3

JOeriodic Table· and

Periodic Properties

PERIODIC TABLE

Historical

The atomic nature of matter {Greek (/.1:0#10(1 = incapable of further

subdivision) was acknowledged as early as Aristotle (384-322 Be) even
though his ideas were of: !l._ philosophical nature only. Aristotle taught
combinations as marriage .and divorce amongst the elements. Paracelsus
(ca AD 1495-1551) tried to correlate the biological functioning of the tria
prima of Albert Magnus (mercury, sulphur and salt).
Following Boyle's theory (1677) 'of atoms-small individual particles of
different shapes and masses-chemists sought to correlate the properties of
the elements with their atomic masses. The early attempts to establish a
correlation between the mass and the properties of the elements using
Dalton's Jaws (1808) were constrained by the fact such as (i) the distinction
'between the atomic weights and equivalent weights was not clear; (ii) a
consistent set of the atomic or combining weights was 110t available; (iii) a
number of elements were not discovered; (iv) combining ratios of clements
in known compounds were erroneous. Nevertheless, a systematic approach
to inorganic chemistry has been synonymous with the study of the periodic
relationships of the elements and their compounds. .
J. W. Debereiner (1829) pointed out triads of elements having similar'
properties: o, Sr, Ba; u, Na, K; CI, Br, I; and S, Se, Te; in which the
atomic weight of the middle element was the mean of the other two.
Pattenkofer (1850) demonstrated that the atomic weight of the similar
elements differed by integral multiples of 8: Li(7), Na(23), K(39);
Mg(24), Ca(40), Sr(88); 0(16), S(32), Se(80), Te(l28). Chancourtois: (1862)
. showed that elements different from each other by 16 or its multiple in
atomic weight definitely had a similar behaviour and concluded that the
properties of the elements arc the properties of the numbers. J.A.R.
Newlands noticed that on arranging the known clements in the order .of
78 Theoretical Principles of Inorsont» Chemistry

increasing atomic weights, every eighth element had similar properties'

(law of octaves) .. Though ridiculed for leaving blank spaces for 'the yet
undiscovered clements, he was the first forerunner of the present periodic
table, and was awarded the Davy Medal (1887) in recognition of his
contribution.

Mendcleev's Periodic Table of Elements

Between 1868 and 1870, Dmitri Ivanovich Mendeleev published tables of

clements (now known as the Mcndclcev's table of. elements) in which
similar clements were arranged in the same horizontal llne called groups.
Lothar Meyer's atomic volume curve, though written in 1868, was not
published till 1870.
The salient features of the Mendeleev's table of elements are:
(1) Two consecutive elements were expected to have a difference (If at
least one unit (and upto four units) in the atomic weights.
(2) Blank spaces were left for the missing or undiscovered elements.
(3) When the table had no space for the known element on the basis of
the properties, Mendeleev, without any experimental evidence, changed its
atomic weight by a factor that would change the atomic weight of the
element to fill up a gap in the table. For example, he changed the atomic
weights of aluminium and boron from 40.5 and 16 to 27 and 10.7 respecti-
vely. Hence aluminium was fitted in between magnesium (24) and silicon
(28) whereas boron filled the. gap between beryllium (9) and carbon
(12) respectively. Consequently, the valencies of aluminium and boron were
also changed from two to three.
Elements without any clash in the position, uranium (116), lanthanum
(94), cerium (92) etc. existed as such in the. table.·

Advantages of the M endeleev's Table

In the modern version of the Mcndclccv's periodic table (Table 3.1) similar
elements are plac;ed in vertical columns, called the groups. The horizontal
rows of elements are called the periods. Such an arrangement had the
following advantages,
(1) The regular gradation in the physicochemical properties of the
clements (arc and spark spectra, crystal structures of the elements and their
compounds; chemical compositions, coordination properties) is similar in
all the groups. .
(2) the group 'number (except for group VUI) gives the highest valence
state possible for the elements. .
(3) Elements of the second row of groups I, Il, and III, show a diagonal
relationship to the next elements of group If, III, and IV respectively. .
(4) A sudden change from highly electronegative halogens (group VII A).
to highly electropositive alkali metals (group I A) made Mendeleev predict
 SO Theoretical Principles of Inorganic Chetnlstry

the existence of thc inert clements with either 8 or 0 valence, The inert
clements should be neither electropositive not electronegatlvc. . ,
(5) From the positions of the gaps in the table, Mendeleev predicted the .
properties of thc missing elements. . . .
The discovery of scandium and germanium in 1875, with properties
similar to those predicted by Mcndclcev, and of the inert gases haying
atomic weights between those of halogens and that alkali metals, put the
Mendeleev's table oil a firm footing.

Limitations of Mendeleev's Table

Despite the advantages, the Mendeleev periodic table has some limitations
which are briefly mentioned below. '
(I) No explanation is given for the presence of only 2 elements in the
first period, 8 in the short second and third periods, 18 in the long fourth
and fifth periods, and 32 in the extralong sixth and the unfinished seventh
period.
(2) Each group in subdivided into A and B subgroups, each subgroup
containing soft electronegative or electropositive clements, .and metallic
elements respectively, The subgroups have only a superficial stoichiometric
resemblance with each other. Much energy was expended unnecessarily in
finding support for the resemblances between alkali metals and coinage
metals, and between, say, halogens and manganese.
(3) The order of the elements' according to their atomic weights was
reversed in some cases to allow for the placement of the elements in the
proper groups. Thus iodine (127) was placed after tellurium (128),'
potassium (39) after argon (40) and nickel (58) after cobalt (59).
. (4) No place is offered to isotopes (atoms of the same element with
different mass) iri different groups, and for the isobars (atoms of different
elements having' same mass) to be grouped together.
(5) Though the adjacent elements are placed in adjoining groups, the
group VIII houses three consecutive elements iron, cobalt and nickel in the
fourth period, ruthenium, rhodium and palladium in the .fifth period and
osmium, iridium and platinum in the sixth period. Group VII[ was in fact
introduced to accommodate all the clements between group VII D (manga-
nese family) and group I B (coinage metals). ..
(6) Though the group number indicated the highest valence state of the
clements, except for ruthenium and osmium', none of the other members of
group VIII shows a valence of 8. Further, a valence of 8 cannot' be
explained on the basis of gain, loss, or sharing of electrons during bond.
formation. . .
(7) The change from highly. electronegative group VII A elements
(halogens) to inert noble gases in group 0, and then to highly electroposi-
tive group I A elements (alkali metals) in totally unrelated' to the atomic
weights of the elements. (In fact, such an attempt is futile as we know now,
 Periodic Table alld Periodic Properties 81

the properties of· the atoms are functions of the electronic configuration and
not of their masses.)
(8) The existence and stability of different valence states cannot be
predicted from the position of the element in the Mendeleev's periodic table.
No explanation is available as to why (i) common elements of group A
-have stable valence states differing by two units; (ii) D subgroup elements
have valence states differing by one unit; and (iii) common valence state
for the B subgroup elements of fourth period is +2 and not the group
number •
.(9)·The different behaviour of the first member of a group and the
diagonal relationship (and that also only for the three members) cannot be
explained.
(10) The lanthanons. The 14 Ianthanons, all different elements, are grouped
'together and placed in a single position in group III B as they show the
common valence of +3. .
(11) The missing elements. Because of the variable changes ill the atomic
weights of consecutive elements (~1 to .+4 units), it is not possible to
determine the. number of the elements present between two elements of
known atomic weights. This assumed .significance due to the close re-
semblances amongst the lanthanons whose number could net be ascertained
a
from knowledge of their atomic weights.
It is therefore obvious that the choice of atomic weights of the elements
as a basis for their classification is in error. A search for determining a
more fundamental property of the elements thut could be used as the basis
for their periodic classification began.

The Atomic Number

Characteristic x-Ray Spectra

Amaj6r step towards' as'signing a fundamental number to an element called

the atomic number Z, was the discovery of what are called the characteristic
x-rays of an element.

Production of characteristic x-rays: When a target is bombarded with high

energy electrons, it emits two types of radiations. One type results in a conti-
nuous spectrum having a continuous distribution of wavelengths (Fig 3.1).
the high energy end of which depends on the energy of the incident electrons,
'The other type, superimposed on the first (Fig. 3.2) is called the characterts-
tic x-ray spectrum of the element, the wavelength of which depends only
on the target material and is independent of the energy of the incident
electrons. This is subject to the conditionthat the energy of the incident
.electrons is greater than some minimum value. Otherwise these radiations
are not produced at all,
 82 Theoretical Principles of Inorganic Chemistr»

2 2

I I

i·
o L...._.,..L..._--'----'
700 900 300 500 700 900
1-. in pm
" in pm
Fig. 3.] The x-ray spectrum of clemen(tW) .~:.-Fig.~3.2~ Characteristic x-rays super-
without characteristic x-rays, imposed on the continuous
. x-ray spectrum of Mo.
Barkla and Sadler (1908 -1911) showed the presence of two groups of fre-
quencies in the characteristic x-ray spectrum of elements, one of which
(called the K rays) had greater penetration power than the other (called the
L rays).
The same characteristic frequencies can be observed under suitable
conditions using anticathode made up of or containing the desired element
and then passing the resultant x-rays through the screen of the same
material to absorb the extraneous radiations and let the characteristic fre-
quencies pass.through.

Moseley's law: H.G.I. Moseley (1919) made a quantitative study of the

characteristic x-rays from 38 clements using a crystal of potassium ferro-
cyanide as n diffraction grating, and a photographic plate as a screen as
developed by Bragg. Rich ray of Barkla and Sadler was found to consist of
two spectral lines (e.g. KG and Kr. for K rays). The plots of square root of
the frequency v of the characteristic x-ray line versus the atomic number
Z' (as determined by Rutherford's experiment) of the element resulted in
straight lines for aluminium (Z = 13) to silver (2 = 47) for the Kline
and zirconium (Z = 40) to gold (Z = 79) for the L lines respectively (Fig.
3.3).. so that Moseley proposed that
4":;==
a(Z - 'b)
.. (3.1)
where a is the proportionality constant (1.0 for K line and 7.4 for L line)
und b is same for all the lines of a given series. No such relation Wasobserv-
ed when Z was replaced by the atomic \IIeit-"t A of the element, so that
Moseley concluded that the nuclear charge Z, or a property closely related
to Z is a fundamental property of the elements.
Later, though' other groups of characteristic frequencies (M, N, 0
series) were discovered, for which the v-Z relationshipis somewhat compli-
cated, broadly speaking, Bq, (3.1) is nearly always valid. The abnormalities
 Perlodk: Table and Periodic Properties 83

15

Lc(
Q) 10
10
.,-
)(

o 30 60 90.
z
Fig.3.3 Plots of the frequency v of the characteristic.
x-rays against the atomic number Z.

or the discrepancies however, have been of great significance in the elucida-

tion of the details of atomic structure.

Origin of characteristic spectra: An explanation of these radiations in

terms of Bohr's theory is simple. The high energy electron from the cathode
knocks off an electron from the K shell of the target element. To fill up· the
vacancy in the L shell, an electron .from the M shell drops into L shell
emitting L rays. A cascade effect then ensues resulting in the emission of
the characteristic x-ray spectrum.
From Bohr's model, the frequency of the radiation v, when the electron
drops from 1/,th shell to II/th shell, is given by

. (3.2)

where f' is the reduced mass of the system, other terms having their usual
meaning; For atoms lravinga numberofelectrons, the charge at the nucleus
as seen by the electron will be less than the actual nuclear charge due to the
shielding or screening of the electron. :z
in Eq. (3.2) should therefore be
replaced by (Z-b) where b is the extent of shielding of the electron. Equation
(3.2) then becomes
v = f'e4(Z-b)2
8£o2/z3·
(_1_ _ Ii;21)
11,2
(3.3)

For a given line, the term

8:~~,3
( U!2 . - II~~)
is a constant. Representing it by a2, Eq. (3.3) becomes
v = a2 (Z - b)2
. ..
 ·84 Theoretical Principles 0/ Inorganl« Chemistry

or
yv = a(Z - b)
which is the Moseley Equation (3.1).

Applications of characteristic x-rays: . As the frequency 'V of the characte-

ristic x-rays are quantitatively related to the atomic number Z, tbese can be
used to determine the atomic number of the elements. Some of the applica-
tions of this idea are:
(1) Inversion of the position of the elements ill the periodic table. The x-ray
ineasurements show that the inversion would not have been necessary at all .
if the order of increasing atomic number of the elements had been followed:
The atomic numbers or the disputed elements arc argon == 18, potassium
= 19, cobalt = 27. nickel = 28, tellurium = 52 and iodine = 53.
(2) Identification OJ new elements. The x-ray method does not require any
chemical separation of the element. TIle line frequency for any clement can
be calculated using Eq. (3.1) and if this line appears in the material being
examined. the element must be present. The elements technetium and
rhenium were discovered this way.
(3) Number of mtssing elements. For technetium and rhenium. chemical
properties of the neighbouring clements could point out the possibility of the
existence of these elements. But in the case of the lanthanons, such a predic-
tion could not be made because of the close similarities of the neighbouring
elements. Characteristic x-rays, however, showed the number of elements
between lanthanum (Z = 57) and tantalum (Z = 73) to be 15. Examina-
tion of the known elements, the rare earths, showed two elements with
atomic numbers 61 and 72 missing. Both were soon discovered, the former
is a radioactive element promethium; the latter is a cogenor of zirconium
and is called hafnium. Doth these elements were discovered by the x-ray
methods.

