CLASSIFICATION OF ELEMENT AND

PERIODICITY IN PROPERTISE

The classification of elements in periodic form is a great achievement in the history

of chemistry. It is difficult to study individually the chemistry of more than one
hundred natural or synthetic elements and millions of their compounds. The periodic
table provides systematic and organized chemical behavior of the elements into few
simple and logical patterns. In periodic table elements are arranged in rows &
columns. From the position of the element, it is possible to predict its chemistry. In
this unit, we will study the historical development of modern periodic table, its
function and some of the periodic trends in the physical and chemical properties of
the elements.

HISTORY OF DEVELOPMENT OF THE

PERIODIC TABLE

All earlier attempts on the classification of the elements were based upon their
atomic weights.

Dobereiner’s Triads:
The first attempt towards the classification of elements was made by John
Dobereiner a German chemist in 1829. He classifies the elements with similar
properties in the groups of three elements (Triads). He could succeed in making only
a few triads. In the triads of elements the atomic weight of the middle element was
the arithmetic mean of the atomic weights of the other two. Some of the triads are as
under.

Li Na K Ca Sr Ba

7 23 39 40 88 137

P As Sb Cl Br I

31 75 120 35.5 80 123

The major drawback of Dobereiner’s classification was that the concept of triads
could be applied only for the limited number of elements.

Newland’s Law of octaves:

The English chemist John Newland in 1865 − 66, developed the law of octaves. He
pointed out that, if the elements are arranged in order of their increasing atomic
weights, every eighth element had similar properties to first one like the first and
eighth note of the musical scale. For example

sa re ga ma pa dha ni sa

Li Be B C N O F Na

Na Mg Al Si P S Cl K

This generalization was also discarded since it could not be applied to elements
having atomic weight greater than that of calcium i.e. 40 a.m.u Furthermore with the
discovery of noble gas, the properties of the eighth elements were no longer similar
to the first one.

Lothar Meyer's Atomic Volume Curve 1869:

Lothar Meyer a German chemist plotted a graph between atomic weight and atomic
volume (i.e. atomic weight in solid state/density) and he find out that elements with
similar properties occupied similar positions on the graph. Strong electro-positive
elements of the IA group except for Li i.e. Na, K, Rb, Cs, etc. occupied the top
position on the graph. IIA group elements like Be, Mg, Ca, Sr, Ba etc. occupied the
positions on the ascending part of the graph. Inert gases except He occupied the
positions on the descending part of the graph. Halogens also occupied the
descending part of the graph.
Mendeleev’s Periodic Law: In 1869 Dmitri Mendeleev, a Russian Chemist used
broader range to physical and chemical properties to classify the elements. The
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 (inert gases
were not discovered then)

MENDELEEV'S PERIODIC TABLE

Mendeleev discovered 63 elements in the periodic table into 7 horizontal rows known
as periods and 8 vertical columns known as groups numbered 1 to 8. When all the
chemical elements are arranged, and there is a recurring pattern known as “periodic
law” in their properties, in which all the elements in the same colu mn (group) have
similar properties. In the mid-19th century, the initial discovery, which was made by
Dmitry. Mendeleyev has been of inestimable value in the development of chemistry.

What is a Periodic Table?

A periodic table is an arrangement of all elements known to man according to their
increasing atomic number and recurring chemical properties. They are arranged in a
tabular arrangement where a row is a period, and a column is a group.

The elements are arranged from left to right and top to bottom in increasing order of
atomic numbers. Therefore,

 Elements in the same group that have the same configuration of valence
electrons and, therefore, similar chemical properties.
 While elements in the same period will have increasing order of valence
electrons. Therefore, as the energy level of an atom increases, the number of
energy sublevels per energy level increases.

The first 94 periodic table elements occur naturally, while the remaining 95 to 118
have only been synthesized in laboratories or nuclear reactors.
The modern periodic table we use now is a new and improved version of certain
models put forward by scientists in the 19th and 20th centuries. Dimitri Mendeleev
presented his periodic table based on the findings of some scientists before him,
such as Antoine-Laurent de Lavoisier and John Newlands. Thus, Mendeleev is given
sole credit for his development of the periodic table.

Mendeleev Periodic Table

Dimitri Mendeleev, who is widely regarded as the father of the periodic table, came
up with the first iteration of the periodic table that is similar to the one we use now.
Mendeleev's periodic law differs from the modern periodic law in one significant
aspect.

 Mendeleev modeled his periodic table based on increasing atomic mass,

while the modern periodic law is based on increasing the order of atomic
numbers.

Although Mendeleev's periodic table was based on atomic weight, he could predict
the properties and discovery of specific elements. Only about half of the elements we
know now were known during his time, and most of the information about all
elements was inaccurate. Mendeleev's periodic table was published in the German
Journal of chemistry in 1869.

Mendeleev Suggested
  He excluded certain elements and assigned them a separate independent
position.
 Leaving gaps for the then undiscovered elements
 When the properties of elements did not correspond to what is expected of
the group they were named by prefixing Eka to the preceding element e.g.
Eka boron (Silicon); Eka silicon (Germanium), Eka aluminum (Gallium); Eka
Maganese (Technitium)

Uses of Mendeleev Periodic Table

 Systematic study of the elements

 Atomic weights of elements were determined with the help of periodic table.
Atomic weight = Valency × Equivalent weight = Group number × Equivalent
weight.
 Atomic weights of elements were corrected. Atomic weight of Be was
calculated to be 3 × 4.5 = 13.5 by considering its valency 3. Mendeleev
calculated it 2 × 4.5 = 9.
 Discovery of new elements – In Mendeleev's periodic table two consecutive
members differs by two or three units in the atomic weight. Where this gap
was more, the gaps were left in the periodic table.

