PERIODIC TABLE & PERIODICITY

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 23 39 7+39 / 2 = 23
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 law of 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.
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’s 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’s 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’s). Later on it was found that properties predicted by Mendeleev’s for these elements
and those found experimentally were almost similar.

PERIODIC T ABLE AND PERIODICITY # 1

 Table-1
eka-aluminium gallium eka-silicon germanium
Proeprty
(predicted) (found) (predicted) (found)
Atomic Mass 68 70 72 72.6
3
Density / (g/cm ) 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 :
He studied (1909) the frequency of the X-ray produced by the bombardment of a strong beam of electrons on
metal target. He found that the square root of the frequency of X-rays (  ) is directly proportional to number of
effective nuclear charge (Z) of metal i.e. to atomic number and not to atomic mass of the atom of that metal (as
nuclear charge of metal atom is equal to atomic number), i.e.  = a (Z - b).
Where ‘a’ is the proportionality constant and ‘b’ is a constant for all the lines in a given series of X-rays.
Therefore, he, concluded that atomic number was a better fundamental property of an element than its atomic
weight. He then suggested that the atomic number (Z) instead of atomic weight should be basis of the classification
of the elements.
Modern Periodic Law (Moseley’s Periodic Law) :
Physical and chemical properties of the 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, elements with similar
properties are repeated.

Periodicity :
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.

Cause of Periodicity :
The periodic repetition of the properties of the elements is due to the recurrence of similar valence shell
electronic configurations after certain regular intervals. For example, alkali metals have same valence shell
electronic configuration ns1 , therefore, have similar properties.
The long form of periodic table is the contribution of Range , Werner, Bohr and Bury.
This table is also referred to as Bohr‘s table since it follows Bohr’s scheme of the arrangements of elements into
four types based on electronic configurations of elements.
The modern periodic table consists of horizontal rows (periods) and vertical column (groups).

PERIODIC T ABLE AND PERIODICITY # 2

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 energy level.

 The number of elements in each period is twice the number of atomic orbitals available in energy level
that is being filled. For illustration.

 st period shortest period having only two elements. Filling of electrons takes place in the first energy
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 energy
level. 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.

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 2 Very short period
(1) n = 1
(2)nd n = 2 8 Short period
(3)rd n = 3 8 Short period
th 18 Long period
(4) n = 4
(5)th n = 5 18 Long period
th 32 Very long period
(6) n = 6
(7)th n = 7 19 Incomplete period

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 Table-3
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
114
Fr Ra Ac** Rf Ha Sg Bh Hs Mt Uun
Uuq
223 226 227 261.11 262.114 263.118 262.12 265 266 269

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.
(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.
 s-block and p-block elements are collectively called normal or representative elements.
(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) d1-10 ns1-2 (except, palladium which has valence
shell electron configuration 4d10 5s0).
 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.

PERIODIC T ABLE AND PERIODICITY # 4

 (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
(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) d0-1 ns2
 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.

Example-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 D : 1s2 2s2 2p6 3s2 3p5
2 2 6 2
E : 1s 2s 2p 3s 3p 4s6 2

Which among these will belong to the same group in the periodic table ?

Solution 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.

PERIODIC T ABLE AND PERIODICITY # 5

Example-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 ?
Solution (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 shinning 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. CrO3).
 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 under stood 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 B, Si, Ge, As, Sb and Te.
 Oxides of metalloids are generally amphoteric in nature.

Typical elements :
 Third period elements are called as typical elements. These include Na, Mg, Al, Si, P, S, Cl.
 The properties of all the elements belonging to a particular group resemble the properties of the
corresponding typical element of that group. For example, the general properties of alkali metals (A)
can be predicted from the properties of Na, not Li, the first member of the group.
 The properties of the elements of second period differ in the many respect belonging to the same group
due to the smaller atomic size and absence of vacant d-orbitals.

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)

PERIODIC T ABLE AND PERIODICITY # 6

 (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 per unit area is nearly similar (Be2+ = 2.36 and Al3+ = 2.50) because the
charges are 2+ and 3+ respectively.

