MCH-011

INORGANIC Chemistry-1

CH3 H
CH3

CH3 OH H
OH
H C N
CH3 ? H
CH3 N
S=O NO2 OH OH

? CH3
OH OH

NO2

H2O
Na O Na H

H O
Na
CH3
H CH3 ?

O2 OH OH

H2 ? CH3

O CH3 CH3
OH
OH
HC O
CH3
O CH2
CH3 H 20 + CH3

Main Group Elements, Transition Elements, Vol - I

Structure of Molecules & Organometallic Chemistry
 MCH-011

Indira Gandhi National INORGANIC CHEMISTRY-I

Open University
School of Sciences

VOL.

1
MAIN GROUP ELEMENTS, TRANSITION
ELEMENTS, STRUCTURE OF MOLECULES AND
ORGANOMETALLIC CHEMISTRY

BLOCK 1
MAIN GROUP ELEMENTS, TRANSITION ELEMENTS
AND STRUCTURE OF MOLECULES 4

BLOCK 2
ORGANOMETALLIC CHEMISTRY 81
 INORGANIC CHEMISTRY-I: INTRODUCTION
The course Inorganic Chemistry I (MCH-011) is the first course on inorganic chemistry being offered in
the first semester of the M.Sc. Chemistry Programme and is worth 4 credits. The course has been
divided into four blocks.
The first block has three units which deal with main group elements, transition elements and structure
of molecules. In this block, the first unit deals with the periodic trends of main group elements &
transition elements along with their electronic configuration and also includes Latimer diagrams.
Thereafter, in the other units phosphorus-nitrogen and sulfur-nitrogen compounds as well as the
structure of molecules has been discussed in the other units.
The second block gives the complete picture of organometallic chemistry. Here there are six units. The
topics that are included in this block are organometallic compounds, metal carbonyls, metal pi-
complexes and metal clusters
The third block is on crystal field theory and the applications as well as the limitations of crystal field
theory and they are covered in two units.
Block four is on basics of magnetochemistry, d-metal complexes magnetism, electronic spectra and d-
d transition and charge transfer spectra. In this block, there are four units.
You are expected to spend a total of about 120 hours for completing this course. This is the average
time which is be spent by a learner on studying the course material, doing self-assessment questions
as well as terminal questions given in the blocks and the assignment, attending counseling sessions,
watching the audio-video programmes and participating in IRC/ teleconferencing sessions related to
this course.
We hope you will find this course quite interesting to study. Our best wishes.
Expected Learning Outcomes
After studying this course, you should be able to
 discuss the periodic trends of main group elements & transition elements along with their
electronic configuration;
 discuss the stability of various oxidation states for Mn, Fe and Cu along with Latimer diagrams;
 describe the postulates of valence shell electron pair repulsion theory;
 predict the shapes of molecules (along with point groups) on the basis of valence shell electron
pair repulsion theory;
 describe Walsh Diagram for triatomic and penta-atomic molecules;
 understand d-p bond;
 discuss Bent’s rule and energetics of hybridization;
 describe geometric and optical isomers;
 understand the synthesis and, structure of phosphorus-nitrogen compounds;
 discuss about the ring and chain Compounds of sulfur-nitrogen compounds;
 define and classify organometallic compounds;
 understand the concept of hapticity;
 discuss about the synthesis, structure and bonding of organometallic compounds of alkali and
alkaline earth metals along with their uses;
 discuss about the organometallic compounds of transition metal alkyls and aryls;
 discuss about the organocopper compounds along with their applications;
 understand EAN Rule and 18 Electron Rule as applied to carbonyls;
 describe the preparation of metal carbonyls through direct combination and reductive
carbonylation;
 understand the structure of metal carbonyls based on Valence Bond approach;
 describe the properties of mononuclear and polynuclear carbonyl of 3d metals;
 understand bonding, -acceptor behaviour of carbon monoxide with reference to MO diagram of
CO, explain synergic effects;
 understand the use of IR stretching frequency data for bonding and structure elucidation of
carbonyls;
 discuss about transition metal nitrosyl complexes;
 discuss the transition metal dinitrogen as well as dioxygen complexes;
 understand tertiary phosphine as ligand;
 discuss the alkene, alkyne, allyl diene and cyclopentadienyl metal pi- complexes;
 understand metal pi-complexes with arenes and other alicyclic ligands;
 discuss higher boranes including Wade’s Rules;
 compare and describe the carboranes, metalloboranes and metallocarboranes;
 discuss compounds with metal-metal multiple bonds;
 describe metal atom cluster compounds and metal carbonyl type clusters;
 discuss electron counting in medium size clusters and the Capping Rule along with their
limitations and exceptions;
 discuss the crystal field theory;
 describe the crystal field splitting in octahedral complexes;
 calculate the crystal field stabilization energy (CFSE);
 discuss the crystal field effects in weak and strong fields;
 come to know about the factors affecting the magnitude of crystal field splitting energy;
 get introduced to the spectrochemical series;
 understand crystal field splitting in tetrahedral complexes;
 compare the crystal field stabilization energy(CFSE) for octahedral and tetrahedral complexes;
 understand crystal field splitting in tetrahedral complexes;
 compare the crystal field stabilization energy(CFSE) for octahedral and tetrahedral complexes;
 understand the tetragonal distortion of octahedral geometry(Jahn-Teller distortion);
 learn about formation of square planar complexes and note the crystal field splitting in such
cases;
 learn about some common applications of complexes including their magnetic behaviour;
 discuss the applications of crystal field theory, in context with lattice energies and ionic radii;
 understand thermodynamic aspects like heats of ligation and site preference energies;
 appreciate the limitations of crystal field theory in context with molecular orbital theory and
nephelauxetic effect;
 discuss pi-bonding and molecular orbital theory
 define magnetic properties;
 understand the types of magnetic bodies and paramagnetism: orbital & spin contribution;
 discuss the magnetic properties specially of the first transition metal ions lanthanoids and
actinoids;
 understand the methods for magnetic susceptibility measurements; and
 derive the Van Vleck equation
 discuss about ferromagnetism and antiferromagnetism;
 understand the mechanism of anti-ferromagnetic interaction, namely the direct metal-metal
interaction and superexchange;
 discuss about spin cross over and anomalous magnetic moments;
 understand the applications of magnetic measurement for structural elucidation.
n
 define spectroscopic terms like the R-S coupling of d system and Racah parameters;
 understand the correlation of spectroscopic terms;
1 9
 discuss the Orgel and Tanabe-Sugano diagrams for transition metal complexes (d -d states).
 define selection rules and d-d transition in metal complexes;
 discuss about charge transfer spectra like LMCT transitions, MLCT transitions;
 understand the Nephelauxetic series;
 discuss the spectroscopic method of assignment of absolute configuration in optically active
metal chelates and their stereochemical information; and
 understand about inter-valence.
 MCH-011

Indira Gandhi National INORGANIC CHEMISTRY-I

Open University
School of Sciences

BLOCK

1
MAIN GROUP ELEMENTS, TRANSITION ELEMENTS,
STRUCTURE OF MOLECULES

UNIT 1
General Characteristics of Main Group Elements and
Transition Elements 7

UNIT 2
The Structure of Molecules 43

UNIT 3
Phosphorus-nitrogen and sulfur-nitrogen compounds 68
Course Design Committee
Prof. H. Surya Prakash Rao (Retd.), School of Sciences,
Department of Chemistry, IGNOU, New Delhi
Pondicherry University, Puducherry
Prof. Sujatha Varma
Prof. Ashok Kumar Mishra, Prof. Sunita Malhotra
IIT Madras, Tamil Nadu Prof. B.I. Fozdar
Prof. Javed A. Farooqi
Prof. Tabrez Alam,
Department of Chemistry, Prof. Sanjiv Kumar
Jamia Millia Islamia, New Delhi Prof. Lalita S. Kumar
Prof. Kamalika Banerjee
Prof. Ghanshayam Bez,
North-Eastern Hill University,
Shillong, Meghalaya

Prof. Sunil Sharma,

Department of Chemistry,
University of Delhi, Delhi

Dr. Pritam Mukhopadhyay

Department of Chemistry,
Jawaharlal Nehru University,
New Delhi

Course Preparation Team

Prof. Kamalika Banerjee Prof. Gurmeet Singh (Editor)
School of Sciences, IGNOU Vice-Chancellor, Pondicherry University

Course Coordinator: Prof. Kamalika Banerjee

Print Production
Mr. Rajiv Girdhar Mr. Hemant Kumar Parida
Assistant Registrar (Pub), Section Officer (Pub),
MPDD, IGNOU, New Delhi MPDD, IGNOU, New Delhi

Acknowledgements: Sh. Sarabjeet Singh for CRC preparation and Sh. Deepak Kumar for word
processing.