Defects of Mendeleev Periodic Table:

1. The Position of hydrogen is uncertain. It has been placed in IA and VIIA

groups because of its resemblance with both the groups.
2. No separate positions are given to isotopes.
3. It is not clear to which group lanthanides and actinides belong to.
4. Although there is no resemblance except valency of subgroups A and B, they
have been put in the same group.
5. The order of increasing atomic weights is not strictly followed in the
arrangement of elements in the periodic table. For e.g. – Co (At.wt. 58.9) is
placed before Ni (58.7) and Ar (39.9) is placed before K (39).

LONG FORM OF THE PERIODIC TABLE

OR MOSELEY'S PERIODIC TABLE

The table which is most commonly used these days is called long form of the
periodic table which consists of eight vertical columns and seven horizontal rows.
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 (√v) is directly proportional to the number of nuclear charge (z)
of the metal. √v = 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.
Moseley's Periodic Law or Modern Periodic Law: Physical and chemical properties of
elements are the periodic functions of their atomic numbers. If the elements are
arranged in order of their increasing atomic number, after a regular interval,
elements with similar properties are repeated.

Characteristics of Periods:

 First period is called 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.
 Lanthanide and actinide series containing 14 elements each are placed
separately below the main periodic table. These are related to sixth and
seventh periods of III B group respectively
 Elements of third period from sodium (Na) to Chlorine (Cl) are called typical
elements.
 Valency of an element in a period increases from 1 to 7 with respect to
oxygen.

Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl2O7

1234567

 Elements of second period are called bridge elements.

 Characteristic of Groups:

 Moseley’s periodic table contains sixteen groups. These are represented by

Roman numerals I, II, III, IV, V, VI, VII, VIII and zero. Groups I to VII are
divided into two subgroups A and B, Group VIII consists of three sets, each
one containing three elements.
 Inert gases are present in zero group.
 The valency of an element in a group is equal to the group number.
 There is no resemblance in the elements of subgroups A and B of same
group, except valency
 The elements of the groups which resemble with typical elements are called
normal elements. For example IA, IIA, IIIA, IVA, VA, VIA, VIIA group elements
are normal elements or main group elements or representative elements.

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

CAUSE OF PERIODICITY
According to the Modern Periodic Law, the Properties of the elements are repeated
after certain regular intervals when these elements are arranged in order of their
increasing atomic number. Therefore the cause of periodicity in properties is the
repetition of similar outer electronic configuration at certain regular intervals.

All the elements of group IA i.e. alkali metals have similar outer electronic
configuration i.e. ns1, which are given below

Symbol Atomic No. Electronic configuration

Li 3 1s22s1 or [He]2s1
Na 11 1s22s22p63s1 or [Ne]3s1
K 19 1s22s22p63s23p64s1 or [Ar] 4s1
Rb 37 1s22s22p63s23p63d104s24p65s1 or [Kr] 5s1
Cs 55 1s22s22p63s23p63d104s24d105s25p66s1 or [Xe] 6s1
Fr 87 1s22s22p63s23p63d104s24p64d104f145s25p65d106s26p77s1 or [Rn] 7 s1
Thus it is because of similarity in electronic configuration that all the elements have
similar properties

 group elements are transition elements.

NOMENCLATURE OF ELEMENTS WITH

ATOMIC NO > 100
The naming of the new elements had been left earlier traditionally to its discoverer
and the suggested name was ratified by the IUPAC, but some of these elements
have been assigned two names/ symbols. To overcome all these difficulties, the
IUPAC appointed a Commission on Nomenclature of Inorganic Chemistry (CNIC). In
1997 IUPAC approved the names based on the following points.

 The names are derived directly from the atomic numbers using numerical
roots for 0 and numbers from 1-9 and adding the suffix ium
 In certain cases, the names are shortened. For example biium & triium are
shortened to bium & trium

Roots for IUPAC nomenclature of elements are given below.

Digit 0 1 2 3 4 5 6 7 8 9
Root nil un bi Tri quad pent hex sept oct enn
Abbreviation n u b T q P h s O e
The recommended and official names of some super heavy elements are given
below

Z Recommended name Symbol IUPAC official name IUPAC symbol

101 Unnilunium Unu Medelevium Md
102 Unnilbium Unb Nobelium No
103 Unniltrium Unb Lawrencium Lr
104 Unnilquadium Unq Rutherfordium Rf
105 Unnilpentium Unp Dubnium Db
106 Unnilhexium Unh Seaborgium Sg
107 Unniseptium Uns Bohrium Bh
108 Unniloctium Uno Hassnium Hs
109 Unnilennium Une Meitnerium Mt
Long Form of the Periodic Table and Electronic Configuration of Elements:

 Each period starts with an alkali metal whose outermost electronic

configuration is ns1.
 Each period ends with a noble gas of outermost electronic configuration
ns2np6 except He. The electronic configuration of He is 1s2
 The number of elements in a period is equal to the number of necessary
electrons to acquire the ns2np6 configuration in the outermost shell of the first
element (alkali metal) of the period. First period contains two elements.