(ionic ch arg e)
Charge per unit area = 4
..(ionic radius )
3
 Similarities between properties of Li and Mg are as follows.
(a) Li and Mg both reacts directly with nitrogen to form lithium nitride (Li3N) and magnesium nitride (Mg3N2)
whereas other alkali metals of IA group does not form nitride.

(b) Fluoride carbonate and phosphate of Li and Mg are insoluble in water whereas these compounds of
other alkali metals are soluble.

(c) Li and Mg both are hard metals, whereas other metals of IA group are soft.

(d) LiOH and Mg(OH)2 both are weak bases, whereas hydroxides of other elements of IA group are strong
base.

(f) Metallic bond in Li and Mg both are strong compare to other alkali metals .
(g) Their melting and boiling points are high.

(h) By thermal disintegration of LiNO3 and Mg (NO3)2 ; Li2O and MgO is obtained respectively.

(i) Thermal stability of Li2CO3 and Mg CO3 is very less compare to other alkali metals and they liberates
CO2 gas easily.
 Similarly Be shows similarity to Al of IIIA group compare to other elements of IIA group which are as follows.
(a) These both elements do not provide colour to Bunsen burner.

(b) They both are comparatively stable in air.

(c) Both are insoluble in NH3 therefore do not form blue coloured solution.

(d) There is no tendency of making peroxide and superoxide by them.

(e) Reducing power is very less due to low value of standard electrode potential in the form of oxidation
potential.

(f) The oxides and hydroxides of Be and Al both are amphoteric in nature.

The periodicity of atomic properties :

(i) Effective nuclear charge :
Between the outer most valence electrons and the nucleus of an atom, there exists number of shells
containing electrons. Due to the presence of these intervening electrons, the valence electrons are
unable to experience the attractive pull of the actual number of protons in the nucleus. These intervening
electrons act as shield between the valence electrons and protons in the nucleus. Thus, the presence
of intervening (shielding) electrons reduces the electrostatic attraction between the protons in the nucleus
and the valence electrons because intervening electrons repel the valence electrons. The concept of
effective nuclear charge helps in understanding the effects of shielding on periodic properties.
The effective nuclear charge (Zeff) is the charge actually felt by the valence electron. Zeff is given by Zeff =
Z – , (where Z is the actual nuclear charge (atomic number of the element) and  is the shielding
(screening) constant). The value of  i.e. shielding effect can be determined using the Slater’s rules.

PERIODIC T ABLE AND PERIODICITY # 7

(ii) Atomic radius :
Probability of finding the electron is never zero even at large distance from the nucleus. Based on
probability concept, an atom does not have well defined boundary. Hence exact value of the atomic
radius can’t be evaluated. Atomic radius is taken as the effective size which is the distance of the
closest approach of one atom to another atom in a given bonding state.
Atomic radius can be
(A) Covalent radius : It is one-half of the distance between the centres
of two nuclei (of like atoms) bonded by a single covalent bond as
shown in figure.

 Covalent radius is generally used for nonmetals.

Single Bond Covalent Radius, SBCR (bond length) -

(a) For homodiatomic molecules dA–A = rA + rA or 2rA
d
so, rA = A  A
2
(b) For heterodiatomic molecules in which electronegativity remains approximately same.
dA – B = rA + rB
 For heteronuclear diatomic molecule, A–B, where difference between the electronegativity values of
atom A and atom B is relatively larger,
dA – B = rA + rB – 9.0 
This formula was given by Stevenson & Schomaker. Electronegativity values are given in Pauling
units and radius in picometers.
 = XA – XB where XA and XB are electronegativity values of high electronegative element A and less
electronegative element B.
Later on modified and more accurate formula was proposed by Porterfield as given below ;
dA – B = rA + rB – 7.0 ()2