December, 2023
@ Indira Gandhi National Open University, 2023
ISBN:
All rights reserved. No part of this work may be reproduced in any form, by mimeograph or any other
means, without permission in writing from Indira Gandhi National Open University.
Further information on Indira Gandhi National Open University courses may be obtained from the
University’s office at Maidan Garhi, New Delhi-110068 or IGNOU website www.ignou.ac.in
Printed and published on behalf of Indira Gandhi National Open University, New Delhi by the
Registrar, MPDD, IGNOU.
Printed at
BLOCK 1: MAIN GROUP ELEMENTS, TRANSITION
ELEMENTS AND STRUCTURE OF
MOLECULES

The course Inorganic Chemistry I (MCH-011) is the first course on inorganic chemistry being offered in
the first semester of the M.Sc. Chemistry Programme. It is worth 4 credits i.e. you have to spend a
total of 10 hours for this course. The course has been divided into four blocks.

The first block has three units which deal with main group elements, transition elements and structure
of molecules. In this block, the first unit deals with the periodic trends of main group elements &
transition elements along with their electronic configuration and also includes Latimer diagrams.
Thereafter, in the other units phosphorus-nitrogen and sulfur-nitrogen compounds as well as the
structure of molecules has been discussed in the other units.

Expected Learning Outcomes

After studying this block you should be able to:

 discuss the periodic trends of main group elements & transition elements along with their
electronic configuration;

 discuss the stability of various oxidation states for Mn, Fe and Cu along with Latimer diagrams;

 describe the postulates of valence shell electron pair repulsion theory;

 predict the shapes of molecules (along with point groups) on the basis of valence shell electron
pair repulsion theory;

 describe Walsh Diagram for triatomic and penta-atomic molecules;

 understand d-p bond;

 discuss Bent’s rule and energetics of hybridization;

 describe geometric and optical isomers;

 understand the synthesis and, structure of phosphorus-nitrogen compounds; and

 discuss about the ring and chain Compounds of sulfur-nitrogen compounds.

Unit 1 General Characteristics of Main Group Elements and Transition Elements

UNIT 1

GENERAL CHARACTERISTICS
OF MAIN GROUP ELEMENTS
AND TRANSITION ELEMENTS

Structure
1.1 Introduction Electronegativity
Expected Learning Outcomes Electrode Potential
1.2 Periodic trends of Main Group Oxidation States
Elements & transition
elements
1.3 Stability of various Oxidation
Electronic Configuration (Along States for Mn, Fe and Cu
with IUPAC Periodic Table)
Latimer Diagrams
Periodic Trends in Properties
Atomic Radii
1.4 Summary
Atomic Volume and Density
1.5 Terminal Questions
Melting and Boiling Points
1.6 Answers
Ionisation Energy
1.7 Further Reading

1.1 INTRODUCTION
This is the first unit in the first block of the Inorganic Chemistry I course of the
M. Sc. In Chemistry program. In the previous courses you must have studied
that the properties of elements are a periodic function of their atomic numbers.
As a result of their similar valence-shell electronic configuration, elements
belonging to the same group of periodic table exhibit similarities in properties.
Further, they also exhibit a gradation in properties with their position in the
group because of the valence electrons occupying different electronic levels.
The differences in the properties of the elements arise due to differences in
the atomic properties like the atomic size, ionisation energy, electronegativity
etc. These atomic properties are directly related to the total electronic
configurations of the elements and form an important link between the 7
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

properties of elements and their electronic configuration. In this unit you will
study the periodicity in these atomic properties of the main group elements in
general as well as those of the transition elements. You will also be learning
about Latimer diagrams. In the next unit you will be learning about the
structure of molecules.

Expected Learning Outcomes

After studying this unit you should be able to:

 discuss the periodic trends of main group elements & transition elements
along with their electronic configuration; and

 discuss the stability of various oxidation states for Mn, Fe and Cu along
with Latimer diagrams.

1.2 PERIODIC TRENDS OF MAIN GROUP

ELEMENTS & TRANSITION ELEMENTS
1.2.1 Electronic Configuration
In the previous courses, you must have learnt in detail about the electronic
configuration of multielectron atoms.

The atomic properties of the elements depend on their electronic

configuration. The electronic configuration of Group I elements are given in
Table 1.1.

Table 1.1: Properties of the Group I metals

Property Lithium Sodium Potassium Rubidium Caesium

Li Na K Rb Cs
Atomic number 3 11 19 37 55
1 1 1 1 1
Electronic configuraiton [He]2s [Ne]3s [Ar]4s [Kr]5s [Xe]6s
Atomic weight 6.939 2.898 39.102 85.47 132.905
Covalent radius (pm) 123 156 203 216 235
Ionic radius (pm) 60 95 133 148 169
Boiling point (K) 1620 1154 1038 961 978
Melting point (K) 453 371 337 312 301.5
3 -3
Density (10 x kg m ) 0.53 0.97 0.86 1.53 1.87
Electronegativity (Pauling) 1.0 0.9 0.8 0.8 0.7
Electronegativity (A/R) 1.15 1.0 0.9 0.9 0.85
-1
Ionisation energy (kJ mol ) 520 495 418 403 374

The electronic configuration of Group II elements are given in Table 1.2. The
alkaline earth metals are quite soft metals, but are harder than the
corresponding Group I elements. This is because of their two valence
8 electrons which participate in metallic bonding.
Unit 1 General Characteristics of Main Group Elements and Transition Elements

Table 1.2: Properties of the Group II metals

Property Beryllium Magnesium Calcium Strontium Barium Radium

Be Mg Ca Sr Ba Ra
Atomic number 4 12 20 38 56.88
1 1 1 1
Electronic configuraiton [He]2s [Ne]3s [Ar]4s [Kr]5s [Xe]6s1 [Rn]7s2
Atomic weight 9.012 24.312 40.08 87.62 137.34 226.02
Ionic radius (pm) 31 65 99 113 135
Covalent radius (pm) 89 136 174 191 198
Boiling point (K) 3243 1380 1760 1607 1413 1700
Melting point (K) 1553 934 1118 1062 998
Enthalpy of hydration -2455 -1900 -1565 -1415 -1275
-1
(kJ mol )
3 -3
Density (10 x kg m ) 1.85 1.74 1.54 2.6 3.62 5.5
Electronegativity 1.5 1.2 1.0 1.0 0.9 0.9
Ionisation energy 900 738 590 549 502 509
-1
(kJ mol ) I
II 1757 1450 1146 1064 965 975

Transition elements have properties which are transitional between the s and
The two terms d-
p blocks. In the s- and p-blocks, electrons are added to the outer shell of the block metal and
atoms. The IUPAC definition of a transition element is an element that has an transition metal are
incomplete d subshell in either the neutral atom or its ions. The latest periodic often used
table by the International Union of Pure and Applied Chemistry (IUPAC interchangeably;
Periodic Table of the Elements) is given below in Fig. 1.1. however, they do not
mean the same thing.

Fig. 1.1: IUPAC PeriodicTable of the Elements.