Number of
Periods Stable electronic configuration
electrons
First 1s2 2
Second 2s22p6 8
Third 3s23p6 8
Fourth 4s23d104p6 18
Fifth 5s24d105p6 18
Sixth 6s24f145d106p6 32
Seventh 7s24f1-146d107p6 Incomplete
 The number of elements in each period may be determined by the number of
electrons in a stable configuration as under

CLASSIFICATION OF ELEMENTS ON THE

BASIS OF THEIR ELECTRONIC
CONFIGURATION

On the basis of electronic configuration, the elements may be divided into four
groups, that is s, p, d & f. This division is based on the name of orbital which
receives the valence electron.

s - Block elements:

Elements in which the last electron enters the s- orbital or their respective outermost
shells are called s- block elements. These are present in the left part of the periodic
table in group IA & IIA i.e. 1 & 2 group in modern periodic table. Electronic
configuration of valence shell is ns1-2
(n 1 to 7)

Characteristic of s – block elements:

 They are soft metal with low melting & boiling points
 They posses metallic character & reactivity of metal increases down the group
 They are highly electropositive and having low ionization enthalpies
 They have valency +1(in case of alkali metals) &+2 (in case of alkaline earth
metals)
 Most of the metals of this block impart characteristic color to the flame
 They are strong reducing agents & are good conductor of heat & electricity.

p − block elements:

These are present in right part of the periodic table and constitute the groups IIIA to
VIIA and zero groups i.e. group 13 to 18 of the modern periodic table. Most of these
elements are metalloids & non metals but some of them are metals also. The last
electron enters in p − orbital of valency shell and electronic configuration of valency
shell is ns2 n1−6(n=2 to 7)

Characteristics of p − block elements:

 It contains both metals & non metals. The metallic character decrease from
left to right along the period and metallic character increases from top to
bottom within a group
 They mostly form covalent compounds
 Ionization energy is higher as compared to s – block elements.
 Reducing character increases from top to bottom in a group & oxidizing
character increases left to right in a period.

d - Block elements:

These are present in the middle part of the periodic table (between s & p block
element) and constitute IIIB to VIIB, VIII, IB & IIB i.e. 3 to 12 groups of the modern
periodic table. The outermost electronic configuration is (n-1) d1-10 ns1-2 (n=4 to 7).
There are four series of d-block elements, which are 3d series−Sc (21) to Zn (30) 4d
series – Y( 39) to Cd(48) & 5d series
–La (57), Hf (72) to Hg(80) 6d series Ac(89), Rf(104) ……………………………….
Unb (ununbium) 112 (incomplete)

Characteristics of d – block elements:

 These are hard, ductile & malleable metals with high melting & boiling points
 Ionization energy is between s & p- block elements
 They show variable oxidation states and are good conductors of heat &
electricity.
 They form both ionic & covalent compounds and compounds are generally
coloured and paramagnetic in nature
 Most of the transition metals form alloys.

f - Block elements:

These are placed separately below the main periodic table and are mainly related to
IIIB i.e. group 3 of the periodic table. There are two series of f–block elements, which
are
4f series – Lanthanides 14 elements Ce(58) to Lu(71) and 5f series Actinides 14
elements Th(90) to Lr(103). Their outermost electronic configuration is (n-2)f1-14
(n−1)s2(n-1)p6 (n-1) d0-1 ns2.
(n = 6 & 7)

Characteristics to f – block elements:

 They are heavy metals with high melting & boiling points
 They show variable oxidation states & their compounds are generally
coloured
 Most of the elements of the actinide series are radioactive
PREDICTION OF GROUP, PERIOD AND BLOCK OF A GIVEN ELEMENT

We can easily predict the group, period & block of any element from it’s electronic
configuration by the following ways

 Principal quantum number of the valence shell corresponds to the period of

an element.
 The orbital containing the last electron indicates the block of an element.
 The group of an element is predicted from the number of electrons in the
valence shell or a penultimate shell (n-1) as follows

(a) For s – block elements, group number is equal to the number of valence
electrons.

(b) For p – block elements group number is equal to 10 + number of electrons in the
valence shell.

(c) For d – block elements, group number is equal to the number of electrons in
(n-1) d – subshell + number of electrons in valence shell (nth shell)

Alternately you can calculate group number = Number of electrons in (penultimate

shell + valence shell) - 8

(d) For f block elements, group number is always IIIrd /3B

BOHR'S CLASSIFICATION OF ELEMENTS

Elements may be classified into four groups on the basis of the number of
incomplete shells present in them

Inert gases

a. s- and p-orbitals of the outermost shell of these elements are filled. The
outermost electronic configuration is ns2np6.
b. Helium is also inert gas but its electronic configuration is 1s2

Representative or Normal Elements:

a. The outermost shell of these elements is incomplete. The number of electrons

in the outermost shell is less than eight.
b. Inner shells are complete
c. s-and p-block elements except inert gases are called normal or representative
elements.

Transition Elements:

a. The last two shells of these elements namely the 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.
c. Their outermost electronic configuration is similar to d-block elements i.e. (n-
1)d1-10 ns1-2.
d. According to the latest definition of transition elements, those elements which
have partly filled d-orbitals in a neutral state or 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 pre-penultimate
shells are incomplete.
b. These are related to IIIB i.e. group 3.
c. The last shell contains two electrons. The penultimate shell may contain eight
or nine electrons and the pre-penultimate shell contains more than 18 upto32
electrons.
d. Their outermost electronic configuration is similar to ƒ-block elements i.e. (n-
2)ƒ1-14 (n-1)s2 (n-1)p6 (n-1)d0-1ns2
e. Elements of the seventh period after atomic number 92 (i.e. actinides) are
synthetic elements and are called transuranic elements.