(B) Vander Waal’s radius (Collision radius) : It is

one-half of the internuclear distance between two
adjacent atoms in two nearest neighbouring
molecules of the substance in solid state as shown
in figure.
 Vander Waal’s radius does not apply to metal and
its magnitude depends upon the packing of the atoms
when the element is in the solid state.
Comparison of covalent radius and van der Waal’s radius
 The vander Waal’s force of attractions are weak, therefore, the internuclear distances in case of atoms
held by van der Waal’s forces are much larger than those of between covalently bonded atoms. Therefore
van der Waal’s radii are always larger than covalent radii.
 A covalent bond is formed by the overlapping of two half-filled atomic orbitals and in this a part of the
orbital becomes common. Therefore, covalent radii are always smaller than the van der Waals radii. For
example,
Table-4

Elements H O F S Br
Covalent radius (Å) 0.37 0.66 0.64 1.04 1.11
van der Waal's radius (Å) 1.20 1.40 1.35 1.85 1.95

PERIODIC T ABLE AND PERIODICITY # 8

(C) Metallic radius (Crystal radius) :
It is one-half of the distance between the nuclei of
two adjacent metal atoms in the metallic crystal
lattice as shown in figure.

 Metallic radius of an element is always greater than its covalent radius. It is due to the fact that metallic
bond (electrical attraction between positive charge of an atom and mobile electrons) is weaker than
covalent bond and hence the internuclear distance between the two adjacent atoms in a metallic
crystal is longer than the internuclear distance between the covalently bonded atom.
For example : Metallic radius Covalent radius
K 231 pm 203 pm
Na 186 pm 154 pm

 Thus, the covalent, vander Wall’s and metallic radius magnitude wise follows the order,
rcovalent < rcrystal < rvander Walls
Table-5

Variation in a Period Variation in a Group

In a period left to right : 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 constant
Effective nuclear charge (Zeff) also increases 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 The effect of increased number of atomic shells
nucleus by the increased Zeff. overweighs the effect of increased nuclear charge. As a
result of this the size of atom increases from top to
bottom in a given group.
rn  1
Z*
Hence atomic radii decrease with increase in
atomic number in a period from left to right.

 The atomic radius of inert gas (zero group) is given largest in a period because it is represented as
vander Waals’s radius which is generally larger than the covalent radius. The vander Waal’s radius of
inert gases also increases from top to bottom in a group.

 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-6
Element Sc Ti V Cr Mn Fe Co Ni Cu Zn
Atomic radius (Å) 1.44 1.32 1.22 1.18 1.17 1.17 1.16 1.15 1.17 1.25
 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

PERIODIC T ABLE AND PERIODICITY # 9

 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.
(iii) Ionic radius :
The effective distance from the centre of nucleus of the ion up to which it has an influence in the ionic
bond is called ionic radius.
Table-7
Cation Anion
It is formed by the lose of one or more electrons from It is formed by the gain of one or more electrons in the
the valence shell of an atom of an element. valence shell of an atom of an element.
Cations are smaller than the parent atoms because, Anions are larger than the parent atoms because
(i) the whole of the outer shell of electrons is usually (i) anion is formed by gain of one or more electrons in the
removed. neutral atom and thus number of electrons increases but
(ii) in a cation, the number of positive charges on the magnitude of nuclear charge remains the same.
nucleus is greater than number of orbital electrons (ii) nuclear charge per electrons is thus reduced and the
leading to incresed inward pull of remaining electrons electrons cloud is held less tightly by the nucleus leading to
causing contraction in size of the ion. the expansion of the outer shell. Thus size of anion is
increased.

For example : Na (metallic radius 1.86 Å) Na+ (ionic radius 1.02 Å)

Number of electrons : 11 10
Number of protons : 11 11
Electronic configuration : 1s2 2s2 2p6 3s1 1s2 2s2 2p6
There is complete removal of one shell leading to decrease in size.
Cl (covalent radius 0.99 Å) Cl– (ionic radius 1.84 Å)
Number of electrons : 17 18
Number of protons : 17 17
So, there is reduction in effective nuclear charge and hence the electron cloud expands in case of Cl–.

