is more ionic and less covalent. The molecule will be
represented in such case as BA (B‘A‘).
The elements having low values Of electronegativityare metals while the elements having high values
of electronegativityare non-metals.
(X0 —XA) difference predicts the nature of the oxides formed by the elements A. X0 is electronegativity
of oxygen.
V

Xo —XA is large, the oxide shows basic nature (e.g. Na20)

XO —XA is small, the oxide shows acidic nature (e.g. SOZ).

Metals, non-metals and metalloids

Characteristic properties of metallic and non-metallic elements:
Metallic elements Non-metallic elements
Distinguishing lustre (shine) Non-lustrous, various colours
Malleable and ductile (flexible) as solids Brittle, hard or soft
Conduct heat and electricity Poor conductors
Metallic oxides are basic, ionic Nonmetallic oxides are acidic, compounds
Cations in aqueous solution Anions, oxyanions in aqueous solution
Metals
Most metals are malleable (can be pounded into this sheets; a sugar cube chunk of gold can be pounded
into a thin sheet which will cover a football field), and ductile (can be drawn out into a thin wire).
All are solids at room temperature (except mercury, which is a liquid).
Metals tend to have low ionisation energies, and typically lose electrons (i.e. are oxidised) when they
.
undergo chemical reactions.
- Alkali metals are always 1 + (lose electron in s subshell).
- Alkaline earth metals are always 2+ (lose both electrons in s subshell). .

- Transition metal ions do not follow an obvious pattern, 2 is common, and 1+ and 3+ are also
o»

observed.
Compounds of metals with non-metalstend to be ionic in nature.
‘

Most metal oxides are basic oxides; those that dissolve in water react to form metal hydroxides:
Metal oxide + water —> metal hydroxide
Na20 (s) + H20 (1) 2NaOH (aq)
——)

CaO (s) + H20 —> Ca(OH)2 (M)

(1)

Metal oxides exhibittheir basic chemical nature by reacting with acids to form salts and water.
Metal oxide + acid ~—> salt + water
MgO (s) + H01 (aq) _> MgC12 (aq) + H20 (1)
Non-metals ‘

Vary greatly in appearance.

Non-lustrous.
Poor conductors of heat and electricity.
VVVVVO

The melting points of non-metals are generally lower than metals.

Seven non-metalsexist under standard conditions as diatomic molecules.
1. H2 (g, 2. N2 (g) 3. 02 (g, 4. F2 (,0 5. Cl2 (g) 6. Br, (1) 7. 12(3)

108
Non-metals, when reacting with metals, tend to gain electrons (typically attaining noble gas electron
configuration) and become anions:
Non-metal + metal —9 salt
3Br2 (l) + 2A1<s) —’ 2MBr3ts)
Compounds composed entirely ofnon-metals are molecularsubstances (not ionic).
Most non-metal oxides are acidic oxides. Those that dissolve in water react to form acids:
Non-metal oxide + water —-> acid
COZ (g) + H20 ,1) —> HZCOMW) [carbonic acid]
Carbonatedwater is slightly acidic)
Non-metal oxides can combine with bases to form salts.
Non-metal oxide + base salt
7

——>

002 (g, + 2NaOH (W, —> NazCO3 m, + H200,

Metalloids
Properties intermediate between metals and non-metals.
Silicon, for example, appears lustrous, but is not malleable or ductile (it is brittle - a characteristic of
some non-metals). It is a much poorer conductor ofheat and electricity than the metals. Metalloids are
useful in the semiconductor industry.
Trends in metallic and non-metallic character
Metallic character is strongest for the elements in the leftmost part ofthe periodic table, and tends to
decrease as we move to the right in any period (non-metallic character increases with increasing ionisation
values).
Within any group of elements (columns), the metallic character increases from top to bottom (the
ionization values generally decrease as we move down a group). This general trend is not necessarily
observed with the transitidn metals.
Increasing metallic character
character
1 *0 character

non-metallic

metallic

Increasing

Increasing

Increasing non-metallic character

. fir _
General trends for the metallic character ofan element
(metallic character is the opposite of non-metallic character)