PERIODICITY IN ATOMIC PROPERTIES

In a period from left to right there is a regular change in electronic configuration of
elements. In a group from top to bottom the outermost shell electronic configuration
is similar. The chemical properties of the elements depend upon their electronic
configuration. So there is a regular change in chemical properties in a period while in
a group element have similar chemical properties. In a period as well as in a group
there is a regular gradation (gradual increase or decrease in a particular property) in
physical and chemical properties of elements with the change in atomic number.
This regular gradation in properties is called periodicity and all these properties
which are directly or indirectly related to the atomic structure or electronic
configuration of the elements are called atomic properties. Periodicity in some atomic
properties is discussed as under

ATOMIC RADIUS

The radius of an atom may be taken as the distance between atomic nucleus and
the outermost shell of electrons of the atom. The size of atom is very important
because many physical and chemical properties of the atom are related to it.
According to the Heisenberg's uncertainty principle the position of a moving electron
can not be accurately determined. So the distance between the nucleus and the
outermost electron is uncertain. Atomic radius can be determined indirectly from the
inter-nuclear distance between the two atoms in a gaseous diatomic molecule. This
inter-nuclear distance between the two atoms is called bond length. Different types
of atomic radii are discussed below.

Covalent radius: One half of the distance between the nuclei (inter-nuclear
distance) of two covalently bonded atoms in a homo-diatomic molecule is called the
covalent radius of that atom. The covalent bond must be single covalent bond. The
covalent radius (rA) of atom A in a molecule A2 may be given as –

i.e. the distance between the nuclei of the two single covalently bonded atoms in a
homo-diatomic molecule is equal to the sum of covalent radii of both the atoms.

dA-A = rA+rA

In a hetero-diatomic molecule AB where the electronegativity of atoms A and B are

different, the experimental values of inter-nuclear distance dA-B is less than the
theoretical values (rA+rB). According to Schomaker and Stevenson (1941) –

DA-B = rA + rB – 0.09 Δx

Where Δx is the difference of electronegativities of the atoms of A and B

According to Pauling – If the electronegativities of the two atoms A and B are xA and
xB respectively then

DA-B = rA + rB – (C1xA – C2xB)

C1 and C2 are the Stevenson's coefficients for atoms A and B respectively.

Metallic radius: Metal atoms are assumed to be closely packed spheres in the
metallic crystal. These metal atom spheres are considered to touch one another in
the crystal. One half of the internuclear distance between the two closest metal
atoms in the metallic crystal is called metallic radius.

Metallic radius > Covalent radius

For example – Metallic radius and covalent radius of potassium are 2.3 Å and 2.03Å
respectively.

 Vander Waal's Radius or Collision radius: The molecules of non metal

atoms are generally gaseous. On cooling, the gaseous state changes to liquid
which is followed solid state on further cooling. In the solid state, the non
metallic elements usually exist as aggregations of molecules are held together
by Van-der Wall forces. One half of the distance between the nuclei of two
adjacent atoms belonging to two neighbouring molecules of an element in the
 solid state is called Van der Waal's radius. It may also be defined as half of
the inter-nuclear distance of two non bonded neighbouring atoms of two
adjacent molecules.

Vander Waal's radius > Metallic radius> Covalent radius

The Vander Waal's radius and covalent radius of chlorine atom are 1.80Å and 0.99Å
respectively

 Ionic Radius: A neutral atom changes to a cation by the loss of one or more
electrons and to an anion by the gain of one or more electrons. The number of
charge on cation and anion is equal to the number of electrons lost or gained
respectively. The ionic radii of the ions present in an ionic crystal may be
calculated from the internuclear distance between the two ions

(a) Radius of a Cation–Radius of a cation is invariably smaller than that of the

corresponding neutral atom

NaNa+

Number of e- = 1110

Number of p =1111

1s22s22p63s11s22s22p63s0

Reasons

The effective nuclear charge increases. For example in Na atom 11 electrons are
attracted by 11 protons and in Na+ 10 electrons are attracted by 11 protons. Thus in
the formation of cation number of electrons decreases and nuclear charge remains
the same.

Generally the formation of cation results in the removal of the whole outer shell due
to which interelectronic repulsion decreases. The interelectronic repulsion in Na is
among 11e- and in Na+ among 10e-
(b) Radius of an anion – Radius of an anion is invariably bigger than that of the
corresponding atom

ClCl_

Number of e- =1718

Number of p = 1717

Reasons

The effective nuclear charge decreases in the formation of anion. Thus the
electrostatic force of attraction between the nucleus and the outer electrons
decreases and the size of the anion increases.

Interelectronic repulsion increases due to which expansion of electron cloud takes

place

Isoelectronic species:

A series of atoms, ions and molecules in which each species contains same number
of electrons but different nuclear charge is called isoelectronic series

N3O2-F- Ne Na+ Mg2+

Number of e- 101010101010

Number of p789101112

In isoelectronic series atomic radii decreases, nuclear charge increases as

(i) Number of electrons is same.

(ii) Number of protons is increasing

(iii) So the effective nuclear charge is increasing and atomic size is decreasing. In an
isoelectronic series atomic size decreases with the increase of effective nuclear
charge.