 The sizes of ions increases as we go down a group (considering the ions of same charge).
For example :
Li+ (0.76) < Na+ (1.02) < K+ (1.38) < Rb+  (in Å)
Be2+ < Mg2+ < Ca2+ < Sr2+
F– < Cl– < Br – < –

 The ionic radius decreases as more electrons are ionized off that is as the valency increases e.g. Cr2+
= 0.80 Å, Cr3+ = 0.615 Å, Cr4+ = 0.55 Å, Cr5+ = 0.49 Å and Cr6+ = 0.44 Å.

 The d and f orbitals do not shield the nuclear charge very effectively .Therefore there is significant
reduction in the size of the ions, just after d or f orbitals have been filled completely. This is called a
lanthanide contraction. Atomic radii of Hf (Hf 4+ = 0.71 Å) and Zr (Zr4+ = 0.72 Å), and Nb (Nb3+ = 0.72 Å)
and Ta (Ta3+ = 0.72 Å) are almost identical due to lanthanide contraction.
 The species containing the same number of electrons but differ in the magnitude of their nuclear
charges are called as isoelectronic species. For example, N3– , O2–, F–, Ne, Na+ , Mg2+ and Al3+ are all
isoelectronic species with same number of electrons (i.e 10) but different nuclear charges of +7, +8,
+9, +10, +11, +12 and +13 respectively.
Within a series of isoelectronic species as the nuclear charge increases, the force of attraction by the
nucleus on the electrons also increases. As a result, the ionic radii of isoelectronic species decrease
with increases in the magnitude of nuclear charges. For example, as shown in figure.
Al3+ Mg2+ Na+ F– O2– N3–

Ionic radii increase

PERIODIC T ABLE AND PERIODICITY # 10

 As effective nuclear charge decrease.

 Following are the examples of isoelectronic series

(i) S2–, Cl–, K+ , Ca+2 , Sc+3 (ii) SO2, NO3– , CO3 2–, (iii) N2 , CO, CN– (iv) NH3 , H3O+
1
 Pauling’s empirical formula for ionic radius  (only for isoelectronic species).
nuclear ch arg e

Example-3 X – X bond length is 1.00 Å and C–C bond length is 1.54 Å. If electronegativities of X and C are 3.0 and
2.0 respectively, then C–X bond length is likely to be ? (using Stevension & Schomaker formula).
Solution rC–X = rC + rX – 0.09 
1.00 1 .54
=  – 0.09[ = 1] = 1.27 – 0.09 ;
2 2
Ans. C–X bond length = 1. 18 Å.
Example-4 Atomic radius of Li is 1.23 Å and ionic radius of Li + is 0.76Å. Calculate the percentage of volume
occupied by single valence electron in Li.
4
Solution Volume of Li = × 3.14 × (1.23)3 = 7.79 Å (– Li = 1s22s1 )
3
4
Volume of Li + = × 3.14 × (0.76)3 = 1.84 Å (– Li + = 1s2)
3
 Volume occupied by 2s subshell = 7.79 – 1.84 = 5.95 Å.
5.95
 % Volume occupied by single valence electron i.e., 2s electron = ×100 = 76.4%
7.79
Example-5 Select from each group the species which has the smallest radius stating appropriate reason.
(a) O, O–, O2– (b) P3+ , P4+ , P5+
Solution (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.
(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+.
Example-6 Mg2+ is smaller than O 2– in size, though both have same electronic configuration. Explain ?
Solution Mg2+ and O 2– both are isoelectronic i.e., have same number of electrons. But Mg 2+ having 12
protons in its nucleus exerts higher effective nuclear charge than O 2– 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 O 2–.

(iv) 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.
(IE1 )
M(g)   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.

PERIODIC T ABLE AND PERIODICITY # 11

(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 in a group from top to bottom with increase in atomic size.
(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.

(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.

PERIODIC T ABLE AND PERIODICITY # 12

Example-7 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
Solution (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.