9
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

The d- block of the periodic table contains the elements of the groups 3-12 in
The f-block consists which the d orbitals are progressively filled in each of the four long periods.
of elements in which
Using the IUPAC definition of transition elements, the elements of Group 12
4f and 5f orbitals are
would not be called transition elements as they do not have incompletely filled
progressively filled.
d shells even in any of their compounds. Thus, two of the Group 12 elements
They are placed in a
(Zn, Cd) are members of the d- block but are not transition elements as they
separate panel at the
do not have any compounds with an incomplete d subshell. The situation for
bottom of the periodic
the third Group 12 element, mercury, is different. Very recently it has been
table. The names
reported that mercury forms a compound in the mercury (IV) state (HgF 4),
inner transition metals
which has the d8 electron configuration. This qualifies mercury as a transition
is often used to refer
metal.
to the elements of
f- blocks elements. Using the IUPAC definition there are four series of transition elements and
they are discussed below.

The first series of transition elements: Sc(21) to Zn (30), here 3d orbitals are
filled.

Table 1.3: Electronic configuration of the free atoms and dispositive ions of the
first transition series

Element Name Free atom Free M2+ ion Element Name Free atom Free M2+ ion
1 2 1 6 2 6
Sc Scandium [Ar]3d 4s [Ar]3d Fe Iron [Ar]3d 4s [Ar]3d

Ti Titanium [Ar]3d24s2 [Ar]3d2 Co Cobalt [Ar]3d74s2 [Ar]3d7

3 2 3 8 2 8
V Vanadium [Ar]3d 4s [Ar]3d Ni Nickel [Ar]3d 4s [Ar]3d
5 1 4 10 1 9
Cr Chromium [Ar]3d 4s [Ar]3d Cu Copper [Ar]3d 4s [Ar]3d

Mn Manganese [Ar]3d54s2 [Ar]3d5 Zn Zinc [Ar]3d104s2 [Ar]3d10

The second series of transition elements: Y(39) to Cd (48), here 4d orbitals

are filled .
Table 1.4: Electronic configurations of elements of the second transition series

Element Name Free atom

Y Yttrium [Kr]4d15s2
Zr Zirconium [Kr]4d25s2
Nb Niobium [Kr]4d45s2
Mo Molybdenum [Kr]4d55s2
Tc Technetium [Kr]4d55s2
Ru Ruthenium [Kr]4d75s1
Rh Rhodium [Kr]4d85s1
Pd Palladium [Kr]4d105s0
Ag Silver [Kr]4d105s1
Cd Cadmium [Kr]4d105s2

The third series of transition elements La(57) and then Hf(72) to Hg(80), here
10 5d orbitals are filled.
Unit 1 General Characteristics of Main Group Elements and Transition Elements

Table 1.5: Electronic configurations of elements of the third transition series

Although lanthanoid
Element Name Free atom means 'like
lanthanum' and so
La Lanthanum [Xe]5d16s2 should not include
lanthanum,
Hf Hafnium [Xe]4f145d26s2
lanthanum has
Ta Tantalum [Xe]4f145d36s2 become included by
common usage.
W Tungsten [Xe]4f145d46s2 Similarly, actinoid.
The ending 'ide'
Re Rhenium [Xe]4f145d56s2
normally indicates a
Os Osmium [Xe]4f145d66s2 negative ion, and
therefore lanthanoid
Ir Iridium [Xe]4f145d76s2 and actinoid are
14 10 1
preferred to
Pt Platinum [Xe]4f 5d 6s lanthanoid and
14 10 1 actinide. However,
Au Gold [Xe]4f 5d 6s
lanthanide and
14 10 2
Hg Mercury [Xe]4f 5d 6s actinide are still
allowed owing to wide
The fourth series of transition elements Ac(89) and then Rf(104) to Cn (112), current use. This is
here 6d orbitals are filled. as per the IUPAC
recommendations.
Table 1.6: Electronic configurations of elements of the fourth transition series

Element Name Free atom

1 2
Ac Actinium [Rn]6d 7s

Rf Rutherfordium [Rn]5f146d27s2
14 3 2
Db Dubnium [Rn]5f 6d 7s

Sg Seaborgium [Rn]5f146d47s2
14 5 2
Bh Bohrium [Rn]5f 6d 7s
The “Inner transition
Hs Hassium [Rn]5f146d67s2
metals” are the
14 7 2 following 30 elements
Mt Meitnerium [Rn]5f 6d 7s
of Lanthanoids and
Ds Darmstadtium
14
[Rn]5f 6d 7s
10 1 Actinoids:
The first series of
Rg Roentgenium [Rn]5f146d107s1 inner transition
elements or
14 10 2
Cn Copernicium [Rn]5f 6d 7s lanthanoids: La (57)
to Lu (71)
You have learnt earlier how the penetration of inner electron core influences The second series of
the radial distribution functions of various orbitals. The extent of penetration inner transition
decreases as elements or actinoids:
Ac(89) to Lr (103)
s>p>d>f

The way in which the energy–levels of different individual orbitals change in

multi-electron atoms, depends a lot on the population of other levels.

You have studied previously that all the subshells of a principal shell (like
those of 3s, 3p, 3d) of a hydrogen atom have the same energy. The same is 11
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

not true for complex atoms, where the ns orbitals, which penetrates most,
have the highest increase in effective nuclear charge. So,the energy of ns
orbitals drops much below the corresponding energies of the np or the nd
atomic orbital. In multielectron system the 4s orbital lies a little lower in energy
than the 3d orbital. But, the situation changes when the 3d orbitals get filled
up with some electrons. If you follow the Fig 1.2 you will understand the radial
distribution curves of the 3d and 4s orbitals. Thus after argon, in potassium
and calcium the electrons enter the 4s orbital rather than 3d. The radial
distribution functions for the two orbitals is shown in Fig. 1.2.

Fig. 1.2: Radial distributions of 3d and 4s atomic orbitals in H-atom (qualitatively).

After the addition of a few 3d electrons, the energy of the 3d orbitals fall below
the 4s level quite fast because the 3d electrons experience more effective
nuclear charge. So, at the beginning you will see that the 4s orbital has lower
energy. But if you look at Fig. 1.2, you will see that, on addition of some
electrons in 3d level, the 3d orbitals becomes lower in energy than those of 4s.

Let us study the last electrons in K and Ca enter the 4s orbital after argon core
as 4s is more stable than 3d. But since the 4s and 3d orbitals are very close
to each other in energy, the last electron in Sc has the 3d orbital occupied,
having the ground state electron configuration as 3d14s2.But the relative
ordering of the energy levels in scandium changes, as the binding energy of
the 3d electron rises suddenly. Thus it would require much more energy to
remove the electron in 3d than that in 4s. Hence the ground state
configuration of the Sc+ ion is [Ar]3d14s1 and not [Ar]3d04s2.

After Zn ([Ar] 4s23d10) that comes the p-block elements as you can see in the
periodic table in Fig. 1.1. The next lowest available orbital is 4p which has the
capacity of taking up a maximum of six electrons. So in the next six elements,
the 4p orbitals are filled in a regular manner. The noble gas Krypton (Kr) has
the configuration [Ar]3d104s24p6. Thereafter comes the question, which orbital
will be filled up first, 4d or 5s and 5p? Well, the 4d orbital has higher energy
compared to 5s and 5p. So, the two s-block elements come after that followed
by the second transition series, with Y as [Kr]4d15s2 and Ag as [Kr]4d105s1.
Thereafter comes Cd as [Kr]4d105s2 and the six p-block elements which ends
at the noble gas Xe as [Ar] 4d105s 25p6. After this the 4f, 5d and 6s orbitals are
available.

Now, if you look at the Fig. 1.2 where the variation of energies of atomic
orbitals are shown against the increasing atomic numbers, you can notice that
around Z=50, the change in energy of the individual atomic orbitals is very
12 complicated. The 4f orbital cannot penetrate much in the xenon core and so
Unit 1 General Characteristics of Main Group Elements and Transition Elements

has little stability. But, the situation changes when the 6s orbital gets filled up
with two electrons, into which the 4f penetrates much, thus the enhanced
nuclear charge sharply lowers the energy of the 4f orbital. You can see in the
Fig. 1.2 that the lines for 5d and 4f orbitals merge in this region of atomic
number.