Some of the examples of isoelectronic series are as under

S2-, Cl-,K+, Ca2+, Sc3+

SO2, NO3-, CO2-3

N2, CO, CN-

NH3, H3O+

PERIODICITY IN ATOMIC RADIUS AND IONIC RADIUS

For normal elements

(a) In a period from left to right effective nuclear charge increases because the next
electron fills in the same shell. So the atomic size decreases. For example the
covalent radii of second period elements in Å are as follows –

LiBeBCNOF

1.230.890.800.770.740.740.72

(b) In a group, from top to bottom the number of shells increases. So the atomic size
increases. Although the nuclear charge increases but its effect is negligible in
comparison to the effect of increasing number of shells. For example the covalent
radii of IA group elements in Å are as follows –

LiNaKRbCs

1.231.572.032.162.35

 The atomic radius of inert gas (zero group) is shown largest in a period
because of its Vander Waal's radius which is generally larger than the
covalent radius. The Vander Waal's radius of inert gases also increases in
moving from top to bottom in a group.
 For transition elements – There are four series of transition elements

3d – Sc (21) to Zn (30)

4d – Y (39) to Cd (48)

5d – La (57), Hf (72) to Hg (80)

6d – Ac(89), Rf(104) …………. Unb (ununbium) 112 (incomplete)

(a) From left to right in a period

The atomic size first decreases due to the increase in effective nuclear charge and
then becomes constant and then increases. In transition elements, electrons are
filled in the (n-1)d orbitals. These (n-1)d electrons screen the ns electrons from the
nucleus. So the force of attraction between the ns electrons and the nucleus
decreases. This effect of (n-1)d electrons over ns electrons is called shielding effect
or screening effect. The atomic size increases due to shielding effect and balances
the decrease in size due to increase in nuclear charge to about 80%. Thus moving
from left to right in a period, there is a very small decrease in size and it may be
considered that size almost remains the same. In the first transition series the atomic
size slightly decreases from Sc to Mn because effect of effective nuclear charge is
stronger than the shielding effect. The atomic size from the Fe to Ni almost remains
the same because both the effects balance each other. The atomic size from Cu to
Zn slightly increases because shielding effect is more than the effective nuclear
charge due to d10 structure of Cu and Zn. The atomic radii of the elements of 3d
transition series are as under.
ScTiVCrMnFeCoNiCuZn

1.441.321.221.181.171.171.161.161.171.25

Inner transition elements - As we move along the lanthanide series, there is a

decrease in atomic as well as ionic radius. The decrease in size is regular in ions but
not so regular in atoms. This is called lanthanide contraction. The atomic radii in Å
are as under

LaCePrNdPmSmEuGd

1.881.821.831.82 –1.802.041.80

TbDyHoErYbLu

1.781.771.761.751.941.73

There are two peaks one at Eu (63) and other at Yb (70). This is due to the
difference in metallic bonding. Except Eu and Yb other lanthanides contribute three
electrons in metallic bond formation. These two atoms contribute two electrons in the
bond formation leaving behind half filled and completely filled 4ƒ-orbitals
respectively.

Cause of Lanthanide contraction – In lanthanides the additional electrons enters

the (n-2)ƒ orbital. The mutual shielding effect of (n-2)ƒ electrons is very little because
the shape of ƒ-subshell is very much diffused. Thus the effective nuclear charge
increases then the mutual shielding effect of (n-2) ƒ electrons. The outer electrons
are attracted more by the nucleus. Consequently the atomic and ionic radii
decreases from La (57) to Lu (71)

This type of contraction also occurs in actinides. The jump in contraction between
the consecutive elements in the actinides is greater than lanthanides. This is due to
the lesser shielding of 5ƒ-electrons which are therefore pulled more strongly by the
nucleus.

(b) In a group

The atomic radius of elements increases moving from first transition series (3d) to
second transition series (4d). This is due to the increase in number of shells with the
increase in atomic number.

The atomic radii of second (4d) and third (5d) transition series in a group is almost
same except Y(39) and La (57). In third transition series, there are fourteen
lanthanides in between La (57) of III B and Hf (72) of IV B groups, so the atomic
radius of Hf(72) decreases much due to lanthanide contraction in lanthanides. The
difference in the nuclear charge in the elements of a group in first and second
transition series is + 18 units while this difference in second and third transition
series is + 32 units except Y (39)→ La(57). Due to the increase of + 32 units in the
nuclear charge there is a sizable decrease in the atomic radius which balances the
increase in size due to the increase in number of shells.
So in a group moving from second to third transition series, the atomic radii of the
elements almost remain the same except IIIB. The difference is about 0.02Å.

IONIZATION POTENTIAL OR IONIZATION

ENERGY

The amount of energy required to remove the most loosely bound electron of the
outermost shell (i.e. the outermost electron) from one mole of an isolated gaseous
atom of an element in its ground state to produce a cation is known as ionization
energy of that element. Ionization energy is generally expressed in electron volts, so
it is also known as ionization potential. Energy required for the removal of first,
second and the third electron from the gaseous atom is called first, second and third
ionization energy respectively.

The order of first, second and third ionization energies may be given as, IE1 < IE2 <
IE3

This is because second and third electron is removed from unipositive and di-
positive cations respectively. Effective nuclear charge increases with the increase of
positive charge. So the attraction between the nucleus and the outermost electron
increases and more energy is required for the removal of electron.

Factors Affecting Ionization Potential:

 Atomic radius: The values of ionization potential of an element decreases as

its atomic radius increases. This is because the electrostatic force of attraction
between the nucleus and the outermost electron decreases as the distance
between them increases. So the energy required for the removal of electron
will comparatively be less

Atomic radii increases

Li Na K Rb Cs → 520 496 419 403 374

ionizaton potential decrases

  Effective nuclear charge: The greater the effective charge on the nucleus of
an atom, the more difficult it would be to remove an electron from the atom
because electrostatic forces of attraction between the nucleus and the
outermost electron increases. So the greater energy will be required to
remove the electron.