Long Form Of Periodic Table

With a better understanding of the role of electrons in the properties (If the
. clements, and the development of the nature of the electrons in atoms, a
better understanding of the periodic properties of elements or the periodic
table was possible. .
The natural result of the auf ball principle is the periodic classification Of
the elements in the so-called 101lg form of the periodic table. The table Is just
a graphical representation of the auf ball principle. Here in the order of the
increasing atomic number Z, the elements are arranged. Z will nlways be an
integral, and will chang« by one unit for 111'0 adjacent elements, The isotopes
arc all grouped together as they have the same atomic number.
. . The periodic table (Table 3.2Ws divided into vertical groups and horizontal
periods or rows. A new period begins when the first electron occupies a new
 Periodic Table and Periodic Properties 85

(principal quantum number) energy shell. Thus a period begins with the
clement having the configuration lIS1 (11 = I, 2, 3, '" for the first, second,
third, ... TOW or period, the inner orbitals being completely filled.
'fable 3.2 Long Form of UICPcriodic 'fable or the Bohr's Periodic Table of Elements

liS" (1I-1) d"IIS2 IIs!np"

II Sl - st d1 (l~ cia cI' dfi dB d7 dS (IV ,IIU pI pi p3 p' p6 pU

1 H He
2 -Li Be B C F No
N o
3 Na Mg Al sr PCl Ar S
4 K Ca Sc Ti V Cr Mn Fo Co Ni Cu Zn Ga So Br Kr
Go As
5 Rb Sr Y Zr Nb Mo To Ru Rh Pd Ag Cd In Sn Sb To I xe
6 Cs Ba La" Hf Ta W Re Os Ir I'l Au Hg 1'1 Pb Bi Po AtRn
7 Fr Ra Ac"
/1 fZ J3 f4 fS /0 f7 t» fO flO t» }'12 f13 fU
-*4f" Ce Pr Nd Pii.l Sm Eu Gd Til Dy Ho Er Tm Yb Lu
"5/" Th Pa U Np Pu Am COl Dk cr Es Pm Md No Lr

Period Orbitals filled before 11.$2 IIPO Number of orbitals that N/(I/Iber .of tile
configuration is acMe~'l!d sllollld be filled up c1emcllts
First ,- Is 1 1 2
Second 2.1",2p 1+ 3 4 8
Third 3s,3p 1+3 4 8
Fourth 4s, 3d, 4p 1+5+3 9 18
Fifth 5s,4d,Sp 1+5+3 9 18
Sixth 6s,4/, Sd, 6p 1 + 7 -I- 5 + 3 .., 16 32
Seventh 7s, Sf. 6d, 7p 1 +7 +5 + 3 = 16 32

. "Fhe members of a group have the same electronic "conflgurations of the

incompletely 'filled energy levels. A group can have any of the following
configurations:
ns
(1) ns1 or 2 giving the $ block elements, .
(2) ns2 lip· (x = 1 to 6) giving six groups of p block clements,
(3) (n-l)d· IIS2 (x = 1 to 10) giving ten groups of cI block elements,
(4) (11-2)/1) IIS2 or (/I-~)J- (n-l)dl1/S2 giving 14 clements in a row,
called the/block elements ". ·
It should be noted that the periodic chart can give us the knowledge of
onlywhat has been put into its composition. It is not a source of knowledge
in itself,. but is useful in portraying information regarding the electronic
configuration and other periodic properties, .
The Icing form of the periodic table offers the Iollowing :advantages over
the Mendeleev's classification.
 86 Theoretical Prlnciplcs 0/ Inorganic Chemistry

(1) The A and B subgroup elements are placed separately.

(2) The three elements of group VIn have been nssigned separate groups
corresponding to dO, d7 and dB elements. Similarly, the 14 lanthanons are not
pushed together, but arc assigned a separate group for each lanthanon in
the I group of clements.
(3) The uniform trivalent state of the Ianthanons can be explained to be
due to the availability of only three electrons in the outer, higher energy
levels, the differentiating electrons going to the inner chemically inert (non-
reactive low energy) orbitals.
(4) Uniform bivalence for the transition elements is due to the presence
of the outer IIS2 electrons, which makes them electropositive in nature.
(5) The variable valence states can be obtained from the electron arrange-
ment of the outer shells (discussed later).
(6) The inert gases with lISZ IJpG configuration are stable having paired up
closed shell octet configuration. These elements arc inert because of the non-
availability of either the electrons for bonding purposes, or the orbitals to
accommodate electrons from other clements. The elements having one elec-
tron more than the .inert gas shell (the alkali metals) tend to lose the high
energy electron rather easily,.and are, therefore, highly reactive and electro-
positive. The elements having one electron less than the inert gas shell (the
halogens) tend to capture one electron and form stable closed shell octet.
Hence, these clements are highly electronegative with high electron afllnity,
Thus the change from a highly electronegative to electropositive character /
through the inert gas structure has been explained on the basis of the
electronic configuration of clements.

Periodic Law

Mendelecv gave his famous periodic law which states that the properties of
the elements are periodic functions of their atomic weights, On this basis.
if the elements were arranged according to (he increasing atomic weights,
similar. elements should occur at regular intervals, as had been observed by
Dobcrciucr, Pattcnkofur, or Chnncourtois 011 II smaller senIe, btlt extended
by Mendeleev to all the known dements at his time.
As we now know, the properties of the clements depend upon the electro-
nic configuration of the clements; and in this. context, it is useful to recall
what Moseley had proposed as the periodic law: The properties of elements
arc a periodic function of their atomic numbers, Hence, if the elements
arc arranged in a sequence according to their atomic numbers, similar ele-
ments would Occur at regular intervals. This is found to be the case when
one looks at the long Iorm.ofthe periodic table of clements (Table 3.2)-
similar elements lie in the same group one below the other. The properties
should vary smoothly in a group as well as in a period. As discussed later
in this chapter, this is more 'or less found to be the case in the modern
 Periodic Table and Periodic Properties 87

periodic table with a few exceptions for w!lich suitable explanations can be
advanced readily.

Limitations of the Long Form of the Periodic Table

.
It should be remembered that the periodic table of clements is not a source
of information in itself, and can project the principles on which the classifica-
tion is based.sand nothing more. Hence the limitations of the modem form of
the periodic table are the limitations of the auf bau principle. Some of the
important limitations are given-below, . ,
(I) It is unduly cumbersome to draw as it has 2 (8) + +
6 (p) 10 (d)+ 14
(/> = 32 columns for each possible type of electronic configuration, and
hence on an average, a division of about 100 elements into so many groups
would leave 3 to 4 clements per .group; so that not many clements are
expected to be similar in behaviour.·
(2) The inner trausition elements are almost thrown out of the main body
of the periodic table. They arc generally shown at the foot of the table
as two separate periods as if they do not belong to the main clements or as
if they do not behave in tha. expected maimer in the main table.
(3) Even though isotopes have similar chemical properties they definitely
have different properties (mostly physical), but then the isotopes of hydrogen
arc so different, that the heavier isotopes arc known by altogether different
names with different symbols: deuterium, D, for the isotope with atomic
mass number 2, and tritium, T, for the isotope with atomic mass number 3.
This problem persists in the periodic table.
(4) The positionof hydrogen is still a matter of dispute: whether it is one-
electron element (group I), one-electron short than the inert gas element (the
group VII), or half thc valence shell filled clement (group IV). It resembles
all these groups of clements in its properties.
(5) Even though the periodic table has groups belonging to almost
all the electronic configurations, there is no group with the electronic
configuration .of the element as .(11 .,.... .1)(/4 /lS~ (a configuration. found for
tungsten with II = 6). Similar situations exist for the Ad and inner transition
elements also. This is directly the consequence of the Hund's rule of
maximum multiplicity, and hence is not a shortcoming of the periodic
table. However, it is not clear from the table why the clements with half-fill-
ed d subshell and completely filled subshclls, viz. chromium and molyb-
denum (with 11.,.... l)dr. IIS1 configuration) and copper, silver and gold (with
(II .,.... l)d10 lISi configuration) do not show properties expected of their .
. ground slate electronic configuration (the stability seems to be vanishing
for all. the chemical interactions of these elements, except perhaps in the
case of silver j all the elements lose the d electrons during chemical reactions
forming higher valent ions).
(6) Though ill the founh period 3d elements, the electronic con-
figurations are almost as 'expected, in the fifth (4d) and sixth period
88 Theoretlcal Principles 0/ Inorrant« Chemistry

clements (Sci), the alii bau principle is violated by most of the clements ..
Hence, elements with different valence shell configurations nrc placed
together in the same group of the d block clements, because in some of the
properties, these clements show resemblances to one nuothcr, Table 2.4
gives thc electronic configuration of the clements.
(7) Similarly, all the fourteen Ianthanons also do not have the expected
(11 - 2)I" (ll - 1) dl IIS2 configuration in the ground state. They are merely
'placed according to increasing atomic numbers. .
(8) As has been discussed later in this chapter, the borderline' clements
zinc, cadmium and mercury for the d and p elements and lutetium for the
I and d elements, as well as the first elements of the d series, e.g. scandium,
yttrium and lanthanum are not much different [rom the preceding elements
(copper, silver, gold, ytterbium, calcium, strontium and barium respec-
tively). Their properties can be obtained by simple extrapolation in a
period. In the long table, they have been separated drastically and differences
in their properties have been dramatized.

Types of Elemcnts
•
On the basis of the electronic configuration of the incomplete shells, the
elements are classified into (1) representative elements, (2) transition
elements and (3) inner transition elements. Although such a Classification
is convenient for the understanding of the chemical properties of the
clements, it overlooks the specific characteristics of the individual elements,

Representative Elements
The representative clements, designated as the R family, have only their
outermost shell incompletely filled up, and have the- general configurations
of ,IIs1 (Rs l), 1IS2 (R-2), IIS2 npl (R-3), ns2 np2 (R.4), 71S2 np3 (R-S),
1IS2 np~ (R-6), 1IS2 1IpG (R-7) and lIS211pG (R·O). The inner shells are com-
pletely filled up. From the chemical viewpoint, they may be further sub-
divided into the following subgroups.
(1) Inert gas ciCIIIC'lItS. Except for helium (ls2), the members of R-O
family have completely filled sand p orbitals of the outermost shell
1IS2lipS, These elements are highly stable because of the stability associated
with 'complete octet in the outermost shell and exist as monomers having
only very low van der Waals forces. It is onl)' after 1962 that compounds
of inert gases, especially of xenon and krypton have .been isolated with
highly electronegative elements (oxygen and fluorine only) which are
extremely reactive and are powerful oxidizing agents.
(2) Representative elements. If the definition is strictly adhered to,
the representative elements would include copper and zinc families as well
as ytterbium and nobelium. Though in the ground state, these elements
have only the outermost shell incompletely filled and copper family in state
I and zinc family in state II resemble the R elements, the more common
 Periodic Table and Periodic Properties 89

and stabler oxidation states for copper family elements have incompletely
filled d orbitals. The zinc family follows the copper family and both these
families resemble the transition elements. Similarly, ytterbium and nobelium
£
resemble 'the inner transition clements in their properties and hence arc
grouped with them. In actual practice, the zinc family' forrus a bridge
between the transition elements and the representative elements.

The Transition Elements

The clements having incompletely filled d orbitals in the ground state or

in the excited or chemically combined state arc called the transition clements
(T families). Though by the definition. zinc family does not belong to the
T family, for chemical reasons. it is classified as the T·tO family having dlO
configuration. The configuration of the incomplete shells for the transition
clements is therefore, (n - l)s2pOd'" IIS2 (x =1 to 10 for the T-l to T-lO
families). Due to the extra stability of the half-filled and completely
filled shells (due to the exchange energy and the Hund's principle),
irregularities in the configurations do take place. especially at Cr and Cu in
the 3d series, and at. other places in the 4d and Sd elements. There are
four T series of elements corresponding to the unfilled 3d, 4d, Sd and 6el
orbitals, beginning with the 'scandium (2 = 21), yttrium (2 = 39),
lanthanum (2 = 57) and actinium (2 = 89) ,respectively, and ending at
zinc (2 = 30), cadmium (2 = 48). mercury (2 =80) and Z = 112
"respectively. By the strict definition, lutetium (2 = 71) and lawrencium
(2 = 103) should be included in the T families, but their properties justify
their inclusion in the inner transition elements. Further, as in these element
the 4f and 5f levels a-re just filled up, these can be termed as the bridging
elements between the inner transition and the transition elements.
The transition elements show striking resemblances to one another in
their physical characteristics (melting and boiling points. metallic nature,
alloy formation). positive (high as well as low) and negative formal oxida-
tion states. coordination compounds, optical .and other spectral properties,
paramagnetism of ions, etc.

The Inner Transition Elements

The electronic configurations of the inner transition elements are 4fl-U

SS~5p65do'1 6s2 for the lanthanons beginning at cerium (2 = 58) and ending
at lutetium (2 = 71) and 5j1-H6s26po6do,l 7s2 for the actinons beginning
with thorium (Z = 90) and ending with lawrencium (Z = 103). Because of
the similar outer shell configurations, and energies of tbe! orbital electrons,
the lanthanons as well as the actinons arc expected to give state III without
exception. All the elements in a series would have similar properties
because of the same size and outer shell conflgurntions, l1\aking their
separation from one another tedious.
 90 Theoretical Princlples 01 Inorganic Chemistry

The tendency to lose / electrons is more in the case of actinons as

these, electrons are less firmly held by the nuclear charge as compared to
the 4/ electrons in the Ianthanons. A useful, criterion for determining the'
other valence states for the lanthanons is the extra stability of empty, half-
filled and completely filled orbitals as' shown by CeH (4/0), Sm2+, TbH
(4f7) and Yb2+ (4fH) ions.
The chemical properties of thorium, protoactinium and uranium
(Z = 90, 91 and 92 respectively) indicate these elements to be transition
elements and 1I0t the inner transition elements, belonging to d2, cl3 and d'i
families or titanium, vanadium and chromium families respectively.
Spectral properties of these clements indicate, however, that these' elements
arc the ~r clements. This is apparently due to the low energy differences
between the 5/ and Gd orbital electrons. The energy released by bond
formation is .sufficient to raise the 5/ electrons to the 6(1 orbitals, and even
take part in the chemical combinations.
As the electrons are added, the relative energy of the 5/ orbital
decreases below [he 6d orbital, and elements neptunium and the ones
following it unambiguously belong to the inner transition series, spectrally
as well as chemically.

Conclusions

A strict classification of the elements On the basis of the electronic con-

figuration is difficult. Several classifications are possible, each having its
own merits and demerits. An appreciation of the principle behind classifi-
cation is, in fact, mqrc important than the classification itself.