109
 Examples
1. Arrange the following in:
(i) Decreasing ionic size: Mg2+, 02‘, Na“, F‘
(ii) Increasing acidic property: ZnO, Na202, P205, MgO
(iii)Increasing first ionisation potential: Mg, Al, Si, Na
(iv) Increasing size: Cl", SZ‘, Ca2+, Ar
(v) Increasing order of ionic sizezN3‘, Na“, 13", 02‘, Mg2”
(vi) Increasing order of basic character: MgO, ’SrO, K20, NiO, Cs20
(vii)Arrange the following ions in order of their increasing radii: Li“, Mg2+, K”, A13+.
Soln.: (i) 0* > F— > Na+ > Mg”. These are isoelectronic ions (each has 10 electrons). In such case
the ionic radii decreases with increase in nuclear charge. The nuclear charge is 8 (for 02“)
9 (for F“), 11(for Na”) and 12 (for Mgz”).
(ii) Na202 < MgO < ZnO < P205
In case of oxides, the acidic strength increases with increase in oxidation state of central atom.
_

(iii) In case of elements of 3rd period the first IE follows the order Na < Mg > A1 < Si.
(iv) The correct order is Ca2+ < Ar < 01' < 82’. These are isoelectronic with 18 electrons. Lower the
nuclear charge, higher is the ionic radii.
(v) The correct order is Mg2+ < Na+ > I" < O?” < Nah. For isoelectronic ions, ionic radii decreases
with increase in nuclear charge. ‘

(vi) The increasing order of basic character is

NiO < MgO < SrO < K20 < Cs20
In a group the basic character of oxide increases as we move from top to bottom. Thus we have
K20 < Cs20 (group 1) and MgO < SrO (group 2)
Also as the group number increases the basic character decreases, so NiO is least basic, Ni is
in group 10.
(vii) Out of the given species Al3+ and Mg2+ are isoelectric (10 electrons) and size of A13+ is smaller,
so Al3+ < Mg2+. Li“ and K+ belong to group I and Li+ is higher up in the group so Li“ < K“.
The correct order is Al3+ < Li+ < Mg2+ < Kfi
2. The first ionisation energy of carbon atom is greater than that of boron atom whereas, the reverse
is true for the second ionisation energy. Explain.
Soln.: Along the period from left to right, as atomic size decreases, ionisation energy increases. So, IE 1
of carbon is greater than IE1 of boron.
IE2 in case of C+ (1822322p1) will be less than the IE2 in case of B*(132232). In C+ the electron has
to be removed from 2p-orbita1 where as in B it has to be removed from 23-orbital.
3. (i) There are only 14 lanthanoids and only 14 actinoids. Explain.
(ii) Why argon (at. mass 39.94) has been placed before potassium (at. mass 39.10) in the periodic
table. .

Soln.: (i) In lanthanoids and actinoids, the differentiating electron enters to (n — 2)f—subshe11. The
maximum capacity of f-subshell is of 14 electrons; Thus, there are only 14 lanthanides (4f1 ‘ 14)
and only 14 actinides (5fi " 14).
(ii)In modern periodic table, elements have been placed in order of their increasing atomic
‘

numbers. The atomic number of argon is 18 and that of potassium is 19. Thus, argon has been
placed before potassium.
4. IE2 for alkali metals show a jump whereas IE3 for alkaline earth metals show a jump. Why?
Soln.: TheJump in IE values are noticed when the successiveremoval ofelectrons occurs from different
shells. In alkali metals (n') remOval of I and II electrons occurs from n, (n— 1) shells réspectively
‘

and thus shows a jump in IE2 values. This condition occurs during removal of II and III electrons
from alkaline earth metals. ‘