In the third transition series, which starts with La, the last electron enters a 5d
orbital. Thus from lanthanum to lutetium, they are classed as lanthanoids. The
electronic configurations of transition elements of 4d, 5d and 6d transition
series are given in Table 1.3, Table 1.4 and Table 1.5 respectively.

In the first transition series, V has the configuration [Ar] 3d34s2, the next
element is Cr which should have another electron entering the d-orbital thus
making it [Ar]3d44s2, whereas the actual configuration is [Ar]3d54s1, which is
half-filled and preferred.

Next let us look at the configuration of Cu (of first transition series) which
follows Ni([Ar]3d84s2). This is also a very interesting case. It should have been
[Ar]3d94s2, but instead it prefers the more stable completely-filled
configuration, which is [Ar]3d104s1.

So, you can see that exactly half-filled and (completely) filled orbitals are more
stable for both the first and second transition series. This is because half-filled
and completely filled orbitals have an exchange energy which is much greater
than the exchange energies associated with any other configuration.

Let us compare the exchange energy for two possible configurations 3d44s2
and 3d5 4s1 for chromium.

Electrons present in 4s orbital in two configurations contribute nothing to

exchange energy as they do not constitute any pair with parallel spin. Four
unpaired d-electrons in first configuration can make six pairs of electrons with
parallel spin which contribute towards exchange energy (six combinations).
Whereas five unpaired d-electrons in second configuration contribute more
towards exchange energy because they can constitute 10 combinations of
pairs of electrons with parallel spin. This gain of exchange energy (worth of 4
combinations) would favour the 3d54s1 configuration for chromium. But, you
should remember that in achieving this configuration, there would be loss of
energy in promoting an electron from 4s to 3d orbital. In case of chromium the
gain in exchange energy is more than the loss in energy and therefore, 3d54s1
is the favoured configuration.

After argon, the 4s orbital is filled in K and Ca while the nuclear charge
increases by two units. As electrons start entering the 3d orbitals, the 3d
electrons exert more screening on the 4p orbitals than on the remaining 3d
orbitals. Hence 3d remains the lowest available orbital. 13
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

SAQ 1
a) Give the electron configuration of sulfur

b). Give the name and symbols for the elements that have the following
valence configurations.

i) 4s23d5 ii) 5s24d10 iii) 4s23d10 iv) 5s14d8 v) 4s23d2 vi) 5s24d4

c) Write the valence electron configurations for the following transition

The radius of an
metal cations:
atom can be defined
i) Mn2+ ii) Ir3+ iii) Ni2+ iv) Mo2+ v) Ti2+ vi) Fe3+ vii) Pt2+ viii) Nb3+
as the distance from
the centre of the
nucleus to the point
where the electron 1.2.2 Periodic Trends in Properties
density is virtually
zero. Atomic Radii

Atomic radii are a measure of the size of the atoms. Atomic radii are important,
because other atomic properties like ionisation energy, electronegativity etc.
The internuclear
can be related to them.
distance rC–C,
between two carbon
We have to specify the bonding conditions under which the size is being
atoms in diamond is
measured. Pertaining to four major types of bonding, atomic radii are of
154 pm, so the
covalent radius of following four types:
carbon, rC is equal to
i) Covalent radius
77 pm. Similarly, the
rCl–Cl for solid Cl2 is
ii) Crystal or Metallic radius
198 pm, rCl is,
therefore, 99 pm. iii) van der Waals radius

iv) Ionic radius.

Covalent radius is defined as one half of the distance between the nuclei of
two like atoms bonded together by a single covalent bond. If in a homonuclear
diatomic molecule of A, type (e.g., F2, CI2, Br2, I2), rA-A is bond length or
Multiplicity of the
internuclear distance and rA is the covalent radius of atom rA, then rA = ½ rA-A.
bond also causes a
shortening of the
In a heteronuclear, diatomic molecule of AB type, if the bonding is purely
bond. Usually a
covalent, then the bond length rA–B is equal to the sum of covalent radii of A
double bond is about
0.86 times and a and B, i.e.,
triple bond about
rA–B = rA + rB
0.78 times the single
bond length for the
If there is a difference in the electronegativities of the bonded atoms, the bond
second period
elements. Covalent
does not remain purely covalent it causes shortening of the bonds. Schomaker
radii of the elements and Stevenson have proposed the following relationship between the
are listed in Table shortening of the bond and the electronegativity difference of the atoms:
1.5.
rA–B = rA + rB  0.07 (XA  XB)2

Here XA and XB are the electronegativities of A and B, respectively, about

14 which you will study in later in this unit.
Unit 1 General Characteristics of Main Group Elements and Transition Elements

Table 1.7: Covalent and van der Waals radii of elements

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

IA IIA IIIB IVB VB VIB VIIB VIIIB IB IIB IIIA IVA VA VIA VIIA VIIIA

H HE

37  Covalent radius in pm 120

120  van der Waals radius in pm

LI Be B C N O F Ne

123 89 82 77 70 66 64

150 140 135 131

Na Mg Al Si P S Cl Ar

156 136 125 117 110 104 99

180 190 185 174

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

203 174 144 132 122 118 117 117 116 115 117 125 125 122 121 117 114

200 200 195 189

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

216 191 162 145 134 130 127 125 125 128 134 144 144 140 141 137 133

220 220 215 210

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

235 198 169 144 134 130 128 126 127 130 134 147 155 154 148 146  215

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

165 165 164  166 185 161 159 159 158 157 156 170 156

Values of van der

SAQ 2 Waals radii are larger
than those of covalent
(i) If it is given that the Si-C bond length in carborundum is 193 pm and radii because the van
covalent radius of C is 77 pm; calculate the covalent radius of Si. der Waals forces are
much weaker than
(ii) The interatomic distance in Br2 is 228 pm, what is the radius of Br? the forces operating
between atoms in a
covalently bonded
molecule.
Fig. 1.3 illustrates the difference between the covalent and van der Waals radii
of chlorine. It is evident from the figure that half of the distance between the
nuclei X and X of the two non-bonded neighbouring chlorine atoms of 15
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

adjacent molecules is the van der Waals radius of chlorine atom, whereas half
of the distance between the two nuclei X and Y in the same molecule is the
covalent radius of chlorine atom. The van der Waals radii represent the
distance of the closest approach of an atom to another atom it is in contact
with, but not covalently bound to it.

Fig. 1.3: Covalent and van der Waals radii of solid chlorine.

Metallic radius is defined as one-half of the distance between the nuclei of two
adjacent metal atoms in the close packed crystal lattice. For example, the
internuclear distance between two adjacent Na atoms in a crystal of sodium
metal is 383 pm, so the metallic radius of Na metal is 382/2, i.e., 191 pm.

Ionic radius is defined as the distance between the nucleus of an ion and the
point upto which the nucleus has influence on the electron cloud. All common
cations are smaller than all common anions except for the rubidium and
caesium cations (largest single atom cations) which are larger than oxide and
fluoride anions (smallest single atom anions). This happens as not only there
is a loss of electron(s) from a partially filled outer shell on cation formation, but
there is also an increase in the overall positive charge on the ion. Conversely,
in anion formation, the addition of an electron to an atom increases the size
due to increase in inter-electronic repulsion in the valence-shell and decrease
in effective nuclear charge. In general, there is a decrease in size from anions,
to covalent radii of corresponding atoms to cations. Thus in a series of
isoelectronic species (e.g., N3, O2, Ne, Na+, Mg2+, Al3+), the greater the
effective nuclear charge, the smaller is the radius of the species. In Table 1.8
radii of some of the common ions have been listed.

The alkali metals are the largest in their corresponding periods in the periodic
table. The size of the atom or its ion increases on descending the group
(Table 1.8). This is due to the addition of an extra shell of electrons as we
move down the group from one element to the next. The addition of the extra
shell of electrons outweighs the effect of increased nuclear charge and thus
there is an increase in size from Li to Cs. This trend is shown in Fig. 1.5.