Example-8 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].
Solution 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.

Example-9 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.

Solution 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.

Example-10 M(g)  M+ (g) + e– ; H = 100 eV.

2+ –
M(g)  M (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.
+ –
Solution M(g)  M (g) + e IE1 of M
M+  M2+ + e– IE2 of M but IE1 of M+
2+ –
M  M + 2e (IE1 + IE2).
Ans. (A,B,D)

(V) Electron Affinity :

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)
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.

PERIODIC T ABLE AND PERIODICITY # 13

 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, Ea of an element
which is the difference in energy between the gaseous atoms and the gaseous ions at T = 0.
Ea = E (X, g) – E (X–, g),
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 ; egH = – 328 kJ mol–1
5 5
Although the precise relation is egH = – Ea – RT, the contribution RT is commonly ignored.
2 2
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.
Exothermic
O(g) + e–(g)    O– (g) ; Ea = 140.9 kJ mol–1 ; egH = – 140.9 kJ mol–1
Endothermi c
O–(g) + e–(g)     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.
 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.
 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.
 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.

Example-11 Consider the elements N, P, O and S and arrange them in order of increasing negative electron
gain enthalpy.
Solution Order of increasing negative electron gain enthalpy is N < P < O < S. For detail refer text.

PERIODIC T ABLE AND PERIODICITY # 14

Example-12 Why do halogens have high electron gain enthalpies (i.e. –egH) ?
Solution 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.
Example-13 Which will have the maximum value of electron affinity Ox ,Oy, Oz [x,y and z respectively are 0, – 1 and
–2]?
(A) Ox (B) Oy (C) Oz (D) All have equal.
Solution 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.
Example-14 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.
Solution 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

Example-15 Account for the large decrease in electron affinity between Li and Be despite the increase in nuclear
charge.
Solution 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.

(VI) 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
Table-8
Variation of electronegativity in a group Variation of electronegativity in a period
On moving down the groups, Z increases but Zef f
almost remains constant, number of shells (n) While moving across a period left to right, Z,
increases, rn (atomic radius) increases. Zef f increases & rn decreases. Therefore,
Therefore, electronegativity decreases moving electronegativity increases along a period.
down the groups.

PERIODIC T ABLE AND PERIODICITY # 15

 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 = O.208 E.A B  E A  A  E 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 = O.1017 E.A B  E A  A  E B 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 isrelated 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.

APPLICATION OF ELECTRONEGATIVIT Y :
(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) Metallic and Nonmetallic Nature :
Generally values of electronegativity of metallic elements are low, whereas electronegativity values of
nonmetals are high.
(c) Partial Ionic Character in Covalent bonds :
Partial ionic characters are generated in covalent compounds by the difference of electronegativities.
Hanney and Smith calculated percentage of ionic character from the difference of electronegativity.
Percentage of ionic character = 16(XA – XB) + 3.5(XA – XB)2
= 16 + 3.52
= (0.16 + 0.0352) × 100
XA is electronegativity of element A (Higher)
XB is electronegativity of element B (Lower)
 = XA – XB
(d) Bond Strength & Stability :
As the difference in the electronegativities between two bonded atoms in a molecule increases, the
bond strength and stability increase. For example H–F > H–Cl > H–Br > H–I

PERIODIC T ABLE AND PERIODICITY # 16

 (VII) Periodicity of Valence or Oxidation States :
The valence of representative elements is usually (though not necessarily) equal to the number of
electrons in the outermost orbitals and / or equal to eight minus the number of outermost electrons.
Nowadays the term oxidation state is frequently used for valence.
Consider the two oxygen containing compounds : OF2 and Na2O. The order of electronegativity of the
three elements involved in these compounds is F > O > Na. Each of the atoms of fluorine, with outer
electronic configuration 2s22p5, shares one electron with oxygen in the OF2 molecule. Being highest
electronegative element, fluorine is given oxidation state –1. Since there are two fluorine atoms in this
molecule, oxygen with outer electronic configuration 2s22p4 shares two electrons with fluorine atoms
and thereby exhibits oxidation state +2. In Na2O, oxygen being more electronegative accepts two
electrons, one from each of the two sodium atoms and thus, shows oxidation state –2. On the other
hand sodium with electronic configuration 3s1 loses one electron to oxygen and is given oxidation state
+1. Thus, the oxidation state of an element in a particular compound can be defined as the charge
acquired by its atom on the basis of electronegative consideration from other atoms in the molecule.
There are many elements which exhibit variable valence. This is particularly characteristic of transition
elements and actinoids.