5. F2 is more powerful oxidant than 012. Why?

Soln.: Of all the halogens, F has highest positive electrode potential (F2-— 2.87, C12: 1. 36, Hr2 = 1. 09
and I2: 0.53 volt). i. e it is most easily reduced hence acts as strongest oxidising agent.
6. The radius of a cation is lesser than the atom while that of an anion is greater than the atom.
Why?
Soln.: In a cation, the nuclear charge acts on lesser number of electrons and thus, the electron cloud
contracts. Hence, the net result is decrease in size. In an anion, the nuclear charge acts on larger
number of electrons and thus, the electron cloud expands. Hence, the net result is increase in size.
This can also be explained on the basis of Z/e ratio. In cation Z/e ratio increases, hence size decreases
while in an anion Z/e ratio decreases and so the size increases.
7. Why Be and Mg atoms do not impart colour in flame?
Soln.: Be and Mg atoms are comparatively smaller and their ionisation energies are very high. Hence,
their electrons are not excited by the energy of the flame to higher energy state. Therefore, these
elements do not give any colour in flame.
8. Chlorine has maximum electron affinity. Why?
Soln.: Cl has more negative electron gain enthalpy than F. The less negative electron gain enthalpy
of F is due to its very small size which has strong electron-electron repulsions. Therefore F has
less tendency to accept an electron and its electron gain enthalpy is less negative than Cl.
9. EA2 of halogens1s zero. Give reason.
Soln.: After addition of one electron halogen acquires nearest noble gas configuration. Addition of 2nd
electrozn is 5not possible and thus EA2 = 0
X: ns2 nps; X :ns 2np“"; X 2‘n.ot possible.
10. The atomic radius decreases along the period but inert gases have maximum atomic radius in a
period. Given reason.
Soln.: Atomic radii of inert gases are Van der Waals radii whereas for rest all atoms covalent radii
are determined experimentally. Van der Waals radii is greater in comparison to covalent radii.
11. (a) Why N has higher 1st ionisation potential than O-atom?
(b) Why Mg has higher 1st ionisation potential than Al-atom?
Soln.: (a) The electronic configurations of nitrogen and oxygen are as follows:
N:132,2322p3222py12p211
0:132,2322px22p:12p21
In N, p--orbital1s half filled which is more stable. It requires more energy to remove an electron.
Hence, the IE of nitrogen is higher than oxygen atom which has less stable structure.
(b) The electronic configurations of Mg and A1 are as follows:
Mg : 132, 2.92 2p6 332
Al : 132, 232 2p6 332 3p1
It is difficult to remove an electron from 33 in comparison to 3p (3s paired (stable) and 3p singly
occupied). Hence, IE of Mg is higher than Al.
12. Why there are 2, 8 and 8 elements in first, second and third periods of periodic table respectively?
Soln.: In first period Is is completed. Its capacity is of two electrons. In second period 23 2p and in
third period 3s 3p are completed. The capacity of these shells is of 8 electrons each. Thus, 2, 8
and 8 elements are present in first, second and third periods respectively.
13. Why is the electron affinities of halogens so high?
Soln.: The electron is easily accommodated as halogens acquire inert gas configuration after gaining
the electron.
14. Why is potassium strongly electropositive element?
Soln.: The ionisation potential of potassium is low. Hence, it can lose electron easily. Therefore, it
is strongly electropositive in nature.
15. (3) Between Na+ and F— which has more electronegativity?
(b) Explain the nature of the bond in the following compounds.
(NaCl, SiOz, PH3, HCl)
‘

Soln.: (a) Na” ion has more electronegativity than F“ ion, as the former is an electrophile having more
tendency to attract electron pair.
(b) NaCl ———> Ionic bond, as the electronegativity difference is, 3 — 0.9 = 2.1
Si02 ————> Polar covalent bond, as the electronegativity difference is, 3.5 1.8 = 1.7
——

PH3 ———» Pure covalent bond, as the electronegativity difference is, zero.
HCl ——> Polar covalent bond, as the electronegativity difference is, 3 2.1 = 0.9.
-—

16. Explain, why electron affinity of fluorine is lower than chlorine?

Soln.: Due to smaller size of the valence shell of fluorine atom, seven electrons are much more crowded
around the nucleus as compared to chlorine atom with bigger outermost shell (3s, 3p). So the
'

interelectronic repulsion is greater in fluorine atom than in chlorine atom. Hence fluorine atom
feels difficulty in entry of the new electron in its valence shell as compared to chlorine atom. Therefore
electron affinity of fluorine is lower than chlorine. Further, as the bond dissociation energy of C12 is
higher than F2, so the former has higher electron affinity.
17. (a) Explain why Mg has zero electron affinity? ‘

(b) Which property of elements does not vary along the group?
Soln.: (a) Mg has fully-filled s-orbital arrangement in its valence shell (332), which is already quite stable.
Therefore, when an electron is added to its atom it goes to the valency shell of higher energy level
(3p). In this process instead of release, energy is to be supplied. Hence the electron affinity value is
—v_e and roughly considered as zero.