EFFECTIVE NUCLEAR CHARGE

A large number of the physical and chemical properties of the elements

show unmistakable periodicity based upon the electronic configuration of
the elements. Some of these properties which attract chemists more than
others arc: the atomic, ionic, covalent and crystal radii, ionization
energies, electron and proton affinities, 'crystal lattice, lattice energies,
melting and, boiling points, electronegativity, compressibility, malleability and
hardness, redox potentials, heats of fusion and formation of compounds,
solvation energies, vapourization and sublimation or clements and com-
pounds, and spectral and magnetic properties. Some of the more important
properties of the elements arc discussed below. In all these properties, it is
important to consider the hold of tfic nucleus of the atom on its electrons.
Presently, let us consider the manner in which electrons in a polyelectronic
system are affected by the nuclear charge.
 Periodic Table and PeriodicProperties 91

TIle Screening or Sbielding Constant

The energy of an electron in a Bohr atom is proportional to Z2/112

lIIe"Z~
En = - -·8(Q~1l21i'i- (1.45)
hence, it is expected that the energy of the outermost electron (most loosely
held) will increase rapidly when the principal quantum number 11 changes.
ThlJS if E(H) is the ionization energy of tbe hydrogen atom (1.312 MI,
13.6 eV), then ionization energy of some other elements will be
E(He) = 4 E(H) =~5.25 MI (54.4 eY); Eob. = 2.372 MI (24.4 eV)
9 . .
E(U) =
4' E(H) = 2.96 MJ (30.6 eV); Eobs =0.520 MJ (5.40 eV)

E(ne) = ~6 E(lI} = 5.25 MJ (54.4 eV); Eobs =0.900 MJ (9.32 eV)

Calculations show that the value of Z corresponding to the observed

ionization energies (IE) using Eq. (1.45) arc Jess than the actual nuclear
charge, being 1.35 for helium, 1.59 for lithium and 1.7 for beryllium. Hence,
the charge of the nucleus as felt by the outer- electrons gels reduced from
2, 3, and 4 to 1.35, 1.59, and 1.7 respectively.
Taking the case of lithium with the configuration IS22~1, it can be seen
that the bulk of the electron density of the Is pair of electrons will be
between the nucleus and the outer 2$ electrons, From electrostatics, the net
effect of any charge present in the form of a cage is the same as if the
charge is concentrated in the form of a point charge at the physical cage-
centre .. This means that ill the case of lithium, the net effect of the 1$2
electrons between the nucleus and the 2$ electron shculd be to reduce the
nuclear charge by' 2 units making the effective nuclear charge Z· as 1.00.
The radial probability distribution curves show that the 2s orbital also has
a maximum at or around the maximum for Is orbital. Thus the electrons in
the 2s orbitals penetrate the lower Is orbital. Taken literally, it means that
the.2s electron will spend some time facing a full nuclear charge of 3.00
units. This does not mean that the energy of the 2s orbita! electron will
change when it is nearer the nucleus and thus penetrates the Is orbital. The
energy of the 2$ orbital electron will be determined by .Z· which is some-
what less than Z due to the presence of the 1$2 electrons. Reduction in Z
will be less than 2 units as part of the .time the Is electrons will be
ineffective in shielding the 2s electron, so that one can write
Z· = Z - a (3.4)
where a is called the shielding or screening constant.

SIMer's Rules

Slater has given a set of empirical rules, which are 'gross generalizations
92 Theoretical Principles 0/ Inorganic Chemistry

based on the average behaviour of the electrons for the evaluation of the
screening or shielding constant G. Though not accurate in giving tbe energies
of the electrons in polyelectronic systems, they are nevertheless, useful in the
estimation of atomic sizes, elcctronegativities, etc.
For ns or np orbital electrons, these rules for G nrc:
(I) Group the electrons present in the order {Is), (2s, 21'), (3s, 3p), (3d),
(4s,4p), (4d, 4f), (5s, 5p), (5d, 5f), (6s, 6p), etc.
(2) Electrons to the right of the (liS, IIp) group are not effective in shielding
the ns or "I' electron and contribute nothing to fl. In other words, higher
energy electrons arc ineffective in shielding rower energy electrons from the
nuclear charge,
(3) All other electrons in the (liS, lip) group contribute to the extent of 0.35
each to the screening constant except for the Is orbital electron for which a
value of 0.30 seems to \\ ork beuer, .>

(4) All the electrons in the (II - 1)lh shell contribute 0.85 each to the
screening constant. . ,
(5) All other electrons in the (II - 2)th shell or lower, contribute 1.00
each to G, meaning thereby that the electrons in the (II - 2)lh and lower
shells completely shield electrons in the 11th shell.
In the case ofa d or anfelectron, rules (I) to (3) remains the same, but
rules (4) and (5) get replaced by:
(6) All the electrons in the groups lying left to the (lid, IIf) group shield
the d (orf) electrons completely, i.e. they contribute 1.00 to the screening
constant.

Example. For the valence shell electrons of fluorine, the orbitals are
grouped .as (ls)2(2s, 2p)1, the screening constant q is
G = 2 X 0.85 +6 X 0.35 = 3.80
and hence

Z'" = Z - C1 = 9.CO - 3.80 = 5.20

Consider arsenic (Z =
33). According to rule (1) its orbitals will be group-
ed as (ls)2(2s, 2p)8, (3s, 3p)8, (3d)io, (4s, 4]1)5. For 4s or 4p electron,

G = 00 X 1.00) + (18 X 0.85) + (4 X 0.35) = 26.70

so that
Z· = 33.00 - 26.70 = 6.30.
For the 3d electrons, grouping remains the same, but
G = (18 X 1.00) + (9 X 0.35) = 21.15
giving

Z· = 33.00 - 21.15 = 11.85.

Hence the electrons indifferent orbitals are differently affected by the same
nuclear charge depending upon their proximity to the nucleus.
 "

Periodic Table and Periodic Properties' 93

Limitations of Slater's Rules

Slater's rules have the following drawbacks.

(1) The sand p orbital electrons are assumed to be affected by the nuclear
charge in a similar manner which is not the picture given by their probability
distribution functions.
(2) All the electrons in the s, p, d, or / orbitals are taken to shield the
higher shell electrons with equal competence. This is not easily digestible
as the widely different (energetically as well as stereochemieally) orbitals
cannot have the same effect on or for the outer shell electrons.
(3) Penetration of the higher orbital into inner (especially the s orbitals)
is completely ignored.

Slater's Orbitals

Slater's orbitals were proposed to get hydrogen like orbitals for polyelectro-
nic systems' for use in the quantum mechanical calculations. They have the
folJowing properties.
(I) They possess no nodes. Though it simplifies the orbitals, it makes them
less accurate.
(2) The nuclear charge Z'is replaced by Z*., calculated using the rules
given above.
(3) For 11 > 3, 1/ is replaced by n«, and II - 11* is called the quantum
defect; the values of 1/*, for some 11 values are: 3.7 for n = 4,4.0 for II = 5,-
I,
4.2 for = 6, etc., leveling off to 4.5 for higher n values.
-Clemen t and Raimondi (1963) have calculated Z* from self-consistent field
wave functions of helium to krypton and have proposed a set or rules for
calculating a which then depends on both II and I.

Penetration or Orbitals
The extent to which an orbital or a shell interacts with the lower quantum
shell orbitals is termed as the penetration or the orbitals. As an example, we
find that the energy of the 4s orbital is lower than that of the 3d orbitals so
thatthe filling of the 4s orbital commences even' before the third shell has
been completely filled up. This is referred to as the penetration of the 3d
orbital by the 4s orbital. . .
The penetration is more as the shell number increases. Thus the 5s orbital
penetrates both 4fand 4d orbitals, whereas 6s orbital penetrates the 4f, 5d
and 51 orbitals. Due tc the presence of more maxima in the radial distribu-
tion functions at the lower shell's orbital radii for the s orbitals than for p, d
or I (ill this order), the penetration of the orbitals or a given quantum shell
is ill the order
s>p>d>/
AS the intensity of maxima in the radial probability distribution functions
for an orbital at a radial distance of lower orbitals is in the order
 r:
94 Thcorcticall'rinciples of Illorganfc Chemistry

s» P > d ~ f, the stability of thc orbitals with thc same principal quantum
number is also ill the order s > p > d > f, same as the proximity of these
orbitals to the nucleus. Secondly, due to the penetration of the orbitals,
order of the shielding of all orbital is s > p > d > f.

ATOMIC VOLUMES

Definition

Atomic volume (A V) is the ratio of the atomic weight A of all element to its
density p
. AV = Aj», (3.5)
Or, AVis the product of the atomic weight A and the specific volume Vu,"
the volume (in Jitres) occupied by 1 kg of the element
AV = A.V,,,, V," = lip. (3.6)

Difficulties in Assigning Atomic Volume to the Elements

The important factors that invalidate the usefulness of the AV concept

arc:
(1) As AVis the volume occupied by a gram atomic weight of the element,
it is the volume occupied by an Avogadro number of atoms. Obviously, A V
wiII change with the arrangement of the atoms in the solid state due to the
variations in the 'free space' in different structures.
(2) The closeness of the packing of atoms depends on the interatomic
forces of attraction which arc different for atoms with different electronic
configurations.
(3) Allotropes of elements have different densities. It is difficult to choose
one allotrope in favour' of the other.
(4) Density changes with temperature, especia!Jy if the change of state
takes place. fhough 0 K should be ideal .temperature to choose as the
standard, it is experimentally impossible to reach absolute zero. It is very
difficult to decide a temperature at which two elements may .be said to be
in a comparable state.

°
(5) While some elements exist as monoatomlc,
e.g, He, Ar, Hz, Ot, 3, Asj, Pj• S$' It cannot be expected
of Xn molecule is n ti mes the volume of X atom.
others are polyatomic,
that the volume

Vnriation of Atomic Volume with Atomic Number

"
The variation of A V with Z is shown in Fig. 3'.4. The volume of an atom
depends. upon the principal quantum number of the outermost electron
 Periodic Table and Pertodic Properties 9.5

and the mass is concentrated at the nucleus, The alkali metals have a
much larger volume than the preceding clements because of the forma-
" tion of a new quantum shell. Hence, they have a low density, and conse-
quently, a high atomic volume. As electrons are added to the outer valence
___~_hc:lI,
illi~iaUy,the attraction force between the incoming electron and the
nucleus is stronger than the interelectronic repulsions. The AV therefore,
decreases. As more .electrons arc added, the .interelectronic repulsions
outweigh the nuclear attractions resulting in decrease in density. The
atomic volume, therefore, increases.
#'

70
60 to Fr
Rb
50 K i
I,
AV 40
," ,
I'

, ,
I I

,, ,,
in rn l 30 Lo I I

20 \h
10 0, Pt \.
Q ~~ __~ J- __.__~~ -L__ ~

0 20 40 60 80 100
Z
Fig. 3.4 Variation of the atomic volume (AV) (in ml) agalns] the atomic
number Z of the clements.
In the case of the transition elements.uhe addition of d electrons results
in increasing densities as the size of the outer shell decreases slightly and
the nuclear charge increases till at diO configuration, a sudden increase in
volume takes place due to the completion of the d sub-shell. Hence AV
increases at the dlO configuration only and the transition elements lie at the
minima of the curve. In the case of the inner' transition elements, the entry
of 14 electrons in the outermost but two shells decreases the atomic size
considerably, Hence, the atomic sizes of the post-lanthanon elements are
. found to be either less than or equal to the atomic sizes of the correspond-
ing pre-lanthanon elements. The decrease in the atomic sizes due to the
increase of Z QY 14 units while the electrons are accommodated in the inner
f orbitals is termed as the lanthanide contraction. This decrease in the atomic
sizes is more than that observed in the transition elements due to greater
increase in the nuclear charge coupled with the proximity of the orbitals
accepting the electron.
Hence the element with the highest density is expected to be the one in
the Sd transition series, which precedes the element having just-filled d10
configuration in the ground state~ The highest density is of iridlum
(SdO 6s0). 23.7 X 10' kg m-3•
 96 Tlrco/'clicall'rillcipics of [ilol'gallic Clr~"'i,!(ry

ATOMIC OR COVALENT RADII

Types of Radii

,As the radius of an isolated atom is difficult to define and more difficult to
, . measure; internuclear distances in compounds or. gaseous molecules are
determined and the radius of the individual atoms calculated therefrom,
The radius therefore. depends upon (i) bond order, (ii) the degree of the
covalent or ionic nature of the bond, (iii) metallic character, (iv) oxidation
state and size of the neighbouring atoms, (v) crystal or molecular structure,
etc. Hence a large number of radii have been defined for· the elements, some
of which are discussed below. Iqnic radii are, however, discussed in the
subsequent section.

Orbital Radii

Orbital radius is determined by the principal quantum number. It is the

maximum in the radial probability distribution curve of the outermost
orbital. For the cations obtained by stripping the atom of its outermost
quantum shell electrons, the orbital radius decreases by a factor of 1.5 to 5
when compared with the atomic radius. Thus the orbital radii (in pm) for
the outer orbitals for sodium, magnesium and aluminium are (2p: 25, 3s:
171), (2p: 25, 3s: 128) and (22for 2p, 104 for 3s, and 131 for 3p) respec-
tively .. The radii for the 2p orbitals correspond to the ions, whereas those
. for tbe 31 orbitals for sodium and magnesium, and for the 3p orbitals for
aluminium correspond to the atomic radii. '
For the anions formed by the gain of electrons in the outermost orbitals,
the radii do not change appreciably, however.

Bragg...,.Slata Radii

Bragg (1920) proposed a set of radii for elements whose sum gave the
I

_ -obscrvcd internuclear distances in tI. few hundred crystals, both ionic as well
as covalent, within 6 pm. Slater (1964) gave an empirical rule that Ionlc
radii of cations are about 85 pm less and those of the anions are' 85 pm
more than the corresponding atomic rltdii. He, therefore, suggested a
. unique radius for an element in multiples of 5 pm which gave the observ-
ed internuclear distances in, the solid crystals within 6 pm. Some of the
typical values of the Bragg-Slater radii are 100 pm for P, S, Cl; 115 pm
for As, Se, Be, 135 pm for Co, Ni. Zn, CUi 140 pm for Cr, Ti, V, J, Mn,
Fe; 150 pm for Mg, Hg; etc.