The atoms of the alkaline earth metals are smaller than those of the
corresponding Group I elements. This is because of the increase in effective
nuclear charge with the increase in atomic number. Due to increase in
effective charge, valence shell electrons are pulled in more firmly by the
nucleus, thereby reducing the size of the atoms. Similarly, their ionic radii are
also smaller than those of Group I elements, because the removal of two
orbital electrons increases the effective nuclear charge even further.
16
Unit 1 General Characteristics of Main Group Elements and Transition Elements

Table 1.8: Metallic and ionic radii of elements

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

IA IIA IIIB IVB VB VIB VIIB VIIIB IB IIB IIIA IVA VA VIA VIIA VIIIA

H HE

208
(1)

LI Be B C N O F Ne

155 112  Metallic radius (CN = 12) in pm 98 91 11 9 7

60 31  Ionic radius in pm with oxidation state in parenthesis 20 15 (+5) (+6) (+7)

(+1) (+3) 140 136

(+2) (+4) 171
(2) (1)
260 (3)
(4)

Na Mg Al Si P S Cl Ar

190 160 143 132 128 29 26

95 65 50 41 34 (+6) (+7)

(+1) (+2) (+3) (+4) (+5) 184 181

271 212 (2) (1)
(4) (3)

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

235 197 164 147 135 130 135 126 125 125 128 137 141 137 129 140

133 99 81 76 74 84 80 76 74 72 96 74 113 93 47 42 39
(+1) (+2) (+3) (+3) (+3) (+2) (+2) (+2) (+2) (+2) (+1) (+2) (+1) (+2) (+5) (+6) (+7)

66 64 63 62 69 62 53 223 198 195

68 60 69
(+3) (+3) (+3) (+3) (+2) (+3) (+4) (3) (2) (1)
(+4) (+4) (+3)

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

248 215 178 160 146 139 136 134 134 137 144 154 166 162 159 160

148 113 93 80 70 68 69 86 86 126 97 132 112 62 56 50

(+1) (+2) (+3) (+4) (+5) (+4) (+3) (+2) (+2) (+1) (+2) (+2) (+2) (+5) (+6) (+7)

62 67 81 71 245 221 216

(+6) (+4) (+3) (+4) (3) (2) (1)

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

267 222 188 160 149 141 137 135 136 139 146 157 171 175 170 176

169 135 115 81 73 68 69 66 96 137 110 140 120 120

(+1) (+2) (+3) (+4) (+5) (+4) (+4) (+4) (+2) (+1) (+2) (+1) (+3) (+3)

64 95 84 74
(+6) (+3) (+4) (+5)

The trend in the variation of the metallic radii in alkali, alkaline earth and
transition metals whose values are given in Table 1.8, is shown in Fig. 1.6.
You can see in Fig. 1.4 that as we move from alkali metals to alkaline earth
metals and from alkaline earth metals to the transition elements, the radii
decrease steeply but within transition elements this rate of decrease is less.
This could be due to an increase in inter-electronic repulsion after the addition
of sufficient number of electrons in the d orbitals to the gradual increase in
size. 17
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

Fig. 1.4: Trends in metallic radii of alkali, alkaline earth and transition metals of
fourth, fifth and sixth periods.

Factors Affecting the Atomic Radii

Before describing periodicity in atomic radii, we shall first discuss two of the
factors which affect them.

a) Principal Quantum Number (n): As the principal quantum number (n)

increases, the outer electrons get farther and farther away from the
nucleus and hence the atomic radius generally increases.

b) Effective Nuclear Charge (Z*): You know that the magnitude of effective
nuclear charge determines the magnitude of the force of attraction exerted
by the nucleus on the outermost electrons. Greater the magnitude of
effective nuclear charge, greater is the force exerted by the nucleus on
the outermost electrons. Hence, the electron cloud of the outermost shell
is pulled inward nearer to the nucleus and consequently its distance from
the nucleus, i.e., atomic radius decreases.

Effective nuclear charge, Z*, is the amount of positive charge felt by the outer
electrons in an atom. It is always less than the actual charge, Z, of the nucleus
of the atom. The effective nuclear charge felt by an outer electron depends
upon the actual nuclear charge and the number and type of inner screening
electrons.

Thus,

Z* = Z – S

Where S is the screening or shielding constant,

You can estimate the value of screening constant, S, with the help of Slater's
rules in the following manner:

i) Write out the electronic configuration of the element in the following

order and groupings: (1s) (2s. 2p) (3s, 3p) (3d) (4s, 4p) (4d) (4f) (5s, 5p)
(5d) (5f) (6s, 6p), etc.

ii) Electrons in any group higher in this sequence than the electron under
18 consideration contribute nothing to S. For example, in Ti atom (electronic
Unit 1 General Characteristics of Main Group Elements and Transition Elements

configuration, 1s2 2s2 2p6 3s2 3p6 3d2 4s2), the two electrons in 4s orbital
will contribute nothing towards the screening constant for an electron in
3d orbital.

iii) Then for an electron in an ns or np orbital

a) All other electrons in the (ns, np) group contribute S = 0.35 each
except for the electron in 1s which contributes S = 0.30.

b) All electrons in the (n-1) shell contribute S = 0.85 each.

c) All electrons in (n-2) or lower shells contribute S = 1.00 each.

iv) For an electron in an nd or nf orbital,

a) All electrons in the same group, i.e., nd or nf contribute S = 0.35

each;

b) Those in the groups lying lower in the sequence than the nd or nf

group contribute S = 1.00 each.
*
Applying Slater's rules we shall now calculate the Z for an electron in K and
Zn atoms.

i) Electronic configuration of K = 1s2 2s2 2p6 3s2 3p6 4s1. Grouping of

orbitals will be (1s2) (2s22p6) (3s2 3p6) (4s1). Value of screening constant
for an electron in 4s orbital will be S = (0.83 x 8) + (1 x 10) = 16.80

Hence, the effective nuclear charge Z* = Z – S = 19 – 16.80 = 2.20

ii) Electronic configuration of Zn = 1s2 2s2 2p6 3s2 3p6 3d10 4s2. Grouping of
the orbitals gives - (1s2) (2s2 2p6) (3s2 3p6) (3d10) (4s2) Value of
screening constant S for an electron in 4s orbital will be S = (0.35 x 1) +
(0.85 x 18) + (1 x 10) = 25.65

Hence, the effective nuclear charge felt by 4s electron will be

Z* = Z – S = 30 – 25.65 = 4.35

If we consider a 3d electron in Zn, the grouping is as above, but the

effective nuclear charge felt by a 3d electron will be

Z* = Z – S = 30 - [(9x0.35) + (18x 1.00)] = 8.85

Thus, you can see that an electron in 3d orbitals in Zn is more strongly

held by the nucleus than that in 4s orbital.

In Table 1.9 values of effective nuclear charge for electrons in valence

shell for the first thirty elements calculated by Slater's rules have been
listed. There is a steady increase in Slater's Z across rows of the periodic
table. Effective nuclear charge felt by electrons also depends on the
oxidation state of an atom in a compound. The higher the oxidation state of
the atom, the higher will be the effective nuclear charge felt by the
electrons and therefore, smaller will be the atomic radius. Thus, the ionic
radius of Fe3+ ion will be smaller than that of the Fe2+ ion. 19
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

Table 1.9: Effective nuclear charge for first 30 elements

Period Elements Z S Z*
1 H 1 0 1.0
He 2 0.30 1.70
2. Li 3 1.70 1.30
Be 4 2.05 1.95
B 5 2.40 2.60
C 6 2.75 3.25
N 7 3.10 3.90
O 8 3.45 4.55
F 9 3.80 5.20
Ne 10 8.80 2.20
3. Na 11 8.80 2.20
Mg 12 9.15 2.85
Al 13 9.50 3.50
Si 14 9.85 4.15
P 15 10.20 4.80
S 16 10.55 5.45
Cl 17 10.90 6.10
Ar 18 11.25 6.75
4. K 19 16.80 2.20
Ca 20 17.15 2.85
Sc 21 18.0 3.0
Ti 22 18.85 3.15
V 23 19.70 3.30
Cr 24 20.55 3.45
Mn 25 21.40 3.60
Fe 26 22.25 3.75
Co 27 23.10 3.90
Ni 28 23.95 4.05
Cu 29 24.80 4.20
Zn 30 25.65 4.35

SAQ 3
Compare the variation in the values of Slater's effective nuclear charge for the
valence 1 electron in the elements of period 2 with that in the elements of 3d
series.