Example-16 Calculate the electronegativity of carbon from the following data :

EH–H = 104.2 kcal mol –1 , EC–C = 83.1 kcal mol –1
–1|
EC–H = 98.8 kcal mol , XH = 2.1
Solution Let the electronegativity of carbon be XC , applying Pauling equation,
1
XC–XH = 0.208 [EC–H – (EC-C + EH–H)] 1/2
2
X – 2.1 = 0.208 [98.8 –
1
C (83.1 + 104.2)] 1/2
2
 X = 2.5 Ans. 2.5
C
Example-17 If electronegativity of x be 3.2 and that of y be 2.2, the percentage ionic character of xy is –
(A) 19.5 (B) 18.5 (C) 9.5 (D) 29.5.
Solution ENx – ENy = 3.2 – 2.2 = 1.
=1
[ = difference of electronegativity values between x and y].
% ionic character = 16 + 3.52 = 19.5. Ans. (A)
Example-18 Which of the following relation is correct ?
(A) 2 IP – E.A. – EN = 0 (B) 2EN – IP – EA = 0
(C) 2EA – IP – EA = 0 (D) EN – IP – EA = 0
I.P.  E.A.
Solution On Mulliken’s scale : E.N. =
2
2E.N. – I.P. – E.A. = 0 Ans. (B)

(VIII) Periodic Trends and Chemical Reactivity :

As the periodicity is related to electronic configuration, all chemical and physical properties are a
manifestation of the electronic configuration of elements.

The atomic and ionic radii, as we know, generally decrease in a period from left to right. As a consequence,
the ionization enthalpies generally increase (with some exceptions) and electron gain enthalpies become
more negative across a period. In other words, the ionization enthalpy of the extreme left element in a
period is the least and the electron gain enthalpy of the element on the extreme right is the highest
negative (except noble gases which having completely filled shells have rather positive electron gain
enthalpy values). This results in high chemical reactivity at the two extremes and the lowest in the
centre. Thus, the maximum chemical reactivity at the extreme left (among alkali metals) is shown by
the loss of an electron leading to the formation of cation and at the extreme right (among halogens)

PERIODIC T ABLE AND PERIODICITY # 17

 shown by the gain of an electron forming an anion. The loss and gain of electron can be related with the
reducing and oxidizing behaviour of the elements respectively. However, it can also be directly related to
the metallic and nonmetallic character of elements. Thus, the metallic character of an element, which
is highest at the extremely left decreases and the nonmetallic character increases while moving from
left to right across the period. The chemical reactivity of an element can be best understood by its
reactions with oxygen and halogens. Elements on two extremes of a period easily combine with oxygen
to form oxides. The normal oxide formed by the element on extreme left is the most basic (e.g. Na2O),
whereas that formed by the element on extreme right is the acidic (e.g. Cl2O7). Oxides of elements in
the centre are amphoteric (e.g. Al2O3, As2O3) or neutral (e.g., CO, NO, N2O). Amphoteric oxides behave
as acidic with bases and as basic with acids, whereas neutral oxides have no acidic or basic properties.