Covalent Radii

Covalent radius r of an atom is ilalf of the distance between the nuclei of

 Periodic Tab/a. Qlld·Perlodlc.PI'Oper:llc3 97

two like atoms forming a covalent bond. Thus the internuclear distance
between two. carbon atoms in diamond crystal.is 154 pm. Hence.ithe single
bond radius of carbon is 77 pm as the two atoms in diamond crystal are
held by a single bond." ::: .
The atomic radii .are additiveand give the covalent bond-radii provided
that the bonds formed are single bonds and the electronegativity of the
bonded atoms does not differ much. If X ... and XB are the electronegati-
vities of the elements A and D having covalent. radii r...· and rs, the bond
lengjh.rA~B betwcen.Aand B is given, by Eq. (3.7)
• , .: l : rA':"D= ri+ 'D - 9', X ... -.
\
Xg I . (3.7)
Equation (3.7) holds if the. bondAc-Ildoes not have.pi character asis seen
by the bond lengths C-I = 214, C-Br = 194, C-CI = 176, Si-I;<: 244,
S-CI = 199 (pm), the atomic (covalent) radii of theatoms being C = 77.
Si = 157, S = 104, F = 72, CI e.s- 100, Br = 114 and I = 135 (pm). How-
ever, where pi bonding is present the observed bond lengths deviate from
the values obtained by using Eq. (3.7), the extent.ofdeviation being.pro-
portional to the pi-character of the bond. Thus the observed and the calcul-
ated bond lengths for such bonds are SI-F = ]56 (182), SI-Cl = 202
(217), S-'-F = 156 (176) (In pm)., , .: " .
'For multiple' bonded atoms, the correspondlngradil are termed as the
multiple bond radii.'Thus carbon has double bonded radius.of 66 pm in
ethylene and triple" bonded radius of 60 pm in acetylene. Since the atoms
approach closer to formmultiple bonds, greater orbital overlap is necessary
and the.covalent bond length decreases with the bond order. However, the
term radius has rio physical significance for the multiple bonded atoms as
they are far removed from' sphericity: ' ,.'.' , .
Then,' there are additional types of covalent radii like the tetrahedral and
the octahedral' radii (important for the ionic crystals and for the. coordina-.
lion compounds). The' tetrahedral radli arc smaller than the 'octi1l1edral
radii. Some values' of the metallic and covalent radii are given below:
" :Radius: ", K _'" Da :., La Cr In
"Metallic '1,'23i 217;' ,,)88 :J'>;
'159 ' 162. pm
, ,yCovalent:, ~03,!!" 198.'" 169 145, 150 pm
:!'jj'().:;. r. 0;:,: i '.: " : i·
Vonder:Waals:/{ad{i.,,·)',! ,;.. ,I

!: ;. :. ! ','·1\ ... :: ! :,

When molecules having no intermolecular attraction in terms of chemical

forces" e.g.: ,the. no.bl~ gases, saturated molecules like. methane, carbon
monoxide, 01' chlorine, condense to.form 11 solid, weak dispersion forces
(discussed' in, Ch., ?) operatc., The, internuclear distances .in .such: cases are
related to tile van der Waals .raotl. If the two atoms are identical and only
weak dispersion forces exist between them, the half of the internuclear
distance is:termed as.. the. vall, der Waals radius. For example, in solid'
helium, neon ,and argon; the' lnternucler.r. ciH~J:cc:s are. ~(;OI m; 3~O,pm and
. . " • .• .• I'
 98 TllttH~tica/"'p'{nclp't,f (If TnorgofliC Clttllli,.tr)l

380 pm respectively, hence the van der Wants' ,raclii f~r He, Ne and Ar arc
180,'160 and 190 pm respectively. (The kinetic energy .of 'the molecules i~
supposed to' be 'zero.) Tf the molecules possess kinetic energy (i.e. arc at a
temperature other than 0 K) the Lenard-Jones radii are 'more useful. They
nrc defined 'as the 1181f of the distance of closest approach of two molecules
having no -kinetic energy other than that obtained from the van der Waals
attraction forces: .. i, ,,' .. ., I','" , "'.,,' .

" Tlic van., der Waals radius' for' an element is not invariant. It depends
upon the compression by the external forces. In a compound, the-nature of
the bonded atoms affect the sizes of the atoms. Some o( the typical values
for the van der Waals radii are H = 120·145 pm; C = 165·170 pm,
N:= 155pm,'Q,= i:SO'pm, F='1~9·160pm,' Na= 230 pill, Mg~ 170
pm, Ni
:
l60'pm::.''= .'
",... .,'.
f
,,""
••• ,' l". .:!! J ; ~:' • ; ;

j!' .. '
IONIC ,RADJI. .: 1:::

E,;'i~tcl~cc'
• ; '.'.'. ',' !".'
or io~s~Th~ED' Map' IhuJii ,
• :',~;. !.', '.' ."",':' " ", ;

F;oL11\v~ve ineci;ani~s. the radius of the isolated ion or atoni will be infinite.
As the electrons are, transparent. to x-rays, the position of the electron~
around the nucleus cannot be determined experimentally in an ionic corn-
'pound, ot ionic lattice., Certain .nssumprlons must be made; therefore, to
have a useful concept or
the ionlc radii. These include (i) existence of the
ions, (i,I) correct. app'qrtioning of the internuclear distances between, the
ions; and (iii), c,~,n,stari'!='}·
o'~the ionic radii (additivity of radii). ' , "
, Though iit the molten state or in aqueous solutions, ions do exist, and
calculations .based 011 ,thr assumption that ions are present in ionic solids
do.'giveremarkably accurate descriptionof ionic compounds, direct evidence
comes only from Hie electron density maps (ED maps), for (a limited
number of). ionic .solids 'i!-ls,ingsophisticated x-ray crystallography, which
gives both the inicrnuclear distances and the electron densities (ED). ,The
charge density e-xtends from one atom to the tither continuously, but, drops
to a very low value of 200· electron nm-3 (0.2 electron A.-S) at, the outer
edges of the ion: Integration of the electron density inwards from 'such a
point gives about 10.05 electrons around sodium and 17.70 electrons around
chlorine nucleus, 0.25 electrons being presumably present inthe in ternuclear
space not included ill the arbitrary integration. This provides direct evidence
for theexlstence 'of ions in the solid state; The regionsof minimum ED can
be'considered to define the 'boundarles' of the spherical ions which contain
most oftheelectrons for which the' ED map radii can be calculated. '
, . The' difference bet\ve~n th~ ED map radll and the ionic radii of Pauling
a
is considered to 'be measure or the covalentbonding in ionlc compounds
'and iilcrases the"~r4er
in K:'-:< Na+, -:< Lit Cu+ and Cl- <: Br-. -<
!'",A: cbr~~ct' appo,i'ti'oinirig··, 'cif' the :Internuclear'distance is possible as these
j'\-;'nir;r~'tidditive.i:pcimnilent table of ibitic radii can, be .constructed, from
 the internuclear distances in the ionic crystals, provided the ionic radius of
one ion is known. Though the radii do not remain constant throughout It
series, the variations are small. Thus for the halides of metals, the radius
r, in pm is
reNa) =:= r(LO + 25 ± 3 r(CI) = reF) + 50 ± 4
r(K) = reNa) + 32 ± 2 r(Br) co r(CI) + 16 ± I
r(Rb) = r(K) + 14 ± 1 r(l) = r(Br) + Z5 ± I.
. . '. . .
Experimental Determioation onooic Radii
~.I , , : .~• i -, " :. : -v • ' • ; i; .

Several empirical and semiempirical methods have been used for thc calcu-
lation of the ionic radii. As the observed internuclear I-I-distance in Lll
was found to be the shortest «.26 pm).
Lande (1920) assumed that the smallest ion that can be found in ionic
crystals is lithium ion (Li+), In combination with larger halide ions, it
would- be too small to keep halide ions from touching. Larger the size 'of the
halide ion,' "more 'Iikely' will this be true. Further, the observed internuclear
distances. showed that the r....:..I distance in Lil crystal is the shortest (426 pm),
Assuming' that in Lil, the two iodide ions touch each other, the ionic radius
of iodide io~! was' taken as half of the internuclear distance = 213 prn, From'
the Internuclear distances in other iodides, the ionic radii' of the cations
could' be' obtained by differencd •. Thus in KI, the internuclear distance of
353 pmglves the ionic radius for K+ = 353 - 213 = 140 pm. Some of the
.values obtained this way areNa+ ~ 99, Rb+ ... 144, Li+ = 74, F- = )32,
CI- .... 172, Br- = 188, in pm. ' .' .. .
Bragg and West (1926) used this principle to obtain the radius for the
oxide ion from the silicates and then calculated the ionic radii of over
80 ions.', "",1 u: I;'
t . I

Molar Refractivityand the Ionic Radii

Using the Lorenz-Lorentz equation (Eq. ~.8), the molar refraction R of'a
substance can be determined experimentally .
n2-1 M
., ,
. 1;

R = 112+2 -P- •
(3.8)

\vlie~e';,: is the ret~acti~e index of the material having molecular weight M

and density p. Th~ molar refraction bas been found to be additive and
refraction equivalents for l',tom5 and bonds can be assigned. As R has
dimensions of M/~, i.e, volume, the ionic refraction for each ion can be
put proportional to r3, tthe radius of the ion =r) so that

, ;.;
100 Theoretical Prillclples 0/ [lIn'rCa/lie ChemlJ'lry

and if k is assumed to be constant f01"different ions,

'r;=(RR2 )1 3 .
", 'Tt t / (3.9)

Thus, as the internuclear distance in NaF is 231 pm and the ionic refrac-
tions of'Na+ and F- arc OS and 2.5 respectively, the ionic radius for
sodium is '

. 231 X ~~if.5 = 85.25 pm.

{l0.5+~2.5
Similarly, the molar polarization of the ions, can also be used for the
determination of the ionic radli using equations similar to Eq. (3.1) and
Eq. (3.9). , .:

Pauling's Univalent Radii

Assuming that the ionic radius of all ion should be inversely proportional
to the effective nuclear charge Z* of the ion" Pauling, proposed a set of
ionic radii \vbich arc the most ~'\~idCly' used ones. 'Pauling, considered the
isoelectronic ion pairs Na+F-, K+Cl-, Rb+Br;- and Cs+I- having the same
ionic radius ratio, and' same percentage of Ionic character. .He made the
assumption that in the solid state the ions touch each other. The internu-
clear distance ~ was determined from x-ray crystallography, whereas Z.
was calculated usingSlater's rules for the lighter elements and from molar
refractivity and x-ray terms for the heavier members:,' ,
Calculation, The internuclear distance in NaP, is 231 pm. If rNa and '
rp be the ionic radii of the ions,
. ,"" ;.::', .
+ rF ;= 231.
TNa (3.10)
The electronic arrangement of both the anion as' well as the cation is'
}s22s22po. Screening constant for the ions is therefore,
8 X 0.35 +2 X 0.85 >= 4.50
so that
ZNa *= 11.00 - 4.50 = 6.50,
, Zp~' = 9.00 - 4~50 .,,;.4.50.
As the ionic radii are supposed to be proportional toZ·-I;
rNa = C/ZNa • and 'p == C/ZF* (3.11)
where cis the proportionality factor depending upon the electronic structure
of t~leion. Inserting the values from Eq. (3.11) into Eq.(3.l0)
c/6.50 + ,c/4.5 == 231
giving
c = 614 (for ions of neon configuration)
and rNIl = 614/6.50 = 95.4 pm
rp' ,= 614/4.!0 = 136 pm.
 Pel;igtJic TClblc 1!(ld P~ri(l;'(ic !,roper,lies ,101

As for the isoelcctronjc systems, the screening constant will be same,

the univafell! radius for oxide and magnes,ium ion comes outas
'0:- = 614/(8.0 -,. 4.5}= 614/3.5 = 175.4.pl11,
'M&2+'= 614/12.0 - 4.5) .= 614/7.5 = 81.3 pm..

Pauling's Crystal Radii'

Pauling's radii calculated as. above, agree very well for the observed
internuclear distances for salts containing. univalent ions. For the multi-
valent ions, e.g, Mg2+ and 02- ions, the calculated radii ('11 values) givc
the internuclear distance in MgO as 257 pm in the, place of observed
205 pm, Obviously the values r., arc too large as thcy are 110t corrected
for the additional compressions which the ions undergo in a 2 : 2 lattice
in comparison with, the 1 : 1 lattice. Radius I'll may therefore be consider-
ed as the size of the multivalent. ion when compressed by the lattice forces
of only a 1 : 1 lattice and can be correlated with the radius I'll of the ion in
an i :jlattice as shown below. ,.; ,'. .,
The equilibrium internuclear distance I'cq in ionic crystals consisting of
ions carrying charges z+ and z.: is given by
I.
1
. '( 47':*'Olln) -,1 .... 1 (3 • 12'J
! ; . ,rcq = Az+z_e:!

. where II isthe Born .exponcat, A the Madclung's constant and B is the

interelectronic; repulsion term (due to Born) .
..: Substituting z+ = Z_,= 1 for'l1 und.z, = i and ;~ = j in Eq .. ;(3.12)
we get
,
: ru, ,= '7/le2 (4 B)I/(1I
1UoII,
- 1)
'
'. (3.13a)
; ;,.
and
:1 .
" , '." . ". " 1/(11-1)
_ (4"(uI/JJ) .. , "(3.13b)
'11- '.J"A"e-
which 011 divisiou yields
1
,,//r11 = (ij) -~
or
i',I!"ii :,::; ,·'rl . ~ 1'::1 :.. /.\~\'I'ln ;~".i····:\·'\;'\'I·.J;.Y:··.'J·l .:::\~ "

'.:;11 w,::.,' r'l.~ ,r:ll(ij) ·"it I'i' ,:.·qi~.14)

",:'1 :;ili/;I ·.,i;',,-Ir.
, When i =.1.::, c, the radius r, is called the,c:l'ysti-tlrradius'6Pthe1ibvalcnt
ion]' and is related tO'n throughiEq, (3.14yi-is'" l1{)iJilllll; :H:T .iI.i. :Ar!,i:r)

;" I': I•.' -:','.:; I.;:;. ; I'~ 'IL~.·:I.:I,,';'',::: ,', :,"'::';;:; ~:;;;;·:J\.\:·'·.'i"'~~:~i';;·.)I'~\'\n,).\i.::~;:'
'. = "11 .C " ' ..:/>:," :';c\·);~,~.J.,.:
 102 'IheortllCllJ Principles of ll11Jrzanic CI,emlslry

where II is the Dorn exponent and depends on the elcct~onic configuration

of the ion. The value of 11 is 2 for He, 7 for Ne, 9 for Ar,:tO for K.r and 12
for Rn configurations. . , , .
Using Bq, (3.1S), crystal radii fOI'Mg2+ and 02- ions (".,;,. 7) can be
calculated as
2
r2 for Mg2+ = 81.3 (2)- 7-1 = 62 pm,

. 2
r2 for 02- = 1,754 (2)--7::':C = 140 pm,
. . .

which now compares favourably with the observed internuclear .distance of

205 pm in MgO (calculated rz values add up to 62 + 140 i.e., 202 pm). : .:
The effective ionic radius increases with the eoordlnatiou number of tlie
ion. For example, the ionic radii for Ca2+ ion. for different coordination
numbers is 102 (6), 107 (7), 112 (8) 118 (9), 128 (10) and 135 (12) and that
of oxide ion is 135 (2), 136 (3),138 (4), 14C(6) and 142·(8) (numbers in
parentheses represents the coordination number and the radii are.in pm,
However the variation in the size of a cation is more than that for the
anion). . ..
Nonsplierical ions cannot be assigned a unique radius~ Majorities of
anions (nitrate, carbonate, sulphate, cyanide, etc.) are nonspherical. How-.
ever, for most such ions the apparent ionic radius can be calculated from
the lattice energy of the compounds containing these ions as discussed in
Chapter 5. Such radii are termed Yatsimlrskt's thermochemical radii. Some
typical values of thermochemical radii arc acetate ~ 160, borate == 191,
carbonate c::a 18S, chromate = 240, cyanide = .182, hydroxyl ~ 140, oxide
= 180, nitrate <= 189, nitrite 1::::1 155, hydrogen carbonate = 163, perchlorate
= 216, sulphate ... 230, phosphate = 238 (all the values are in pm),
Except for the tetrahedral ions (sulphate, phosphate, : chromate, per-
chlorate) which arc closer to spherical symmetry (and probably octahedral
[PFG]-, [AIFo]3-) these values have no use except in the thermochemical
calculatlons. , \