Ionization potential α Effective nuclear charge (Zeff)

 Penetration effect of the orbitals: The order of energy required to remove

electron from s,p,d-andƒ-orbitals of a shell is s>p>d>ƒ because the distance
of the electron from the nucleus increases. For example – The value of
ionization potential of Be(Z=4, 1s22s2) and Mg(Z=12, 1s22s22p63s2) are more
than the I.P.s of B (Z=5, 1s22s22px1) and Al (Z= 13, 1s22s22p63s23px1)
because the penetration power of 2s and 3s electrons is more than 2p and 3p
electrons respectively. More energy will be required to separate the electrons
from 2s and 3s orbitals.
 Shielding or screening effect: The shielding or screening effect increases if
the number of electrons in the inner shells between the nucleus and the
outermost electrons increases. This results in decreases of force of attraction
between the nucleus and the outermost electron and lesser energy is required
to separate the electron. Thus the value of I.P. decreases.

Ionization potential α 1/ Shielding effect

 Stability of half-filled and fully-filled orbitals: According to Hund's rule the

stability of half filled and completely filled degenerate orbitals is comparatively
high. So comparatively more energy is required to separate the electron from
the atoms having half filled and full filled electronic configuration.

For example:

 Removal of electron is comparatively difficult from the half filled configuration

of N (Z=7, Is22s22px12py1pz1).
 The ionization potential of inert gases is very high due to stable ns2np6
electronic configurations.

PERIODICITY IN IONIZATION POTENTIAL

 For normal elements: One moving from left to right in a period, value of
ionization potential of elements increases because effective nuclear charge
also increases.

Exceptions:
  In a period, the ionization energy of IIA group elements is more than the
elements of IIIA because penetration power of s-electrons is more than that of
p- electrons. The value of ionization energy of Be(1s22s2) is more than B
(1s22s2px1) because the penetration power of 2s-electrons of Be is more than
the 2px electrons of B. Moreover the electrons are paired i.e. completely filled
s-subshell.
 In a period, the ionization energy of VA elements is more than the elements of
VIA because the half filled p3 configuration of VA elements is comparatively of
higher stability. VIA group elements (p4) have the tendency to acquire
comparatively more stable (p3) configuration by the loss of one electron?
Ionization energy of N(1s22s22px1py1pz1)>O

Thus P>S, As>Se.

But the value of I.P. of Sb (VA) & Te (VIA) and Bi (VA) & Po(VIA) are according to
general rule i.e.

Sb (VA) <Te (VIA)

Bi (VA) < Po (VIA)

On moving from top to bottom in a group the value of I.P decreases because the
atomic size increases.

Exceptions:

 In group IIIA the ionization potential of Al (13) is equal to the ionization

potential of Ga(31). Before Ga (31) the electrons are filled in 3d – orbitals of
ten transition elements. These 3d orbital electrons do not completely shield
the 4p – electron. So the increase of +18 units in nuclear charge results in the
greater increase of effective nuclear charge. Due to increase in nuclear
charge the I.P. increases which counter balance the decrease in I.P. due to
the increase in number of shells.
 The values of I.P. of Ti (81) and Pb (82) of sixth period is more than that I.P.
values of In (49) and Sn (50) of same groups in period fifth. This is because of
the electrons are filled in 4ƒ-orbitals before Ti (81) and Pb (82) which do not
completely shield the outer electrons. Thus increase in + 32 units in nuclear
charge results in the increase of ionization potential values

For transition elements: On moving from left to right in a transition series –

 As the atomic number increases the effective nuclear charge also increases.
Hence the I.P. increases.
 The shielding effect of (n – 1)d electrons over ns electrons increases with the
addition of electrons in (n-1)d orbitals. Hence the I.P. decreases.
 The increased values of I.P due to the increase of effective nuclear charge
almost balances the decreased value of I.P. due to increase in shielding
effect. There is a very small increase in the values of I.P. or it may be said
that I.P. almost remains the same.
  In first transition series from Sc to Cr the value of I.P. increases because
effect of increase in effective nuclear charge is more than the shielding effect.
I.P. values of Fe, Co, Ni and Cu are almost same. Due to (n-
1)d10ns2 configuration of Zn, the first I.P. increases.

On moving from top to bottom in a group in transition series:

 In a group on moving from first to second transition series, the values of I.P
decreases because atomic size increases.
 When moving from second to third transition series the value of I.P some what
increases except IIIB group [Y(39) → La(57)]. This is because of 14 electrons
are filled in 4ƒ-orbitals of lanthanides which do not shield the 5d electrons
effectively. Thus the increase in +32 units in nuclear charge results in the
increase of I.P., on moving from left to right this effect decreases and
becomes negligible in the later part.

Applications of Ionization Potential:

 Metallic or electropositive character of elements increases as the value of

ionization potential decreases. So in a group moving from top to bottom
metallic or electropositive character increases because I.P. value decreases.
In a period moving from left to right the values of I.P. increases so metallic or
electropositive character decreases. Non metallic character increases.
 The relative reactivity of the metals increases with the decrease in I.P. values.
The I.P. values of IA and IIA metals are comparatively low. So they are
comparatively more reactive. The I.P. values of inert gases are very high. So
they are almost inactive.

In a group moving from top to bottom the reactivity of metal atoms increases
because their I.P. value decreases.