In general, metallic oxides (O2–), peroxides (O22–) and super oxides (O21–) are ionic solids.
The tendency of group IA metals (alkali metals) to form oxygen rich compounds increases from top to
bottom i.e. with increasing cation radii and decreasing charge density on the metal ion.
IIA metals also show the similar trend. Except Be, the IIA metals react with oxygen at normal conditions
to form normal ionic oxides and at high pressure of O2, they form peroxides (CaO2, SrO2, BaO2). Oxides
of metals are called as basic anhydrides as most of them combine with water forming hydroxides with
no change in oxidation state of metals.
Oxides of IA and IIA dissolve in water forming basic solutions where as other oxides do not dissolve in
water.
Na2O + H2O  2NaOH
Oxygen combines with many nonmetals to form covalent oxides such as CO, CO2, SO2, SO3, P4O10,
Cl2O7 etc. Nonmetals with limited supply of oxygen usually form oxides in which nonmetals are present
in lower oxidation states where as with excess of oxygen, oxides with higher oxidation state are formed.
Oxides of nonmetals are called as acid anhydrides as most of them dissolve in water forming acids or
oxy-acids.
P4O10 + 6H2O  4H3PO4; SO3 + H2O  H2SO4 ; Cl2O7 + H2O  2HClO4 .
 In a group, basic nature of oxides increases or acidic nature decreases. Oxides of the metals are
generally basic and oxides of the nonmetals are acidic. The oxides of the metalloids are generally
amphoteric in nature. The oxides of Be, Al, Zn, Sn, As, Pb and Sb are amphoteric.
 In a period the nature of the oxides varies from basic to acidic.
Na2O MgO Al2O3 SiO2 P4O10 SO3 Cl2O7
Strongly basic Basic amphoteric Weakly acidic Acidic Acidic Strongly acidic

 Oxides of the elements E in H2O produce EOH.

If electronegativities of E and O is greater than that of H and O in H2O then EOH is basic due to the
formation of OH–.
E—O—H + H2O  [EOH2]+ + OH–
If electronegativities of E and O is less than that of H and O in H2O then EOH is acidic due to the
formation of H3O+.
E—O—H + H2O  H3O+ + EO–
Across the 3d-series from left to right, the change in atomic radii is much smaller as compared to those
of representative elements. The change in atomic radii is still smaller among inner-transition metals (4ƒ
series). The ionization enthalpies of transition metals are intermediate between those of s- and p-
blocks. As a result, they are less electropositive than group 1 and 2 metals.
In a particular group, the increase in atomic and ionic radii with increase in atomic number generally
results in a gradual decrease in ionization enthalpies and a regular decrease (with exception in some
third period elements) in electron gain enthalpies in the case of main group elements. Thus the metallic
character increases down the group and nonmetallic character decreases. This trend can be correlated
with their reducing and oxidizing property.
In the case of transition elements, however, a reverse trend is observed. This can be explained in terms
of atomic size and ionization enthalpy as shown in figure.

PERIODIC T ABLE AND PERIODICITY # 18

 Electron Gain Enthalpy

Electron Gain Enthalpy

Ionization Enthalpy

Ionization Enthalpy
Electronegativity

Atomic Radius
cter
lic chara
nonmeta
haracter
metalic c

Atomic Radius

Electronegativity

Example-19 Arrange the following in decreasing basic nature LiOH, NaOH, KOH, CsOH.
LiOH, NaOH, KOH, CsOH

Solution The basic nature of hydroxides of elements of group 1st increases on descending the group with increase
in size of cation as CsOH > RbOH > KOH > NaOH > LiOH.
Example-20 Arrange the following compounds in increasing order of acidic strength Al2O3, SiO2, P2O3 and SO2.

Solution Along the period acidity of oxides increases as the electronegativity difference between element and
oxygen decreases.
Ans. Al2O3 < SiO2 < P2O3 < SO2.

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+ ; Ga3+ < 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 Tl3+(I3)–.

PERIODIC T ABLE AND PERIODICITY # 19

 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 : Be 2+ , 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.
Ionisation energy  Electron affinity
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 Ans. P = 3.726
2. 8

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.

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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) d5 ns1 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) Aluminium
(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.
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.

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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
(D) An element with the ground-state electron configuration [Ar]4s23d10 (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.

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