.;'1 .:;.;:;

Iouic Radii And Periodic Table

; .:
'I

Variatlon ill a Group

.For the representative elements, the atomic and ionic sizes increase with
the increase in the atomic numbers. The increase is maximum between the
two lighter members and minimum between .the two heaviest members
(Table 3.4). The addition of-the electrons to .the .new quantum .shell..Is
simply not compensated/or, by the increased nuclear charge, due to the poor
shielding capacity of the d and / orbital electrons durlng'thc fourth and
hishej;,periods... ' ",. I

f
;
l\IfILrv
,,: l'tJ\..
r-,,-'
r'l::"
J
 .PeriodicTabl« and Periodic Properties 103

Table 3.4 (a): Ionic radii (in Pili) 01 Jsoelcctronic lous ,',~' \',

i-.' '. ,'i, . 'Cllarge onthe {Oil' .' , , ;:- .o"i •

I.~!:~ 'j!
" "
, COllfigura/ioll -3 -2 -1 0 +1 +2 +3 +4 +5',,, ; ,; ~
i,l'2 H He Li . ,_
., ISO' 120 66
2s22pG N 0 F 'Ne Na Mg Al ',:;r_,.' ., J • ~ .' .
Si
150 140 136 140 97 . - 67 55 42
3s23p6 P S CI Ar' . K CiL Sc Ti
190 184 181 170 133 99 81 68
·,.3323p0311IO 'J. i'l c«: .ze ' Ga Gc',' .
.. , . ~, . 96 .14 ·62 . S3
.4$14po As Se llr Kr Rb . Sr· .. Y Zr Nb
:, .. . ' 200 200. 19S 18~ .. 14r ,1~2 - 92 .. 79 69 .
.i,'
4~%4pG4dJ~ ,. All . Cd In pi Sn , .','

';' .
126 ,.
97 .81 71
4s24p64dl0Ss~
.. i
511 'ss ,',
93 79
~s2SJla Tc 1 Xc Cs Da La
. ¢c "
:

: , ",
200 216 200 167 134 114 • ; 94 I'"

·.t/uSsI5pS ;1,
'" Yb Lu" .fir l' a-
93 ' 85 .' 78: : 68' :1':. i

5s25p65([10 Au Hg TI Pb
137 119 95 85
S~·25poSd106s2 Au TI Pb ni \ \ "

202 147 120 93

. Table 3.4 (b) Ionic and AloDlic 'Radli (or TrilllsiUolI' and Inner Transition Elem'clIls in poi
Sc ':'Ti VCr' Mn" Fe ce '. Ni' ~" Cu':~ zri
AtoUlic 164 147' 135 129 127 126 125 i.," 125' '128' : 137
. ·Ionic MH ., 100 93';',89 ,··80 76 ,i 7~ ,'::,72-' 87 !;6Z
:.":" MH 89 •. ·81-..'78-.76· .75· :70, .68:.70.:68 ...•. :
Y Zr Nb Mo Tc Ru .' ) Rh·;', .Pd :.. AC ; Cd
:Atomic ,182: 160:-,147 )40 13S'i.13~ ..,·13'\.i;p7),:)44 152
MH ;... ,,'., ".,.".;.78, ~13
MH 104 . 86 83 82 80
·,,:·oi ..,· .. c::;. M4+ "86': .,.:,1"-'" .: 78.. :16" '74 : ;'1 '76':"
.:; 'La ·'iHf" Ta 'W::'Re 'Os·'j'Ir-; "p{ .'Xi<-:IH't;
",Atomic"::': ":';'188';'·'159';:147 ·141' 137' -,135 136"; "'139"'144,: 155
......
Ionic .. " M2:+ 'J 'iil .'.'::" ';,;i;J'l ,!ii .•;,' ;i1i,94'·."i ".iUO
,.,; .. , M3+, .. ,,117
. ~ ;./ ',." ,.' •.. ,:,;·.~2 ;,;:1 '" "i.<~?;
~."" 86., ,,'ij'(''''
MH . 80, .
'. 77 ,77 85' 82
77 . 76 . ' ...
". -' 'I ll : :',!'
,:' I ' " -. .:. -t r • 'I I .' I : . I J.
.: . j '•• " ,,: ~~ , : '. s: ~-:'; I,'_,I
• " t • ""1 ", ..... La Cc "".Pr J' Nd ,.).Pm.• ;, Sm,.,.Eu 1"IIJ.Gd ,;; Tb ,;, Dy
-»,

" Atomic'" ,. ',188 '182,' 183 _ 'i82 " "-: "180 204' .. 180' '. 178 .. '177
,'Ionic' I! 'M2+' "iii ',,:.,-,,);,' ,")J! 11i '1381'.131 J!_,'HIIJ ... ·;·.· •.a

', .. :' -, ;:'11: MH'<":'117 i. 115":;],13';[1112 (,,1111';":109 ',,,iIO'S }'·'·'·108 ,1:10'6:-:.105 .

·Ii.; II :.11 ': M4+//',li; .. 101:·"/:99.~jli' 1.)'\ .r. 11.: 'I~;"'~':' V!ilbI.;;id ....·~!.lr99 ~J!I '.~
!":J,-'.-·k,.:, r:.;,~! ,flo·il Er.'I:TmrlfJ)Yb Lu.u.! L:::i .;rflilliJ.' :.Jill .ii •..·;",1·
l;~\Olllic', ,", :i'1177,.176.:)7S"~9~"'\,,F3~\I1'~ .dli.~ji'·:J ,:Ii ,:',,: s, 1) -;,;1

M2+ ,.' j,: ; :'j,.116, Ii: _.', 11l':'·".iiU !' . .<I ~:"'''i,)"'Jili!':)':' Ii
Io~i~: ,;" MI:~ 10'4 103 :'102 '101 100' . __ , ",
(0)

Ac .' Th Pil (J Np l'u'" A~ ~1:~i~'I'Bk

cr '.Nt)
Ionic 126 118 116 lIS 114 112 III 110 109
124 135 124
i08 J04 103 101 100 99 99' 97 96
'104 '1'II~ref/cat Principles a/Inorganic Chemistry

III the transition elem ents, the increase is much Jess as can be seen by
comparing the values for the representative and transition elements
(Table 3.4) I

GeH SnH PbH TiH ZrH HCH

Ionic radius S3 11 84 68 79 78 pm
Increase in radius 18 13 11 -1
Increase in Z 18 32 18 32 pm
r • ~

This can be explained 'on' the basis of the fact that between the 3d and 4d
transition series, IS'electrons are added of which 10 are poorly shielding
c/ orbital electrons. Hence, the -cflect of the increase of a new quantum
shell is not fully reflected (as is reflected by the increase between the two
lightest members) in 'the increase in the atomic and ionic sizes. 32 electrons
are added between the 4d and Sci elements, of which 10 are the poor
shielding d electrons and 14 arc the extremely poor shielding jelectrons.
Hence, the size of the ions becomes either the same or decreases for the
elements immediately following the 4[ elements. For the latter members
however, the sizes may increase but the increase is ,only nominal in Com-
parison with the 4d:members.

Variation ;/1 a Period

For the isoelectronic ions, 'the ionic radius decreases with the increase in the
nuclear charge as expected (Table 3.4). The variations in ionic sizes shows
the following trends. .
(I) A sleep fall in size after IIS1 electron, signifies poor shielding of the
s electron by the s electron of the same shell' and the large penetration
of the s -orbital electrons.
"(2) Small' variations in the decreasing' radii of the transition elements
are duc'to the electrons occupying the if orbitals. Although the.initial 'filling
of the d orbital .electrons with an concomitant increase in the nuclear
charge produces the decrease in. the sizes, there appears to be a substantial
Increase ' in" the size as .the d:orbitals, are :completely filled up (completion
of the 18 electron shell), This corresponds to the greater increase Ilt· the
completion of the outermost shell of the inert gases with a stable octet.
(3) Sizes of the isovalent transition lensdecrease with Z;
(4) As the outermost'shell electrons determine the radius of the atom, or
ion, addition of J.clcctrons in the ("':""2)th shell for the inner transition
clements docs, not quite counterbalance the increased .nuclcarchprge Z due
to tgo poor shielding power of the [ orbital 'electrons. Therefore, a regular
decCe~~ein the atomic and ionic radii from-cerium to -lutetium is observed.
The -d¢'crease, culled the lanthanide contraction. is somucn that theeffect
of~hri~4dilioll of the new quantum shell fo~ th~ p;ost;lari'tlinnq? el,emel)t~)s
althu·sfi:ompletcly offset. ,.
 Conclusions

The ED map radii.are between the.atomic or covalent radii r and the ionic
radii "e.
but are closer to r. (Table 3.5). For general consideration. atomic
radii should be used when the atoms arc covalently bonded. For a covalent
bond, maximum overlapping of the orbitals in the incompletely filled valence
shells of the bonded atoms should take place. Tliis requires the maxima of·
the radial probability functions of the atoms to overlap. 'Hence the atomic
radii in covalent bonds are closer to the orbital radii.
Table 3.5: The ED Map Radii and Other Radii for Soine E1emen(s.
/', i
· Ato/ll Atolllic radius Covalent radius ED map radius Palllil/g's ionic
(Pill) (Pili) ; : . (pili) radius (P/ll)

Na 186 154 118 95

K 227 196 145 .133
MI: 160 :, 102 ' 65
en 197 126 99
F 71 71 110 136
CI 100 I()O 125 (CII)-170 (~) 181

Wlu;n electron transfer from one atom to the other takes place, the cquili-
briurn distance of the atoms is determined by 'the balance of the electro-
static forces and the interelectronic repulsions amongst the closed inert gas
shells. Hence, the atoms approach only to the extent' that they just touch
the tail of the radial functions of valence shells. This is sufficient to produce
the interelectronic repulsions to offset the electrostntic attractions, The
Pauli's exclusions principle strictly forbids overlapping ofthe filled inert gas
closed shells of the two atoms.
The two compounds KCI and CuCI (ionic and ionic. having partial
· covalent character, respectively) can be taken for a consideration. (l) The
sum of the ionic radii, or the ED map radii, gives a better value for the
observed internuclear. distances in KCI (314 pm) than. in CuCl (235 pm),
for which the sum .of the atomic ..radii works better. (ii) The ionic radii
are closer to tile lED map radi_ifor KCt'than for ~uCI. (iii) The radial
functions 'for;',.. the outer electrons.
I I
nearly;
. :.
.coincide
.
'for :.CuCl,
.1.. " I'
but are far :
· apart (01" the ionlc compounds.' \ !..!:." .' ,; '\ 1\ .) I \ '.. ; ':

IONIZATION ENER~~S
\.~' :.1 .. :
'.1 ... j ,.;1:'.1>', :'"-\ /
.;! 1.
\. j . I~

", I
: t,,;i ;
q !...
~ ;;: ..
. ;:1
Definitions if
., . ., .. i··. .
Ionization energy (of tell mistakenly called the ionization pole/itial) is t11C
energy necessary to remove the most loosely held electron from the ground
stale of nn Avogadro number of the i,solated atom, molecule, pl: ion In the
ga~cou!!~tate.;Thu~ the ionlzation.encrgy (IE), ,is .thc energy required to
c#ry oo(tlle reactions! ">, ,. "', .. ,, / J,'~' :., "(.,, .. ,\',
 106 Theoretical Pri/lciples 0/ rllol'tallic Chemistry

H -f-H+-I-l'- 1E= 1.312 MJ (13.6 eV)

O;l-t02++e_ IE= 1.35 MJ (14.2 eV) 1 .
NO-+NO++c- . IE=O.90 . MJ (9.3 tV) ..
'. I" • \

All the reactions are carried out in the gaseous slate. TIle JOIl so formed
may lose further. electrons. ,and· we have the successive ionization energies
(Ilrst, second, third, ...) for the removalof the first, second, third, ..., electron
in the gaseous state, e.g., . . ...
AI(g)-+AI+(g)j-e-· IE1=O.577 MJ (5.98 eV)
Al+(g)-+Al2(g)+e-· '. 'IE2=18.82 MJ (18.82 eV)
AI2+(g)-+AI3+(g)+e- TE3=2.75 MJ (28.44 eV)
Ionization energies are. usually determined by the potential gradient
through which 'the electron is accelerated, so that the term 'ionization
potential' is also used to refer to the same values. However, it should be .
noted that the potential is tile intensive properly (with. units as volt v)
whereas the ionization potentials arc quoted in eV or MJ 11101-1, the energy
'unit, and arc extensive properties, i.e. it depends upon the amount of the
substance: hence the two should not be confused. .
The ionization energy is the energy difference between the highest
occupied energy level ill the species and 'that corresponding. to
complete removal of the electron. Ionization energies are therefore always
endothermic and assigned positive values. The first ionization energies of
some clements arc plotted in Fig.15.

.
2,Or F ,',
Ar
..,-1.5 . N
. . i

~. :;
.. Xc
.s
Rn
1.0
.:
I1J
....
. .
0.5 Li
• ~.~.; I .-: _:

Cs

..-1-.~:-1..J.~L-
O.~.:L.,,""'.,.-,.:.-) -,:~"-2L-0-,"";~ ...-:i'~!,-.--.i::-:-:~"'0~
..... eo 100
z·
" I • ij I • .•.. r ,_ . ..;
; ,'. '. . '.' ' : I" i .. . • . , . ', •• ~.:' . I . '. :'.

Fig. 3.5 : Variation of the first ionization energy of clements with the atomic
. :, '. : number Z. '(Adapted whh permission : rrOril TI~erald Moeller:
TIt(,ol'(Uic(lltIlOl'gOIl(c Chemistry, John Wiley, New York, 1952);' ..
 Periodic T~bll! and Periodic Propertles 107

Facto~s Affecting the Ionization Energies ,

. '.~'. ( , -', :. , " ~', : '

Successive Ionizations . ' "

• . '., ~ '! •

Ionization energy increases (or successive' iouizatlons, as the successive

electrons are to be removed fron) positively charged species having increa-
sed Z* (due to the loss: of successive' electrons). With each removal of
, electrons. Z* forthe outermost electron.increases, hence these electrons go
to a lower energystate. ',' , ',:" .