Periodicity in the Atomic Radii

We will now consider the periodicity in the atomic radii. Two general periodic
trends are found for all four types of atomic radii. These are: the atomic radii
decrease along a period and generally increase down a group in the long form
of the periodic table (Fig. 1.9). These changes in effective nuclear charge and
the principal quantum number in the periodic table.

As shown in this Table 1.9, there is a steady increase (by 0.65 units) in the
20 value of Z* from alkali metals to halogens for the elements of period 2 and 3.
Unit 1 General Characteristics of Main Group Elements and Transition Elements

But there is no change in the value of n because the electrons fill the same
principal shell. As a result of this there is a steady decrease in the covalent
radius from 123 and 156 pm, for Li and Na to 64 and 99 pm for and CI,
respectively.

Fig. 1.5: Variation of covalent radius with atomic number.

In comparison to the above, the decrease in covalent radii across a transition

series is much smaller. It is already discussed that across a transition series,
there is only a small increase in effective nuclear charge (by 0.15 units),
therefore, only a small decrease in atomic radius from one element to another
takes place. Across ten elements of the first transition series, there is an
overall decrease in covalent radius by 19 pm which is much less than that
across seven normal elements of period 2 (59 pm) and period 3(57 pm). But
due to this, the covalent radii of elements from Ga to Kr, following Zn, become
much smaller than that expected by simple extrapolation of the values for
elements of period 2 and 3. For example, the covalent radii of Al and Ga are
equal whereas the covalent radii of elements Ge, As, Se, Br are only slightly
larger than those of corresponding elements (Si, P, Sand Cl) of period 3.

In the lanthanoid elements, filling of (n–2) f orbitals takes place, while

simultaneously the nuclear charge increases. The electrons in the (n–2)f
orbitals shield the ns electrons, which largely determine the size, from the
increase in nuclear charge almost completely (S = 1.00). As a result of this,
there is only a small decrease in the atomic radius from one element to
another. But there are 14 elements in the series, there is a total contraction of
13 pm across the series from La (Z = 57) to Lu (Z = 7 1). This is known as
lanthanoid contraction, because of which the atoms of elements (Hf to Hg)
following Lu are unusually smaller than they would be if the lanthanoids had
not been built up before them. Lanthanoid contraction almost exactly cancels
out the effect of the last shell added in the sixth period and therefore, the
transition elements of 4d and 5d series have almost the same atomic radii.

On descending any group of the periodic table, the number of electrons in the
valence shell remains constant but the number of shells around nucleus
increases monotonically. The effective nuclear charge felt by valence
electrons stays nearly the same. So, with the increase in principal quantum
number (n) of the valence shell, an increase in atomic radii is generally 28
observed down any group of the periodic table. There is an increase in the 21
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

atomic radii of alkali and alkaline earth metals as we proceed downwards in

the group. But as discussed earlier, with the inclusion of 3d transition elements
in period 4., increase in the radii of elements from Ga to Br is smaller than
expected. Similarly, because of inclusion of lanthanoid elements in period 6,
atoms of the transition elements of this period (Hf to Hg) are almost of the
same size as the atoms above them in period 5(Zr to Cd). After that only a
small increase in size of the remaining elements of period 6 (TI to At) as
compared to the size of elements above them in period 5 (In to I) is observed.

Fig. 1.6 Shows the variation in radius of the M2+ ions for six-coordiante
complexes of the transition metals of 3d series. You should remember that the
three of 3d orbitals (t2g: dxydzxdyz) point between the ligands and the other two
(e.g. d 2 2 ,d 2 point towards the ligands. In “low-spin complexes”. The
x y z

electrons occupy the t2g orbitals first, so the radius decreases along the series
till it reaches d6 ion (Fe2+). If we consider that the effective nuclear charge
increases then the decrease in size is more than this reason only. After d6, the
electron enters eg orbital and so they repel with the ligands which are pointing
towards them. So, if we consider the metal-ligand distance, the effective ionic
radius increases. If we look at the “high spin complexes, all the five 3d orbitals
are filled before getting paired up. So far d2, d3 the radius decreases but when,
it becomes d4 the electron goes to e.g. orbital and the radius increases.

At d5(Mn2+), the value of ionic radius gives values for which the increase in
effective nuclear charge is the answer. In d6, there is pairing of electrons, first
in t2g, which does not repel with those of the ligands. Lastly the electrons pair
with those in e.g. orbitals and so they repel with ligands.

2+
Fig. 1.6: The ionic radii of the M ions of the 3d metals. Where there are
alternatives, red represents high-spin and blue low-spin complexes. In
the orbital energy diagrams, the three lower levels are the d orbitals that
point between ligands and the two upper levels are the d orbitals point
22 directly at them.
Unit 1 General Characteristics of Main Group Elements and Transition Elements

SAQ 4
a) For each of the following pairs, which one is larger in size?

i) Na, Na+; ii) Br, Br; iii) Br, I; iv) O, S; v) K+, Cl; vi) Li, F

b) Arrange the following isoelectronic species in order of decreasing atomic

radius giving reasons: Na+, Mg2+, Al3+, Si4+, N3-, O2-, F, Ne.

1.2.4 Atomic Volume and Density Related to atomic

size is the density of
There are two general trends observed in the densities of the elements in the the elements. density
periodic table. Along a period there is a general increase in density because of can be defined as
the increase in atomic mass and decrease in the size of the atom. Thus, in a mass per unit volume.
For solids, the density
particular period the alkali metals have the lowest density, considering the is a function of atomic
solid elements structures are often the same within any group, the factors weight, size of the
which determine the density are atomic mass and volume. As you can see atom and the
from Table 1.1, density increase as we move from Li to Cs. This means that structure of the solid
the increase in atomic weight from one element to the next in passing down which determines the
closeness of the
the group overweights the effect of increase in the size of the atom. There are,
packing of the atoms.
however, some exceptions to this general trend and in this particular group of
alkali metals. You can see from Table 1.1 that the density of potassium is less

than that of sodium. Thus, potassium is an exception in this trend. The alkaline
earth metals are denser than the Group I metals because they have two
valence electrons per atom for bonding the atoms into a metallic lattice and as
a result more mass can be packed into a smaller volume. The density
decreases slightly on moving down the group from Be to C but increase
considerably thereafter up to Ra.

The size of an atom of an element is related to its atomic volume. So their

trends are the same. Similarly density is also related to the size of the
elements. So, across the period, the smaller the size, the higher is the density
of the elements. Thus there is a general trend of increasing density across the
elements of a transition series. This is well represented in Fig 1.7 which gives
the variation of the densities of alkali, alkaline earth and the transition metals
of the fourth, fifth and sixth periods. For 4d and 5d elements, this increase is
not that regular as the increase in densities for 3d elements. Along the group
also, the density increases (Fig. 1.7). The increase in density within the d
block groups is greater than that within the s and p block groups.

On descending one of the main groups of elements in the s- and p- blocks, the
size of the atoms increases because extra shells of electrons are added. The
elements in the first group in the d- block (Group 3) show the expected
increase in size (ScY La). But in the subsequent Groups (4-12), there is
an increase in radius of (0.3-13 pm) between the first and second member, but
very little increase between the second and third elements. This trend is
shown both in the covalent radii (Table 1.7) and in the ionic radii (Table1.8).
Between lanthanum and hafnium are the 14 lanthanoids, in which the
antepenultimate shell of electrons is filled. 23
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

The atomic volumes of the transition elements are low as compared with
elements in neighbouring Groups 1 and 2. Can you say why is it so? Well, it is
because the increased nuclear charge is poorly screened and so the electrons
are attracted more strongly by the nucleus. Again, the extra electrons added
occupy inner orbitals. As a result the densities of the transition metals are high
and are greater than 5 gcm 3. (The only exceptions are Sc 3.0 gcm3 and Y
and Ti 4.5 gcm3.) The densities of the second row are high and third row
values are even higher. The two elements with the highest densities are
osmium 22.57 gcm3 and iridium 22.61 gcm3.