(b) Along the group, valency of elements remains same, due to similar electronic configuration.
For example, the general outer electronic configuration for the members of group-2 is n32, {so they
have common valency of 2.
18. Explain that electron affinity of oxygen is smaller than sulphur.
Soln.: The valence shell of O atom is much smaller than the valence shell of S atom. Therefore 6 electrons
in the valence shell of oxygen atom are much more crowded, than in the valence shell cf sulphur atom.
Hence oxygen atom feels a little bit difficulty in entry of an electron to its valence shell as compared to
sulphur atom. So the electron affinity of oxygen is Smaller than sulphur atom.
19. In a particular period, the noble gases have highest ionisation energy, although they have largest size,
explain.
Soln.: Although the noble gases possess largest size for a particular period, but their ionisation energy
values are quite high. Because in their atoms not only the valence orbitals are full-filled but also valence
shell is saturated in some cases. So high energy is required to disturb their extra stability and hence
they have highest ionisation energy.
20. (a) Arrange the following in increasing order oftheir electron affinity. (K, Ca, P, S)
(1)) Explain, why A] and Ga have same atomic size although both belong to same
group?
Soln.: (a) Along the period electron affinity value increases, but due to stable fully filled s-orbital
arrangement in the valence shell of Ca atom, its electron affinity is zero. Therefore the increasing order
of electron affinity value is —'
Ca<K<P<S
112
 (b) 13A1 ————> 132, 232, 2136, 332, 3p1;
31Ga —> 182, 232, 2p6, 332, 3p6, 3d10, 432, 4p1
From the electronic configuration of both we can see that Al does not contain any d-electron, but Ga
contain 10 d—electrons in the inner shell. As the inner shell 3d-electrons have comparatively poor
screening effect and the nuclear charge of Ga is higher than Al, so the effective nuclear charge increases.
Therefore atomic radius of Ga decreases and the two radii (of Al and Ga) happens to be same, i.e.
1.26 A although both belongs to same group.
21. (a) Why group-1 metals and their salts impart characteristic colour to flame?
(b) Why the electron affinity of noble gases is zero?
Soln.: Group-1 metals have very low ionisation energy for which their valency electrons are excited to
higher energy level by absorbing heat energy from Bunsen flame. The excited electrons then return
back to ground state, emit energy in the form of radiation. These radiations appear as different
coloursin flame. Therefore group-1 metals and their salts impart characteristic colours to flame.
(b) The noble gas elements possess extra stable fully filled orbitals and saturated shellsin the
valency shell of their atom. So they have no tendency to accept an electron. Even if an electron
is added to their atom, then it enters next shell of higher energy level. Therefore in this process
instead of release, energy is to be supplied. Hence electron affinity values ofnoble gases are —-

ve and roughly considered as zero.

22. (a) The atomic no. of three elements A, B and C are Z — 2, Z and Z + 1 respectively. Of these ‘B’ is inert
gas, then predict:
(i) Which element has highest electronegativity?
(ii) Which element has highest ionisation energy?
(iii) What is the formula of the compound between ‘A’ and ‘0’?
(iv) What is the nature of the bond between ‘A’ and ‘C’?
(b) The successive ionisation energies for an element are 899, 1757, 14849, 21000 KJ/mole respectively
Predict the number of valence electronsin its atom.
Soln.: B (atomic no. = Z), an inert gas (group-18)
A (atomic no. = Z — 2), a member of group-16
C (atomic no. = Z + 1), a member of group-1.
(i) ‘A’ has highest electronegativityas it is a non-metal.
(ii) ‘3’ has highest ionisation energy, as it is an inert gas element.
(iii) The valency of ‘A’ is 2 and ‘C’1s 1. So the formula of the compound between‘’and ‘C’1s CZA.
(iv) The nature of the bond1s either1onic or polar covalent, as one is electropositive (C) and other is
electronegative (A).
’

(b) The number of valence electrons in its atom is 2, as there is suddenjump from 2nd ionisation energy
value to 3“1 ionisation energy value, which indicates that the removal of 3rd electron needs disturbance
of stable noble gas configuration.
23. OF2 is called as oxygen di-fluoride and not written as F20, where as 0120 is called as chlorine oxide and
not written as OClZ, explain.
Soln.: While writing the formula of a compound less electronegative element is written first, followed by
more electronegative elementand accordingly the name is written. As electronegativity values of Cl, 0,
and F are 3, 3.5 and 4 respectively. So the compound of oxygen and fluorine is written as OFZ, while
compound of oxygen and chlorine is written as 0120.
24. Ionisation potential andielectron affinity of fluorine are 17.42 and 3.45 eV respectively. Calculate
the electronegativity of fluorine.
‘

Soln.: According to Mulliken equation

T
IP+ EA
X = 5 6 when both [P and EA are taken in eV
17.42+3.45
XF = = 3.726

25. The electron affinity of chlorine is 3.7 eV. How much energy in kcal is released when 2 g of chlorine
is completely converted to 01‘ ion in a gaseous state?
'

Soln.: Cl + e ——-> 01‘ + 3.7 eV

35.5 3.7 x 23.06 kcal
Energy released for conversion of 2 g gaseous chlorine into 01‘ ions
3.7 x 23.06
= -—§5—5——X2 = 4.8 kcal