. Atomic Size

10 a group, the ionization energy decreases with the increase in the size of
the atoms. Thus. IE decreases with Z ill a group except where the lanthanide
contraction
. ~. . results in the decrease
'.
of the. size, c.g, Zr~Hf
.. . '.' . . .. or Sn- Pb pairs:
: ,

.
• • t" ~ •.
~
"
;:,:

Nature of Electron
:. I

The IE depends on (i)Z* (higher Z* gives higher IE). (ii). the distance of
the electron from the nucleus. (iii) the extent to 'which this' orbital electron
is shielded by the inner electrons and (iv) the extent to which this electron
penetrates the lower quantum shells. The shielding effects help in decreas-
ing the coulombic attractions between the nucleus 'and the electron by parti-
ally neutralizing the attraction forces and repelling the other electrons.
Since the penetration of the orbitals is in the order s>p>cl> J, the s elec-
trons will be ionized from the atom by the input of higher' energy than the p
electrons, etc. Hence the IE of group 1[[ A elements (IIS2I1PI) is less than the
IE for the group II A elements (IIS2) because in the former case, the electron
, to be ionized is the p electron and It is rather loosely. held in comparison
with the s orbital electron to be ionized in the latter case. This is' more than
compensatedfor the inc;:rcllsednuclear c=ll~rge'of U~~group IlIA elements..
'. ';':, '",: , ',,","'" .1',:" ",.,", : I:" ".,::"", " ,

i" ·'·i!:

Nature of the Shell .t j' " '.'

Io~izati~n energy
inctease/ if 'th~ electron to be ionized 'from 'the species
belongs to a half-filled'shell (p3: or dG) or a! completely' filled shell (dIO or
p6). The relative stability of these configurations is in the order ,',' I,· "

dG<p3<dIO<p6 . , " ',' . " I.~,· ..,~

so that very high energy is required to' 'remove electrons' from the closed
inert gas .shell' (S2p8) .: This explains' (i) the' very' 'large' decrease' in the, IE of
the 'halogens' as compared: with the inert; gases; . values" for' 'IE' being
F'"",'16S1, Ne 2081'; Cl"", 1251,' Ar
== 152(; '11r =' 1140. Kr'=1350;
I o;=-lOOS,'Xc =·1370 (kJmol.,.l), (ii)'decrease in thc"IE of groups,VIA
elements 'with IIs'lnp' configuration' in comparison': with-the 'IE
:··tt
the or
 108 Theoretical Principles o/.llIorgollic C/mil/slry

corresponding group V A (IIS~lIp3) elements (values of the first .ionization

energies being N = 1402, 0 = 1314; P = 1012, S == 999.6 ; As ~ 944,
Se = 941 kJ mol'<). This may he due to the (a) breaking up of the p3 sub-
shell in the case of group VIA clements requiring higher energy' and (b) the
formation of a half filled p3 shell in the case of group Vl A elements by, the
loss of the fourth electron, reducing the ionization energies of the elements.
However, it is seen' that for the heavy elements (Sb ==
813.6 kJ mol-t,
Te = 869.6 kJ mol-lor Hi = 703.3.kJ moJ-l und Po == 812 kJ mol-I), this
is not the case indicating that the stability of p3 configuration, if any, is .but
only marginal. .

Change ill the Quantum Shell

. ." ,

When during the successive ionizations, the electron to be ionized belongs-

to the lower quantum shell, the IE increases manifolds because of the com-
.'blued effects of (i) effective nuclear charge Z*, (ii) sta bility of the completely
filled shells, and (iii) closer proximity of the lower shell to, the positively
charged nucleus. This can be seen from the IE values involving the ioniza-
tion of the electrons from the lower quantum shell: IE3 for zinc (3.833 MJ)
and IE.~for indium (5.2 MJ) vs, IE: for zinc (1.733 MJ) and lE3 for indium
(2.70 MJ) for the ionization of the dlO shell; and IE;! for sodium (4.56 MJ)
and lE3 for magnesium (7.73 MJ) vs. lEI for .sodium (0.496 MJ) and IE2
for magnesium (1.45 MJ) for the ionization of the S2pG shell. ,:1
•~I , •• ~• ;

-.,;';

ELECTRON AFFINITY
/ "

Dcrin~tio~

Electron affinity (EA) is conventionally defined as the el1er~y released. when'

electron is added to the valence shell of the isolated gaseous atom orion.
TItis is in contradiction to the thermodynamic convection tl;at theenergy
released is always taken as negative (exothermic). As it is not possible to
overthrow the accepted convention ofEA, i.e for ,;
F -I- c- --+
. F- , EA = 320, kJ motl" ....(3.50
;." :.:
c'y>
.
the discrcpency can be removed by considering the EA.of the atoms to.be
the same as the IE of the corresponding anion: ' ,,'1

,." F- --+- F +e- '" .'

'. IE==320~JJp,o~~l(3:SPeV) .. ,.. ,' "
.:.J ";,,, r ,

Now the.posltlvc EA corresponds to theendothermic.reaction. ,. I :,,:

... This japproach .,shows tbe closeness of the IE and)~A concepts. Infuct.,
~r.
;:\,.plot tbe EA: and lp, values.for tl!~ ~~me atom ugniast.tbe c11:ljTgerq on,
the-species is a smooth.curve (Fig. 3,6). which can be expressed as, :":I: I
. 'J .. :E=#j(,(q;+ ~q2 ,;;,." :', . '" ,I '., n, '.' ./" .. lil·.:;::'·

where exand ~ arc constants.

 Periodic Table and Periodic Properties 109
+
0.,1 1_
."'.1',". .. eo
Ii'"

, • ; r • i .~: ..; i rr J .' J

q
Fig. 3.6 Ionization encrgy and electron am- .
nity curves for the different oxlda-
;'! ( I;', ', ;; :": .. ! I" 'j 'lion states of the clements. .',.
:;':
Sucqes$iv~iElect'rOlI. AjJilliiies' .
<!!~J!f~}lIl!J _··,{;.,':d; ':.' .:" l'~;~;,"

The ifirst EA of actlve nonmetals is positive (exothermic). But the addition'

ora second electron to an already formed anion makes the reaction such as
X- + e- -+X2.,.., ..
endothermic, even for"'thd formation' of oxide or sulphide ion. The effect
Is so much that the 'overall EA 'for the' formation of oxide or sulphide ions
Isendothermlc to the extent'o( 640 and 390 kJ mol-1 respectively.' '
..t'~;:i ,,:~, jj.tL~·'.,
:_.:·~-·I· \';. . .: . .
. ~;
!'
',;

~: I ! ;', I :: ,i
The, ~A.trenQs are similar. to. those shown by the IE values .. The salient
featuresIn.the.trends are.the following. ';,;'.1,'"
(1) .The' elements with a higher IE.have higher EA also, e.g- halogens.
(2) The EA values of the second perlcdelements are lower in comparison
with the values of the third row clements : .
.:'; i·'Li "d ;·'Be·.!;' "::B""",;"C """'N"" 0 F"
59.8 .i.l;i~ r, '!!'.:',: .• : 23 ;122' 20," r-: 120 ,'320 kJ mol-1 "j

i':':"Nai .,',Mg' .' "AI' .' Si···· If,p;" ·:S·. "Cl ':,
I" :53.:: ,'" '1:" " . i,. 44' -: : 120, 74., 2Q~ ~48.7 kJ mol~l.
"This may be due to .the increase in the interelectronic, repulsions which
are more for the smaller elements because of bigher electron densities.
. (3)' Effective' nuclear shielding by the s electrons and the necessity of
using higher. ~nc=rgyorbitals to accept the·p electrons, turn the .EA of group
n A .elements negative ,(theoretically calculated values are e- 240, .'- 230
and ':""156lcI mol-1 for Be, Mg, Ca respectively; those for alkali metals as
well as the gro.up II[ A elements ilr~ positive). , . " .
,. (4) 'Gold, 'of all the metals, has a comparatively high EA (222.7 kJ mol-1).
This may be due to the higher effective nuclear charge and poor shielding
110 Theoretical Principles 0/ Inorganic Chemist f)'

of the nucleus by the tI electrons. Ionic aurides like Cs+ Au- arc known.
However, the transition metals have been shown to have a positive electron
affinity.
Ti V Cr Fe Co Ni Cu Zn
Calculated 37.7 90 97 56 90 123 174 -87 (kJ mol-I)
Observed . 63 III 123 (kJ mol-I)
(5) The electron affinity of clements having a d10s2 configuration is also
negative due to the need to accomodate the incoming electron in the higher
p orbital (zo = - 87, Cd = r: S6 kJ mcl'<).

O~IDATION NUMBERS

Valence, Oxidation Number lind Formal Charge.

Valence in its broadest sense can' be defined as the power or capacity of an

element to combine with' other elements. It is just a number without
any sign. The reference atom used is hydrogen which is always univalent.
Thus oxygen in H:P is divalent, chlorine ill HC) is monovalent, in CI02 is
tetravelent, in HC)03 is pentavalent, etc. Elements. may display variable
valence states in different compounds.
Oxidation number (ON) of an element in an compound is the total number
of electrons it appears to have gained. or lost (negative and positive oxida-
tion slates respectively), when the bonding electrons are supposed to be
present on the more electronegative atom i.e., the compound is considered
to be purely ionic.
Formal charge on an atom in a compound can be 'defined as the calculated
charge present on the atom in a compound. Thus the formal charge present
on nitrogen atom in NH,+ is +1, and that on nitrogen and boron atoms
+
in the coordination compound H3N -+B~3 is 1arid. -1 respectively •. ' .'

Calculation of Oxidation Numbers

For complicated molecules, certain empirical rules have to be used for

ascertaining the oxidation number of an element in a compound.
(1) Atoms in elemental form have' zero oxidation number. Thus each
atom in H2: o, P" SB' Cu, Na, Ar has zero oxidation number or state.
(2) Monoatomlc ions have ON equal to the algebraic charge present .on
them. Thus the ON of atoms in Fet+. Cr3-, N3+. is 2. '3. -3 respectively.
(3) Hydrogen is always assigned ON of +
1 except in the. ionic hydrides,
where it is present as H- and is asslgned ON of ~ 1. .
(4) Oxygen atom always has ON of -2. except in peroxides (621-)
superoxides (O:C) and OF:!. in which 0 atom hastl\~ ON of -,I. -1/2 and
. • I .• " ••. " • .-,

+2 respectively. . .. . , '"," '. " .

(5) Fluorine, being the most electronegative element; is always assigned
• • . . - : I •• ~ ~ • • : • . .: . • •

an ON of~l. " :1 "

 , Periodic Table and Periodic Properties 111

(6)"The algebraic sum ,of.thc ONs' of all the atoms in a species must be
equal to the charge present, on it. Thus the sum of the ON of all the atoms
in Cr02Ci:i, NOa:" [Fe(CN)o]'~ must be 0, -1 and -4 respectively .
. (7) ,In complexes, ON of the ligand can be considered as its charge. Thus
inTAg(CN2)]-or'[Cu(CN),]2-, theON of CN group is -1 (the charge on
the CN- ion); that of CO or NO in metal carbonyls or nitrosyls will he
zero, the' charge 'present onthese 'nlQlecules. " , . ,', ,,'. " , " " ,
:; The oxidation number 'calcuiated as above; is ,1I0t ileces~aril)' integral,
numerlcally eq'lal to its valence, and is 1I0t always 'a useful qua;,lity to know •
'\ ! I:" ", "\'. :'1. .! .
Calculation of Formal Charge

The coordinate bond results unequal .distrlbution of, electronic charge, so

that the term formal charge can be calculated as
Formal charge = z-u-is (3.16)
where z is the number or the ou~er (valence .shell) electrons of the atom, ZI
Is'the number of the'unshared electrons and s is the number of the shared
.electrcns around the !lto~,i!t',t11~compound, In NH,~ (or .example, z = 5,
tI == 0 and s'~ 8, so that' .". ' ",' " . : ....
«n j-. .• ;~ ;H':! j"(," r ' .;1:: :.:I~ , ,~.' I,.p" :i;_,' '! "'!'; \ . " .
i; ..',:;" p ,:, Ro.~al charge Q~ nitrogen atom = 5 .,...0 -'. t X 8 = 1

whereas in S02, z '= 6,11 = 2 and s:= 4, so that' ~'

, ;"'.:.:' ,,', Formal charge sulphur atom e-' 6""': 2 .: Ix4 ;",'2.
, .·':~'1~!-· ',. .:~:' :;' }". ;',.!: :',,.;,; :. r ,,:.:1,' ': .. -':1' "

, Uses of 'he Concept of the Oxldatlon' Nl(mbe;s. ;;.: I" .: . ",: ::' , ' ' "

.... ;'1)( ••. ;:. '.~:i ; :.;:_l '.~. ti!;l~~.r· :1: " .':! ~. .';, ", ~!"'" .: . :'!' :.: .... : i ;':'

us
Let. calculate the 'oxidation number of say Cr 'in K2Ci'~07; [Cr(NH3)olCI~
and [HCr(CO),CI]: This; can be done'by assuming the ON' or Crin the
compound as x. Then, for K2Cr20~,.:2+2x+(":_14)'= 0, i.e.. x';';', 6 (as the
molecule has two 'Cr atoms, total contribution' due to 'the :Cr atoms is taken
as 2;t). For [Cr(NH3loJCI~;' contribution due= to'<each NH; 'molecule to
the' ON is zero; ..
the
. ','
corresponding'
"
equation
.
'x+6.0..,_3.;;
,',
0;
I
gives• '
x';';' 3•
For [HCr(CO),Cl], . contribution'! of CO" to ON .be,ingzero, ' the equation
-1+,x.:.:.;.'l =',0 gives x'='O." ,,: "", 'ii, !::'U~'''': ".":';.1 ,".J ,",,' '.

! :·I~~a.nge ',in ~he.,O.~s, is: related " the l:equivalent' '\ve,jg~ts'!(EW). of the 'to'
oXldtzlOg(and:reduclDgagents. The ~W of 'a redox .substance is the ratio
. oftheimolecular'weigbt:and the ~liang~,fn'the ON'I'~fth~ specles unde':.
, goirig 'redox i!reaction." Hence,' for' 'the 'oxidizing agent 'jvlnOc in acidic
solutlons.: the' EW is' 1/5tl1its ionic \Yeig~t the, oxidation 'number as of
manganese changes by'S units in the reduction IromMn (VII).in MnO,- to
:to Mn(lI) in M02+;' .. ,' :.!' , .i.: "~I (,'. ::,' ",', :"','''" ... ' "., ',: ' .