Fig. 1.7: Trend in densities of the alkali, alkaline earth and transition metals of
fourth, fifth and sixth periods.

There is a gradual decrease in the size of the 14 lanthanoids from cerium to

lutetium. This is called the lanthanoid contraction which we have already
discussed. The second and third row transition elements have similar radii.
As a result they also have similar lattice energies, solvation energies and
ionization energies. Thus the differences in properties between the first row
and second row elements are much greater than the differences between the
second and third row elements. The effects of the lanthanoid contraction are
less seen towards the right of the d-block.

SAQ 5
a) Of the following pairs, which element is larger in size. Justify your
answer.
(i) Calcium or scandium
(ii) Vanadium or titanium
(iii) Chromium or molybdenum
(iv) Iron or osmium
b) Why is the size of the elements of third transition series almost similar to
that of the elements of second transition series?
24
Unit 1 General Characteristics of Main Group Elements and Transition Elements

1.2.5 Melting and Boiling Points

The alkali metals are soft and can be cut with a knife. As a result of increase in
size and repulsion of the non-bonded electrons, their cohesive energy and
tendency for metallic bonding decrease down the group and thus softness
increases as we go down from Li and Cs. These metals have low melting and
boiling points which also reflect the low values of cohesive energy between the
atoms. Their melting and boiling points decrease as we go down the group. As the process of
boiling requires
The Group II metals have higher melting points when compared to the Group I almost complete
metals. The reason being + 2 charge on the cations in the metallic lattice, breaking of bonds
causing them to be more strongly attracted to the ‘sea of electrons’ and and such metallic
making it difficult to pull them apart. bonding exists in the
liquid state to some
The melting and boiling points of the transition elements are generally very extent, high
high. Transition elements typically melt above 1000°C. There are a few temperatures are
necessary. Therefore,
exceptions. The melting points of La and Ag are just under 1000°C (920°C and
the boiling points of
961°C respectively). Other notable exceptions are Zn (420°C), Cd (321°C) and
the metals are much
Hg which is liquid at room temperature and melts at 38°C. The last three higher than melting
behave atypically because the d shell is complete, and d electrons do not points.
participate in metallic bonding. The high melting points are in marked contrast
to the low melting points for the s-block metals Li (181°C) and Cs (29°C).

Second ionisation
energy is much larger
Fig. 1.9: Trends in melting points of alkali, alkaline earth and transition metals than the first
of fourth, fifth and sixth periods. ionisation energy, as
in this case an
The melting points of the transition elements depend upon the strength of the electron is being
metallic bond which increases with the availability of the electrons to removed from a
positively charged
participate in bonding. If you look at Fig. 1.10 then you can see that between
cation. Similarly you
calcium and scandium (where d electron first appears), there is a jump of
can define third.
nearly 700 degrees (in Centigrade scale) in the melting point. The unpaired d fourth and higher
electron leads to higher interatomic forces and therefore the increase in ionisation energies.
strength of the metallic bond which is reflected in high melting and boiling
points. But, this cannot be generalized and there are anomalies. When we 25
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

move across any period in the periodic table, the values of the melting point,
first increases till the middle of each transition series and then it decreases
with the onset of pairing of electrons. If you look at the values of melting points
for the first transition series (Fig. 1.10), there is a sharp decrease of melting
point at manganese, which has five unpaired d electrons. This is because of a
complex crystal structure of manganese. Now, the reason for the softness and
low melting point of Zn, Cd and Hg (Hg is a liquid) is that the electrons are
paired up in these atoms. The melting points of the elements of the first
transition series are comparatively lower than those of the elements of the
second and third transition series. This trend is very well illustrated in the
Fig. 1.10.

The periodic trends in the boiling points are similar to those in the melting
points.

Ionisation Energy

The energy required to remove the least strongly bound electron from an
isolated gaseous atom in its ground state, is known as the ionisation
energy. You can represent this process by the following equation:

M(g)  M+(g) + e

Since more than one electron may be removed from an atom, the energy
required for the above is called the first ionisation energy. Second ionisation
energy is the energy required to remove an electron from a univalent cation,
that is, to cause the following reaction to occur:

M+(g)  M2+(g) + e

The ionization energy, I, of an outer valence electron is related to the effective

nuclear charge felt by the electron and its average distance from the nucleus
SI unit of ionisation as given below:
energy which we will
Z * . e2
use throughout this I . (1/ r ) av
course is kilojoule 2
per mole.
where Z is the effective nuclear charge, e is the charge on electron and (1lr)av
is the average value of I/r, r being the distance of the electron from the
nucleus. Thus, the higher is the effective nuclear charge felt by the electron,
the higher will be the ionisation energy; also the farther the electron is from the
nucleus, the lower will be the ionisation energy and vice versa. Also,
completely filled and half filled subshells are comparatively more stable
because, removal of an electron from them requires more energy. The valence
shell electronic configurations of noble gases are exceptionally stable and,
therefore, their ionisation energies are the highest in the respective periods.
Try the following SAQ to see whether you understand the effect of various
factors on ionisation energy.

Periodicity in Ionisation Energy Across Periods

Now, we shall examine the variation in ionisation energy across the periods
and down the groups in the periodic table. Values of ionisation energies of
26 elements are given in Table 1.10.
Unit 1 General Characteristics of Main Group Elements and Transition Elements

Table 1.10: Ionisation energies of elements in kJ mol 1

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18

IA IIA IIIB IVB VB VIB VIIB VIIIB IB IIB IIIA IVA VA VIA VIIA VIIIA

H HE
1312 120

LI Be B C N O F Ne
520 900 800 1086 1403 1314 1681 2081

Na Mg Al Si P S Cl Ar
495 738 577 787 1060 1000 1255 1520

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
418 590 633 659 650 653 717 762 759 736 745 906 579 760 946 941 1142 1350

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
403 549 615 659 664 688 697 711 720 804 731 867 558 707 833 869 1007 1170

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
374 502 541 674 745 770 761 837 879 870 890 1006 589 715 703 813 912 1037

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
540 527 527 540 540 547 594 577 573 582 586 561 598 594

However, the variation of ionisation energy in a particular group or period is

best shown by plotting ionisation energies against atomic number.

Group I elements acquire the electronic configuration of the preceding noble

gas elements. Thereby they have a high tendency of giving up the single
outermost electron to form univalent cations. Their first ionization energies are
the lowest in the respective periods and so, they are the most reactive of all
the metals. As we go down the group, their atomic size increases, their
ionization energies decrease, resulting in an increase in their reactivity. The
effective nuclear charge felt by the electrons increases after the removal of
one electron from the atom of any element and hence, their second ionization
energies are always higher than the first. However, in the case of alkali metals,
the unipositively charged ions (Li+, Na+, K+, etc.) have the stable electronic
configuration of the preceding noble gases. Removal of an electron from a
stable noble gas configuration is extremely difficult. These metals, therefore,
form univalent cations only.

So you see, these elements have high electropositive or metallic character

which increases as we move down in the group from Li to Cs. In fact, Rb and
Cs are so highly electropositive that they emit electrons even when exposed to
light; that is, they exhibit photoelectric effect.