 The reducing power of elements increases as the values of I.P. decreases

because tendency to lose the electron increases. The reducing power
increases going down a group because the I.P. value decreases. Li is
exception in IA group. The reducing power of Li is highest in its own group.
The order of reducing Power of IA elements is as under

Li>Cs>Rb>K>Na

 Determination of oxidation state or valency electrons of an element –

(a) If the difference of two consecutive I.P.'s of an element is 16 eV or more, the

lower oxidation state is stable. For e.g. the difference of first and second I.P. of Na is
42.4 eV which is more than 16 eV. So Na+ will be stable. It can also be explained
from its electronic configuration

Na (11) = 1s22s22p63s1

Na+ = 1s22s22p6
Neutral Na atom has the tendency to acquire the stable 2s22p6 configuration by the
loss of one electron. Due to 2s22p6 configuration of Na+, the further separation of
electron is difficult. So IA group metals form unipositive ions.

(b) If the difference of two consecutive I.P.s. of an element is 11.0 eV or less, the
higher oxidation state is stable. For e.g. the difference of first and second I.P. of Mg
is 7.4 eV which is less than 11.0 eV. So Mg2+ will be stable. It can also be explained
on the basis of its electronic configuration.

The electronic configuration of Mg2+ is stable 2s22p6 configuration (Ne gas

configuration)

Mg2+ = 1s22s22p6

So IIA group elements form di-positive ions.

(c) The difference of first and third I.P. of Al is 12.8 eV which is more than 11eV.
Therefore first oxidation state of Al i.e. Al+ must be stable. In gaseous state Al+ is
stable. This is due to the proportionate distribution of lattice energy and the
difference of second and third I.P.s 9.6eV<11 eV.

ELECTRON AFFINITY

The amount of energy released when an electron is added to the outermost shell of
one mole of an isolated gaseous atom in its lower energy state is called electron
affinity. Electron affinity just defined is actually first electron affinity since it
corresponds to the addition of one electron only. In the process of adding further
electron, the second electron will be added to gaseous anion against the
electrostatic repulsion between the electron being added and the gaseous anion.
Sometimes energy instead of being released is supplied for the addition of an
electron to an anion.

Factors Affecting the Magnitude of Electron Affinity:

 Atomic size: In general electron affinity value decreases with the increasing
atomic radius because electrostatic force of attraction decreases between the
electron being added and the atomic nucleus due to increase of distance
between them.

Electron affinity α 1/Atomic size

  Effective nuclear charge: Electron affinity value of the element increase as
the effective nuclear charge on the atomic nucleus increases because
electrostatic force of attraction between the electrons being added and the
nucleus increases. As the electrostatic force of attraction increases, amount of
energy released is more.

Electron affinity α Effective nuclear charge (Zeff)

 Screening or Shielding effect: Electron affinity value of the elements
decreases with the increasing shielding or screening effect. The shielding
effect between the outer electrons and the nucleus increases as the number
of electrons increases in the inner shells. Electron affinity α 1/Shielding effect
 Stability of half filled and completely filled orbitals: The stability of half
filled and completely filled degenerate orbitals of a sub shell is comparatively
more, so it is difficult to add electron in such orbitals and lesser energy is
released on addition of electrons hence the electron affinity value will
decrease.

PERIODICITY IN ELECTRON AFFINITY

 In general electron affinity value increases in moving from left to right in a

period because effective nuclear charge increases.

Exceptions:

 The electron affinity value of alkaline earth metals of IIA group is zero. (only
Be and mg)
 Electron affinity value of alkali metals of IA group is also approximately zero
because these elements have the tendency of losing the electron instead of
gaining the electron.
 Electron affinity values of nitrogen and phosphorus (VA) are lesser than the
electron affinity values of carbon and silicon respectively. It is due to the
comparatively stable half filled configuration (np3) of nitrogen and phosphorus
and the tendency to acquire the stable np3 configuration by the gain of one
electron in carbon and silicon np2 orbitals.
 The theoretical value of the electron affinity of zero group inert gas elements
is zero due to stable s2p6 configuration.
 In a group moving from top to bottom the electron affinity value of elements
decreases because the atomic size increases

Exceptions:

 Electron affinity values of second period elements are smaller than the
electron affinity values of third period elements. This unexpected behaviour
can be explained by the very much high value of charge densities, (which is

equal to ) of second period elements due to much smaller size. The

electron being added experiences comparatively more repulsion and the
electron affinity value decreases.
  The electron affinity of fluorine (Second period) is less than the electron
affinity of chlorine (third period). 2p-orbitals in fluorine are much more
compact than 3p- orbitals of chlorine. So the electron being added in 2p-
orbitals experiences comparatively more repulsion and the electron affinity
value decreases.

ELECTRONEGATIVITY

It may be defined as the tendency of an atom to attract shared pair of electrons

towards itself in a covalently bonded molecules. The numerical value of the
electronegativity of an element depends upon its ionization potential and electron
affinity values. Higher ionization potential and higher electron affinity values implies
higher electronegativity value.

ELECTRONEGATIVITY SCALES

The relative tendency of an atom to attract the shared electron pair towards itself is
called electronegativity. This is the property of a bonded atom.

Some arbitrary scales for the quantitative measurement of electronegativities are as

under

 Pauling's scale: Pauling related the resonance energy (Δ)AB of a molecule

AB with the electronegativities of the atoms A and B. If xA and xB are the
electronegativities of atoms A and B respectively then

0.208 √ΔAB = xA – xB if xA > xB

or 0.043 ΔAB = 23.06 (xA – x-B)2

ΔAB = EA-B(experimental) – EA-B(theoretical) where EA-B is the energy of A-B

bond. In a purely covalent molecule, AB, the experimental and theoretical values of
bond energy A-B are equal.