In acomplete redo~ reaction, the change in the oxidation .. numbers for

the oxidizing ·::"aridIthe' reducing' agents 'should be equal; Thus in the
permangiinate~oxalaie redox reaction, .
:inON·are';:,.,.:·L'~) )" "". ,',.1..
"wbich the individual changes
'. ' .... ,
for , ,
',n :.;1 :!:;:;t: .;,~!\)"
", I'I .~,:.<\~'~ r ...!!,' " ::.i("):'
,I;. ;.. i
':-'";"~:..,OJ ~,:.'
~~. ~ .'!~:,',
 112 Theoretical Pr(IIciples 01 [llorgallic ChclIIls Iry

ON of Mil changes from +7 to +2

i.e., 5 units per MnOe ion .
ON. of each C changes from +3 to +4
l.e., 2 x r = 2 units per ~O.2- ion ..
Hence, two MnO,- ions will undergo a change of tenunits whereas' five
C2042- ions will be required for the same change in oxidation number. In
other words, two MnO.j.- ions are equivalent to five C20,2- ions •. Thus we

M
a
can write balanced equation for the reaction between MnOe and. C20,~-
.

2 MnOc+5 C!lO,2--H6 H+~2 Mn2++ 10 CO2+8 H20.

Oxidation Numbers and Periodic Table

Representative Elements

Though the oxidation slates of the. representative (R family)· elements can

be predicted from (a) tendency to attain. stable IIS~lIpG (the electron
stable octet), ns1llpOm[10 (the 18-electron shell) or (II-I)S2 (lI-l)pG~
(1I-1)d10IlS2 (the inert pair) configurations of the outermost shells and (b)
the fact that paired electrons are lost or shared' in' pairs, though unusual
oxidation states like Xe(IV), CI(lV), AI(I) exist.
The 1JS1 and IIS2 (group I and II) elements arc highly reactive elements
that give only the 'oxidation states I and II respectively. They attaln the
inert gas configuration by the loss of outer s electrons.
Group III elements (Ils2npl) can give two oxidation state: I by the loss
of the p1 electron and III by the loss of pi +S2 electrons. The. stability
of the lower state. increases with the increasing Z In a.group, whereas
that of the higher state decreases gradually. Thus boron, aluminium and
gallium show' trivalent. state only. Indium shows both mono and trivalent
state and thallium in monovalent shows greater stabllity •.
Group IV elements' (lIs!np2) show. oxidation states of II. and IV.; The
stability of (II) state increases, and that of IV decreases with: the increase
in the atomic number, A formal - IV state also exists, in which the clements
may be thought of as having attained the octet of the next inert .gas,(lIs2npG)
by acquiring four electrons. This state can exist only with the .hlghly electro-
positive elements in carbides, sillcldes .and germanldes (which erceovalent) ..
The ns2np.' configuration of the group V elements leads to the. oxidation
states of -IIf, III and V. The stability of -III and.V states decreases, with
increasing Z, whereas that of III state increases. Nitrogen is unique in the
group in giving a large number of oxidation states, including· fractional
ones ill simple compounds (-1 in HN3).
The characteristic 1I~2n.,j4 configuration of group VI elements being two
short of the next inert gas structure makes the lighter members \·crYreleclro.
negative. AU the elements ~ive"':"U state, stability decreasing down; the
group. The positive oxidation states of these elements may be II, IV or VI.
 Periodic Table and Periodic Properties 113

M . [IG]s2 Pm2p,,tp.,1
M2- . [IG]S2 Pm'!Pv2p,?
M(IJ) [IGJSII p.P
M(IV) [IG]sl!
M(Vl) [IGJ Lower shell, no outer shell electrons.
Oxygen, gives peroxides, superoxldes and fluorides (oxidation 'number
-1, -l and +2 state respectively) and a uniform -II state in compounds.
All other elements of group VI f01'111compounds in all the oxidation states
expected: The II state is not very stable but -IT, IV and VI are quite
stable. . -•
. Nearly closed - shell configuration (I/S2I1p5) of group VII elements makes
these elements highly electronegative. Fluorine has the highest electro-
. negativity of all the elements and cannot give a positive oxidation state.
Other members can show the oxidation states of I, Ill, V and VII. Besides
the -I state (common to all) the stability of the states are V>VlI>III:::;.I.
Chlorine. gives IV and VI states also in CIOz and CI03 respectively.
The closed shell configuration (11.1'2111'6) of the inert gases forming the
.group 0 makes these elements stable towards chemical combination. After
1962, inert gas compounds having the element in oxidation states of lV,
vr, II· and vnr (in order of decreasing stability) . have been characterized.
Only the most reactive clements, fluorine and oxygen,. form inert gas
compounds ..

The Transition Elements

The general electronic configuration (1I-1)d"'ns2 (with a few exceptions) of

the: transition elements suggests' 0) lowest common oxidation state of II by
the lossof 1l~2 electrons and (ii) the. maximum oxidation state of 2+x,by
the loss of·ns and the (Il-I)cf electrons .
. (1) In the 3d series, the Ti(lT) is unstable and strongly reducing; The
stability of 11 state increases with a decrease in the reducing character as d
electrons are added. In 4d and Sd . series, II· slate is unstable except for
Pt(I1) and Pd(II).
(2) The highest oxidation state in the 3d series upto manganese becomes
more oxidizing as' we move ~Iong the period from Sc(lU) to Mn(\~II).
Beyond Mn (dr. in the ground state), electron pairlng commences in the d .
orbitals:in the ground state and the higbes; oxidation state for the subse-
-quentmembers does-not 'exceed VI. In the 4d and Sd series, the higher states
are more stable and less oxidizing than those in the 3d series. Thus Nb(V),
Ta(V), Mo(VJ}, ;W(VI), Tc(VIl) and Re(Vll) arc. almost nonoxidizing. The
. stability of the higher states is in the order .
3d«4d<Sd.
r(3) The transition elements give coordination compounds in zero and
negative oxidation states also by accepting electrons in the vacant d and p
orbitals and thus attain the' inert shell structure of the next inert gas in
. 114 .Theoretical Principles of Inorgunlc C"I'/IIi,\'lry

many cases, Examples include the mctul carbonyls, nitrosyls and phosphine
complexes,. .
(4) Transition clements prefer II coordinatiou numbcr of 6 and 4. (Though
other coordination numbers are also found in complexes).
The; oxidation states of the inner t rnnsition clements have already -bccn
discussed.

ELECTRONEGATlVITY

Electronegatijjry is defined as the power of an atom in a molecule to

attract electrons to itself. Though the clcctronegativity X can be related to
the properties of isolated atoms, it depends on the environments around the '
atom.

Pauling's Electronegativlty X"

Pauling established a scale of clectronegativity based 011 the excess bond
. energy-in hcteronuclear covalent bond A-D. The energy of the bond DA-D
can be considered to be the sum of a nonpolar contribution DnfJ and a polar
contribution, D", which gives additional stability to the covalent bond due to
the coulornblc attractions arising out of the partial ionic nature of bond:
.DA-B = Dn;p+Dl" (3.17)
Pauling assumed that the nonpolar bond energy D..~ is the average energy
of the bond energies .DA-A and Dl1-D
(3.18)
sO that
(3. t 9)
The polar contribution D;p. also called the ionic resonance energy 6.,. 'is a
relative measure of the polarity of the A-B bond. The tendency of the
bonded atoms to attract electrons towards themselves results in the displace-
ment of the bonded pail' ofthe electrons towards one of the atoms. This
makes a bond polar. The negative 6. values for some bonds (metal hydrides)
can be avoided by using .. . .

Dn'P -= .f DA-A·Dil-B
but the ionic contribution is then termed as 6.', It is observed that the A or
6.' values .are not additive, but .f 'K or .fA' values are (table 3.6), provided
that they are not too large. By assuming that .["£., values (or the .[ K'
values) are proportional to the elcctroncgativlty differences (AX) a table of
6.K values can be constructed. Assigning an arbltrnry value to one of the
clements, the whole set of X values can be compiled.
Pauling assumed that"

XA,-Xn = 0.088'.fA" (3.20)

-this and other equations nrc written in S1 Units. '
 rerioatc 'la/l/e mill Periodic Propertles 115

Table 3.6 Elcctl'OlIe.l:ativilY Difference Irum the EnlhalllY oe Formation of Compounds.

Atoms AI'cl'(1ce D _ 11
DA-A Dn-ll A lJ VI1
A D kJ fIIol-1. .kJ /110/-1 kJ 1110/-1
-
II F 4S8 ISS JOG 565 :259 16.1
H Si 4S8 222 340 318 22 4.3
st F, .... 222 ' ISS 188 565 377 19.4
As H 146 458 252 24S -7 2.6
As F 146 ISS 150.5 406· 256.5 160
484·· 334.5 18.3
·AsPa, ··AsPG

and
Xp = 4..0 (3.21) .. ~
and assigned electronegativity values to 14 elements. '
A combination of Eqs. (J..l7J and (3.21) gives
DA-n = E(DA-.d-Dn-nH 129.4(XA,-XlI)2 (~.22)
which shows the contribution of the new bond to the enthalpy of formation
-aH,. As the enthalpy of formation of a compound. AB is defined as
the net enthalpy change for the reaction
~A2+~B2\-~.;\B .
it becomes obvious that
-afl, = ..oA-n-HDA-A+Dn-n) (3.23)
and in general for the. formation of the compound AB",
!A2+ill Dz --? An,. .
-6.H~-;.,.nDA-n-}DA-A--~1/ Dn-n. (3.24)
It can be shown that for the compound An formed from A2 and B2,
Eqs. (3.22) and (3.23) give
, -6.H, = 129.4 (XA-Xn)2 (3.25)
and if the' compound AD" is' formed, uH, would be found by assuming
similar expressions for all the bonds in All" so that
~f:1ll, = 129.411(XA-Xn)2
This implies that
XA-Xn = r _~6.H,
\j 129.411 - (3.25a)

if the number of the covalent bonds does not change during the formation '
of AB" from Az and D2•. '
However, a correction is' necessary for the nitrogen and oxygen com.
pounds because of the extra stability of these elements in the elemental
states. Thus Nz and O, arc stable over the hypothetical molecules contain-
ing three single bonds and two single bonds respectively by
Extra stability ot' N2 = (945,.- 3 X 164)/2 ee 226 kJ/N atom
Extra stability of O2 = (496-2x 138)/2 = 110 kJ/O atom.
 IIG Theoretical Prlnctplcs of Inorganic Chemistry

164 and 133' arc the N__:N and 0-0 single bond energies. These correc-
tions change Eq. (3;25) to '
-Mi, = 129.411 (XA - XlJf-22611N - 110110 (3.26)
whcr? liN and 1,10 nrc the number of Nand 0 at0J11Sin the compound.
By applying these corrections, the clectronegativltics for most of the
elements can'be determined from the enthalpies or
formation of com-
pounds. Some of the values observed nrc: H = 2.2, Li = 0.93, Na = 093,
Mg = 1.31, Al = 1.6, Oa = 1.8, Sc = 1.4, C = 2.55, N = 3.0, P = 2.2,
O = 3.44, S = 2.6; F = 4.0, CI = 3.2, Dr = 3.2, I = 2.7.

Mulliken's Elcetrollcgath'ity X m

For the formation of a pure covalent bond between A and D, the two
hypothetical structures A+B- and A-B+ should ha\;e equal energies. In
A+B-, A loses an electron requiring an input of lEA followed by the accep-
tance of the electron by B with the release of EAB• Hence the energy
change for the formation of A+B- is given by Eq, (3.27), where U is the
su, = IEA-EAB- U (3.27)
lattice energy of the compound A+B-. Similarly, the energy change, for the
formation of A-B+ from gaseous A .and D will he given by Eg.' (3.28),
t.H2 = IEB-EAA- U (3.28)
provided that the internuclear distance in the two forms remains the .sume,
For the pure covalent bond, t.lli = t.lf2, so that, from Eqs. (3.27) and
(3.23),

or
(3.29)
If, however, A+B- and A-B+ are not equivalent, let A+D- be more stable.
In that case, (a) the EAD should be more than EAA so that the formation
of B- is favoured, and (b) IEA should be less than JED so that the Ionization
of A proceeds, i.e.
EAA <EAJl and lE ..,<JEn·
Hence,
EAA+IEA < EAB+IEn.
~imilarJy, if A-B+ is the mo~e favoured structure,
EA,,+JEA > BAn+IEn.
Since, EA+IE becomes the measure of the pull of the electrons by the
atoms, Mulliken defined electro negativity Xm of the atom as
EA+JE
, Xr~ ,""7 2 (3.30)
 , Periodic Table and Periodic Properties, 117

. " As, both EA and IE arc determined in cV units for XII" Mulliken's
electroncgativlty is related to Pauling's electro negativity X" as
X" = 0.336 (Xm-O.615).
" If.EA and IE are dc,term~ncd in MJ mol-oJ (3.31)
'X,,'= 3.47(X~-O.0595). '
"The IE and EA values in Eq, (3.30), arc not the experimental values
determined for the ground state of the atom but arc the calculated values
for the atom in the valence state us it exists in the molecule. Thus for IJcz+
ion which bonds through the sp hybridized orbitals, the IE and EA should
be the' values which refer to the average energy required to remove one
electron from the excited state (ls'2s12pl), or to add one electron to it in
the excited state, viz. for the reactions

'Be (IS22s12pl) -~ ,De+ (ls~2pl) (IE,)

IE"';' t(IE,,+IE.). (3.32)
The Mulliken's scale has the advantage that it can account for the diffe-
rent hybridizations of the element in chemical compounds.

, Allred-Roehow's 1~lectrollcg::lIivj(y X.m

. ,::
Allred and Rochow (1958) defined elcctroricgativity as, the force exerted by
the nucleus of an atorn Oil its valence electrons

X"Alt -- 3590Z·"+,' 0 744

0 r:!. • (3.33)

where Z*' is the effective nuclear charge calculated using Slater'S rules
counting all the electrons for shielding constant' (hence Z·' = Z*-O.35)
and r is the covalent radlus.Iin pill) of the elements. For Is electron shell,
Z·' = Z· - 0.30.'
Gordy plcturized : clectronegativity as a potential due .10 the partially
screened nuclear charge Z* at the surface of the atom and suggested that
Z*e
XG =" --.I' X 100 (3.34)

Of the two, Allred-Rochow's scale has been, widely accepted as an

alternative to Pauling's scale for electronegativitics. The values are similar
to each other.

Stability Ratio sn.

Sanderson (1962) has proposed n scale of clcctroncgntlvitles, or stability
 118 Theoretical Prlnclples of Inorganic Chemistry

ratios (SR) based on the compactness of (he electronic cloud in the valence
.shell of the atoms:
SR = DID; (3.35)
where D is 'the electron density of the atom and D, is the ideal electron
density for the atom calculated by the Iincar interpolation between the D
values of the next higher and next lower inert gas clements.
The SR values are similar (0 the X values and have been extensively used
by Sanderson to explain a large amount of data.

Other Elcetroncgativity Scnlcs

Jaffe's Electronegativlty

.Taffe defined clectronegutivity as

X = dEJdq (3.36)
where E is the total energy of the atom related to the partial ionic charge
q by the quadratic equation, Eq, (3.37).
E ::0 IXq+ ~q2 (3.37)
differentiation of which gives
X = dEldq = «+i~q = a-s-bq. (3.38)
When q = 0, X = a, so that a corresponds to the elcctronegativity of the
. neutral atom. h is culled the coefficient of clectroncgativity or the rate of
change of X with the ionic charge q 011 the atOI11. Large and soft atoms have
low values of b, while small and hard atoms have a larger value of b
(Fig. 3.7).

-:~
>-

"0
8

..
01
c
6

-..
...
0

Ui

-0.5 o 0.5
Charge q
Fig,3.7 ElectronegativiLy (X) of sulphur,
chlorine and fluorine atoms as n fun-
ction of partial charge q on the
atoms.
 Periodic Table and Periodic Properties 119,

Orbital Electronegattvlty

Hinze and Jaff!) (1%2) calculated the promotion energies f~r different states
of an atom and ions for a number of clements and termed the correspond-
ing electronegativity Xo a; the orbital electro negativity. The orbital electro-
negativity is found to increase with the s character of the orbital due to the
penetration cirec!s and also witii rhe occupancy of th~ orbital.
:" ";'; 31E-EA ;,: IE+EA ,.·.·3 EA-IE (3.39)
'\0 = . 2 ' '\1 =, :-2'..' ,-1:2 =: 2"
where X, stands for the orbital clcctroncgativity of the system having i elec- .
trans in the orbital. .

Bo;,,1 Electronegativity

Bond elcctrouegativity Xb is defined as the elcctroncgativity of the bonding

. orbitals after the partial charge transfer has taken place in a bond. The
'\ orbital electrouegativity
.'
XI can be defined as
oE
,
X,=- (3.40)
011/
where "I is 'the number of electrons occupying the orbital having energy E.
If, of the two electrons utilized for the bond formation, II ... electrons reside
on' A and n» on B (11,1 + 11.11 = :;),the electron distribution will be such that
XS(1I0) = X ...(II,,). A plot of X ... against IIA and of Xs against 110 will give
two intersecting lines. The point of' intersection will give the equilibrium
values II... and lis ill a bond.
:~., Ir ; , ' '

. Group Electronegativittes

The electronegativities of the atoms adjusted for the presence of substituents

'are called the group electronegatlvities. Thus, we may say that the electro-
negativity of CH3 is 2.3, CFa is 3.35, cci,
is 3.0, CN is 3.3, COOH is 2.85,
. N02 is 3.4, CaH~ is 3.0, OH is 3.5-3.9. The group clectroncgativlties have
been calculated from the kinetic data, dipole moments and atomic electro-
nega ti vi ties.

Elcctroncgativity Neutralization

The 'formation of a covalent bond between two elements having different.

elecjronegatlvities will result in shifting of tile bonding electron pair towards
tile more electronegative atom, resulting in the partial charge separation.
Initially, the more electronegative atom will have a greater attraction for the
electrons but as the electron transfer takes place, its clcctronegativity will
. decrease with the increasing partial negative charge. 011 the other hand, the
other atom will lose the electron pair becoming positively charged and its
electroaegativlty will increase. The process of charge transfer will continue
till :the electronegatlvitles
• 4" '"
of both the atoms become' equal. Thus for the for-
,'-'" •. ",. • • "
 120 Theoretlcal Prillcipl.·s 0/ Inorgalllc Chemistry

Illation A+B- having partial charge separation of q units, Eq. (3.38) gives
X,4 == oA-bAq
and
Hence,
Q,c-OB (3.39)
q :s: bAi-b» .
The charge separation can therefore be calculated from the electron ega ti-
vities of the atoms using Eq. (3.39). For HCI,
9.38-7.17 - 0-09?"
q = 11.30+12.85 = . -'
Though this approach (Sanderson) may be correct, the q values are always"
low. This may be due to the neglect of (i) exchange energy associated with
the orbital overlap which _decreases with the charge separation and (ii) the
Madelung energy "resulting from the electrostatic attraction of A+ and B-
within the molecule. "
Pauling has proposed the electroueutralttv p/'il/~ju_le' that the electrons are
displaced in a molecule in sucll a way that the residual charge on each atom
is zero or very nearly zero, being slightly positive for the electropositive
elements and slightly negative for the electronegative elements, The charge
on the bonded atoms can be decreased by (i) a change in the polarity of the
bond or the ionic character of the bond, (ii) change in the multiple character
of the bond. Thus a formal charge of -f-3 on the hypothetical structure in
Fig. 3.8(a) is reduced to +2 in Fig. 3.8 (b) +
I in (c) and zero ill (d) for
the perchlorate ion. The actual bond order of CI-O bond in CIO, - ion
is 1.6 indicative or' the relative importance of the structures (a) to (<I).

eo eo 0
""-3m "" " CI
/09
' "-2V CI

90/ ""-09 e 0/ "'09

101 Ibl

e O""-e/O o 0
" CI
~/ CI

/ "'06 / ""-09
Icl Idl

Fig. 3,8 The canonical forms of perchlorate ion.

Fllc~ol'!- Af~ccting Elcctrollcgntlvily

Blcctronegatlvlty of an atom is not a fixed quantity. but' depends 'upon a

large numberol' Iactors.iboth of isolated us well as bonded atoms. 'Some of
 Periodic Table and Periodic Properties 121

the important factors nrc given below:

(1) Valence state.
The electronegativity increases with the positive oxida-
tion state of the atom, as the tendency to attract all electron will increase
with the positive charge of the cation. For anions, however, the electro-
negativity decreases with the increasing charge of the ion (Eq. 3.38).
(2) Hybridization. As an s electron is nearer the nucleus due to its pene-
trating power, the elcctroncgativity increases with the increasing s character
of the hybrid orbitals. Thus Xm for carbon.is 2.48, 2.75 and 3.29 for thc
Sp3, sp~ and sp slate respectively. For the nitrogen atom, the values of the
electronegativity (Xt" values) arc 3.68, 3.94 and 4.67 for Sp3, sp'f and sl'
hybridization respectively. . , .' .
(3) Partial ionic charge. The electrouegativity increases with the (partial)
positive charge on the .atom [Eq. (3.31i)]. Thus the electroacgutivity of 1+
(4.5) is greater than that of F (4.0).

PROBLEMS

J. On what basis have atomic numbers .been assigned to the clements? What is
their. significance? . .
2. What is the relationship between the atomic number and the periodic classifica-
tion of elements ?, "
; 3. Select as many triads as possible from the pcriodlc table which arc similar to
those of Doberelner,
4. Why was Newland's law of octaves ridiculed when proposed in 1864 ?
S. Enumerate the weaknesses of Mcndclcev's form of the chart of the clements.
How valid is the chart in the light of modern discoveries ? .
,6. Describe Moseley's contribution towards the development of the modern form
of the periodic table of elements.
7. Give the rcliltionsllip between the atomic number and atomic weight, if any.
8. Why is the periodic table divided into short and long periods 'and groups? How
do the properties of elements change in a period and in a group? .
9. To what extent, if any; is' .the long form of the periodic table an improvement
over the periodic table of Mendelcev ? .
10•. What are s, p, d and! types of chiments? DIscuss the ,main characteristicsof these
element with reference to the kind of electrons present in the outer orbitals?
11., Discuss the position' of potassium;' argon, hydrogen, chlorine, metals, and non-
metals In: the periodic table.
12. . From the positions in the periodic table, predict the properties or astatine
(Z,= 85), radon (Z co 86) and francium (Z ... 87).
13. Describe the properties of element with Z = 104, 112, 126 and 164.
14. WhliJ are the different properties of clements which arc periodic Iunctions of the
atOmic numbers?
IS. hi which columns (period and group) pf the periodic table arc found elements
having (a) llighest densities, (b) highest meltillg points, (c) lo\vest melting point~,
(d) light metals, (c) beavy metals, (0 highest tensile strength, (g). highest con-
Il2 Theoretical Principles of lnorsanlc Clu!/Ilistry

duetivlty, (h) strong oxyaclds, (i) volatile. hydrides, (j) high electron affluirles,
(k) highest elcctroncgatlvities, (I) lowest lonlzatlon potentials, (01) highest
ionizntlon .energy? '
16. How docs the ionization energy or an element vnr)r across the pcrlod and down
the group in a periodic table '/
17. Define successive ionlzation energies for lin clement.
IS. Why is tho ionization energy of (l) B and AI less than that of Be and MS; (ii) 0
. and S less than that of N-and P ; (iii) Nz more than that of NO or O2 ?
19. Which will have higher loofzatlon energy: Nz or CO '/ Why?
20. What, if aDY, is the electron afliDity of gold ? Why? _, . .
21. Define electron afliility, Why is the electron affinity of almost nll the clements
negative? ' _. .
22. Define and distinguish between (a) Pauling's clectroncgatlvity, (b) Mulliken's
elcetroneglUivily, Cc) orbital cleetrollcgativity. '
23, How docs elcctrouegativlty depend upon (a) the size of tnc atom, (b) hybridit.a-
tion, (c) the valence, (d) ionization energy, (c) ionic potential? -'_
24. "Highcr elcctronegativlty difference docs not always lead to bi~her bond energy."
Comment. See Ch. 7 also.
2S. Despite the differences in clectronegativity between carbon and hydrogen, the
C-H bond is nonpolar, Give possible reasons. -
26. How is the electronegatlvlty diITerenee related tv the ionic character of a covalent
bond? From the clcctroncgatlvity values, determine the percentage ionic
character of the C-F, C-CI, C-O, Si-CI, I-I-CI, H-., N-H, N-F, O-~~
and O-CI bonds.
27. Which is more electronegative and why: K or Cs; Dr or CI; Mg or AI; P or
As; AI or Ga; Li or Be; Cu· or Ag ? '
28. Define atomic, covalent, metallic and ionic radii for an clement and clearly
distinguish between the diITeront values.
29. Distinguish between the ED map radii, ionic radii, orbital radii and covalent -
radii. -
30. What are the factors that determine the covalent or' ionic radii? '
31. . Why arc the sizes of inert gas atoms larger than their corresponding halogen
atoms? .
32. Why are the atomic radii of alkali metals very large?
33. Whieh ODe has n larger radius (i) Ni, Cu or Zn; . (ii) Ni2+, CuH or Zn2+ ions ;
(iii) F-, Ne or Na+; (iv) Zr or Hf; (v) As or Sb; (vi) N or 0; (vii) P or S?
34. Why is the decrease in the size between Li and Be greater than the decrease from
K toCa?
3S,. Explain tho smaller dilrcrences in the sizes of Cu, Ag,' and Au lind their ions us
compared with the alkali metals.
36. Distinguish between the valence,' oxidation number, coordination number, the
formal charge, and the residual charge on an atom ill a compound, taking s~itable
examples. (Look up Ch. 12 also.) ,
37. Which Is more polar iltld why: Water or ]-125; NH3 at' PHa; AsCI~, PCI~ or
NCla; NHa or NFa '/ Use the data tllat you need,
38. Explain wby (i) carlonlc mdll nrc lower but anionic radii arc larger than atomic'
radii, (il) the ionization energies of the elements are In the order Ar>CI>K,
(iii) Cs is :I. better photo-emitter thuu Na, (iv) As has a higher first ionization
energy than So, (v) the first ionization energy of N is more, but the second ioniza-
tion energy is less than that of O.
39. Why Is tbe atom oC sodium bigger than tho atom of both lithium lind magnesium ?
40. How docs the discovery oC 'the inert gases strengthen our bellef III the fundu-
mental nature of the "crlodie table? .
41. ,Why do normal clements ill tho same family show similarities and also gradual
changes in their chemical and the physical properties?
 Periodic Table and Periodic Properties 123

42. The values for three of tho quantum numbers for the last electron in elements are
listed below. To what period and group of the periodic table do these elements
belong, and what arc their main characteristics?
I /11· S
A I -I-I -H
U :) -2 -i
C 3 0 -i
n 2 -H.
~3. Cite examples to show that half-filled II ot i! orbitals have extra stability.
44. Writeeloclr\'nic configurations or (i) ulkari metals (atomic numbers 3, II. 19. 37,
55.87). (il) carbon family (atomic numbers 6, 14.32. SO, 82), (iii) nitrogen family
{atomic numbers 7, 15.33. 51. 83) and (iv) halogen fumily (atomic numbers
9,17,35,53.85). Prove ihat elements wilh a similar configuration of incomplete
orbitals show similar properties.
45. Trace the development of periodic law. or what usc has the poriodic table of the
elements been 7 •
46. lxplain why (i) lir.>! ionization energy of boron. (O.S MJ) is less than that of
beryllium (0.9 MJ). (ii) there is a bill jump from 1.8 MJ to 15.3 MJ for the second
and third ionization energy of beryllium as compared with a change from 2.45 MJ
to 3.7 MJ for boron. (iii) the third ionization energy of nitrogen (4.6 MJ) is less
than that for chlorine (4.7 MJ), (lv) electron affinity of halogens is in the order
F <Cl > Br > I. (v) the third ionization energy of nitrogen Is less than that of car-
boo, while others are higher, and (vi) generally the atomic sizes increase with the
increase of the atomic number in a group (the increase is more for the lighter
members ofthe Ilroup) ..
47. Someone claims to have discovered au clement with an atomic weight of 2 or 3.
This supposedly Ilts between hydrogen and helium in the periodic table. Criticize
or defcnd the case. .
. 48. Which of the followins has a higher:
(a) first ionization en~rgy. F or CI;
(b) electron affinity 0 or 0-;
(c) ionic radius K+ or Cl-;
(d) polarizing power Na+ or F-.
Give reasons. . .
49. Less energy is needed to remove one electron trom a neutral atom than is requir-
ed to remove the electron from the resulting iou. Explain;
50. Arrange the following species in the order of their Increasing radii: 02-. F-,
MgH, Na+, .
51 •. The wavelengths of iho K« lines of the characteristic x-ray spectrum of iron
(Z"'" 26) and potassium (Z .. 19) arc 19.3 nm and 37.4 um, respectively, Calcu-
la.to the atomic number and name the clement for which characteristic Ka. line
is at 22.9 nm. . .
52. Both transition as well as nontransition elements show variable valencies. Wby?
53. In general. univalent lens of the transition metals do not exist. Why 7

\.