So ΔAB = 0

or 0=23.06 (xA – xB)2

or xA = xB

In an ionic molecule AB, EA-B(experimental) is more than EA-B(Theoretical).

Pauling assumed the electronegativity value of fluorine to be 4 and calculated the

electronegativity values of other elements from this value.

 Mulliken's electronegativity: According to Mulliken, the electronegativity of

an element is the average value of its ionization potential and electron affinity.
Mulliken's electronegativity (xM) – 0.615)

or xp = 0.336 xM – 0.2

Mulliken’s values are ≈ 2.8 times greater than that of Pauling value.

 Alfred Rochow’s electronegativity: The electronegativity of an element is the

electrostatic force of attraction between the electron present on the
circumference of the outermost shell of its atom and the atomic nucleus. If the
distance between the circumference of outermost shell and the nucleus is r
and the effective nuclear charge Zeff then –

, Zeff = Z - σ

Z = The actual number of charge present on the nucleus i.e number of protons σ =
Shielding constant

Factors Affecting the Magnitude of Electronegativity:

 Atomic radius: As the atomic radius of the element increases the

electronegativity value decrease.

 Effective nuclear charge: The electronegativity value increases as the

effective nuclear charge on the atomic nucleus increases.

Electronegativity α Effective nuclear charge (Zeff)

 Oxidation state of the atom: The electronegativity value increases as the

oxidation state (i.e. the number of positive charge) of the atom increases.
 Hybridization state of an atom in a molecule: if the s- character in the
hybridization state of the atom increases electronegativity also increases
because s-electrons are having more penetration effect. For example the
electronegativity values of C-atom in various hybridization states are as under
—

Hybridization states sp3 sp2 sp

s-Character 25% 33.33% 50%

Electronegativity 2.48 2.75 3.25

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→

s-character is increasing

So the electronegativity value is increasing

PERIODICITY IN ELECTRONEGATIVITY

 In a period moving from left to right, the electronegativity increases due to the
increase in effective nuclear charge.
 In a period the electronegativity value of IA alkali metal is minimum and that of
VIIA halogen is maximum.
 In a group moving from top to bottom, the electronegativity decreases
because atomic radius increases.
 The electronegativity value of F is maximum and that of Cs is minimum in the
periodic table.
 The electronegativity of Cs(55) should be more than Fr(87) but it is less. This
is due to the increase of +32 units in nuclear charge of Fr which makes the
effective nuclear charge comparatively high.
 On moving from second to third transition series in a group [except Y(39) →
La(57)] electronegativity increases due to the increase of +32 units in nuclear
atoms.
 The electronegativity of inert gas elements (zero group) is zero due to stable
ns2np6 configuration. Inert gases are monoatomic molecules and the
electronegativity is the property of bonded atoms.

Applications of Electronegativity:

 Partial ionic character in covalent Bond: The ionic character of a covalent

bond increases as the electronegativity difference of bonded atoms increases.
According to Haney and Smith if the electronegativity difference of bonded
atoms is Δx then.

Ionic character percentage of the bond =16Δx+3.5Δx2

If the value of Δx is 1.7 then ionic character percentage is about 50. For example the
order of ionic character in H–X bond is as follows–

H–F > H–Cl > H–Br > H–I

Because the electronegativity difference of bonded atoms (Δx) decreases.

 Bond strength If the electronegativity difference of covalently bonded atoms

(Δx) increases, the bond energy of the covalent bond also increases. For
example – the order of the H–X bond strength is
 H– F > H–Cl > H–Br > H–I

As the bond strength is decreasing the acid strength is increasing. So order of

increasing acid strength is HF < HCl < HBr < HI
  Acidic and basic nature of oxides of normal elements in a period: The acidic
nature of the oxides of normal elements increases as we move from left to
right in a period. In a period from left to right the electronegativity of the
elements increases. So the difference of the electronegativities of Oxygen and
the elements (x0 –xE) decreases. If the (x0 – xE) values is about 2.3 or more
then oxide will be basic. If (x0 – xE) values is less than 2.3 the oxide will be
acidic. The oxides of the IIIA elements are amphoteric.

The order of acidic or basic nature of the oxides of third period elements may be
given as under

Na2O MgO SiO2 P2O5 SO3 Cl2O7

⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯

The value of x0 – xE is decreasing

Basic nature is decreasing

Acidic nature is increasing

Metallic and non metallic properties of elements:

(a) The metallic character decreases as the electronegativity of the element

increases

(b) On moving from left to right in a periods, the electronegativity of the elements
increases. So the metallic character decreases.

(c) On moving down a group, the electronegativity of the elements decreases. So the
metallic character increases.

Basic nature of the hydroxides of elements:

A hydroxide MOH of an element M may ionize in two ways in water.

M–O–H + H2O MO– + H3O+ …….(1)

M–O–H +H2O MOH2+ + OH– …… (2)

If the ionization is according to eqn (1) then it is acidic. It is possible when ionic
character of O–H bond is more than the ionic character of M-O bond i.e. x0 – xH >
x0–xM where x0, xH and xM are the electronegativities of oxygen, hydrogen and
element respectively. If the ionization is according to eqn. (2) then it is basic. This is
possible only when ionic character of O –H bond is less than M–O bond i.e x0 – xH
<x0 –xM