The first ionization energy (Table 1.10) of alkaline earth metals is more than
that of corresponding alkali metals. This because the alkaline earth metals
have higher effective nuclear charge and are smaller in size, thereby the
electrons are more tightly held to the nucleus. The second ionisation energy of
these elements is almost twice their first ionisation energy. This is because
once one electron has been remove, the effective nuclear charge felt by orbital
electrons is increased, so that the remaining electrons are more tightly held
and hence, much more energy is needed to remove the second electron.
However, their second ionisation energy is less than that of the corresponding 27
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

alkali metals because of stability of closed shell configuration of the univalent

cations that are formed in the latter cases. The ionisation energy of alkaline
earth metals also decreases on moving down the group.

Lower second ionisation energies of the alkaline earth metals as compared to

those of alkali metals can be exemplified as below:

Fig. 1.10 shows the plot of first ionisation energies of the elements of first six
periods against their atomic numbers. As is evident from the figure, the first
ionisation energy generally increases from alkali metals to noble gases across
any row of the periodic table. But the increase is not perfectly regular. We will
consider this aspect a little later.

Fig. 1.10: Variation of ionisation energy with atomic number. (Source: Ponor,
CC BY-SA 4.0)

You have already studied in that across any row of the periodic table, the
effective nuclear charge steadily increases and the atomic radii decrease.
These two effects reinforce each other to increase the ionisation energy
across a period. Thus, the ionisation energies of the alkali metals are the
lowest and those of the noble gases are the highest in their respective period:.
But as pointed out earlier, the increase is not smooth and some anomalies are
observed. For example, in the elements of period 2, inspite of increase in Z*
and decrease in r, the first ionisation energies of B and O are lower than those
of Be and N, respectively. However, these anomalies in the trend in ionisation
energy can be explained by electronic structures of these elements. In case of
beryllium, the electron is removed from the filled 2s subshell, whereas in
boron, the electron is removed from the singly occupied 2p subshell. The 2p
subshell is higher in energy than the 2s. So, the 2p electron of boron is more
easily removed than a 2s electron of beryllium. When we come to nitrogen, we
find that we have a half filled 2p subshell (electronic configuration Is2 2s2 2p3,
while in oxygen the 2p subshell is occupied by four electrons. The fourth
electron in this 2p subshell is in an orbital already occupied by another
electron. So, it experiences considerable repulsion. As a result, this electron is
more easily removed than one of the electrons from a singly occupied orbital
in nitrogen atom. Thus, the ionisation energy of oxygen becomes less than
that of nitrogen. Similar anomalies are observed in elements of period 3,
where the first ionisation energies of magnesium and phosphorus are higher
than those of aluminium and sulphur, respectively. You have already studied
in that across a transition series, the increase in effective nuclear charge and
28 consequent decrease in atomic radius is small. Therefore, increase in their
Unit 1 General Characteristics of Main Group Elements and Transition Elements

first ionisation energies is also small. But following the transition elements, the
first ionisation energy drops abruptly in gallium, indium and thallium. This
again is due to the removal of an electron from the singly occupied np orbitals
which are of relatively higher energy than the ns orbitals of Zn, Cd and Hg.

Trends in Ionisation Energy Down the Groups

You have already studied that on moving down a group of s-and p-block
elements in the periodic table, effective nuclear charge remains almost steady.
But there is a general increase in the atomic radius due to increase in the
value of the principal quantum number, n. Thus, the dominant factor in
determining the ionisation energies of the elements on moving down the
groups, is their atomic radius rather than the effective nuclear charge.
Therefore, as expected, the first ionisation energies decrease down the groups
in case of the main group elements in the periodic table. But in the case of
transition elements opposite trends are observed. Thus, the first ionisation
energies of the corresponding elements of 3d and 4d series are almost similar
but these are smaller than the first ionization energies of the elements of 5d
series. Certainly, the higher values of ionisation energies of the 5d transition
elements are consistent with the relatively smaller size of their atoms.

Trends in Successive Ionisation Energies

We have already defined successive ionisation energies, i.e., second, third,
etc. Values of eight successive ionisation energies of first twenty elements are
listed in Table 1.11.
Table 1.11: Successive ionisation energies (kJ mol-1) of first 20 elements

First Second Third Fourth Fifth Sixth Seventh Eighth

H 1 312
He 2 372 5 250
Li 520 7 297 11 810
Be 900 1 757 14 850 21 000
B 800 2 427 3 658 25 024 32 824
C 1 086 2 352 4 619 6 220 37 820 47 280
N 1 403 2 858 4 578 7 473 9 443 53 270 64 360
O 1 314 3 391 5 300 7 469 10 983 13 326 71 330 84 050
F 1 681 3 381 6 046 8 418 11 017 15 163 17 870 92 000
Ne 2 081 3 964 6 150 9 367 12 200 15 230
Na 495 4 563 6 912 9 540 13 350 16 732 20 110 25 490
Mg 738 1 450 7 730 10 550 13 625 18 035 21 735 25 660
Al 577 1 816 2 745 11 575 14 850 18 370 23 350 27 460
Si 787 1 577 3 230 4 355 16 090 19 795 23 770 29 250
P 1 060 1 869 2 908 4 954 6 272 21 270 25 413 29 840
S 1 000 2 258 3 381 4 565 6 995 8 494 27 112 31 720
Cl 1 255 2 297 3 849 5 163 6 540 9 330 11 029 33 600
Ar 1 520 2 665 3 947 5 770 7 238 8 810 11 965 13 840
K 418 3 069 4 439 5 875 7 950 9 619 11 384 14 950
Ca 590 1 146 4 941 6 464 8 142 10 500 12 350 13 830
29
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

It is evident from the values in the Table 1.11 that the successive ionisation
The tendency to form
energies of an element inevitably become larger because the removal of
cation, i.e. metallic
character decreases successive electrons leaves a higher charge on the nucleus to hold the
across a period and remaining electrons. It is also clear from the Table 1.11 that the difference
increases down the between successive ionisation energies of the same element is not constant.
group. For example, Big jumps occur whenever an electron from a subshell of lower principal
in period 3 metallic quantum number is removed for the first time. For example, for alkali metals
character decreases
the second ionisation energies are much higher than the first; for alkaline earth
from Na to Cl
whereas in the metals the third ionisation energies are much larger than the second and for
elements of Group the halogens the eighth ionisation energies are much greater than the
14, C is a nonmetal, seventh. These cannot be explained on the basis of increase in nuclear
Si and Ge are charge alone. The stabilities of closed shell configurations similar to those of
semimetals or noble gases are more important in these cases.
metalloids whereas
Sn and Pb are In this section so far you have studied that the ionisation energy generally
metals. increases across a period and decreases down the group in the periodic table.

SAQ 6
a) Which of the atoms having following electronic configurations will have
the highest first ionisation energy and why?
i) [Ne] 3s2 3p2; ii) [Ne] 3s2 3p3; iii) [Ne] 3s2 3p4; iv) [He] 2s2 2p3;
v) [Ar] 3d10 4s2 4p3.

b) The order of increasing ionisation energy for the atoms N, Ne, Na and P
is

Partial charges on the i) Na < P < N < Ne ii) N < Ne < Na < P
atoms are separated iii) N < Na < < Ne < P iv) Na < N < P < Ne
due to difference in
electron attracting Give reasons.
tendencies of A and
B, i.e., the difference
in the Electonegativity
electronegativities of
Next you will learn about electronegativity of an element, The tendency of
A and B.
attracting the electron pair towards itself by an atom in a molecule has
been termed as electronegativity of the element. It is not a directly
measurable physical quantity, but rather a theoretical concept for which
several numerical scales have been developed.

This concept was first developed by Pauling. He defined it on the basis of the
patterns discernible in the single bond energies of elements, which were
derived from the thermochemical data. Where E A  A and EBB are bond
energies of A–A and B–B homonuclear bonds. The excess bond energy,
E A B  E A  A . EB B , is due to the electrostatic attraction between partially
charged atoms (A δ   Bδ  ) in the molecule. So,
E A B  E A  A . EB B  96.49 ( X A  X B )2

where XA and XB designate electronegativities of the elements A and B,

respectively and are assumed to be the same for all molecules containing A
30 and B. You can write this relationship as
Unit 1 General Characteristics of Main Group Elements and Transition Elements

or
This formula,
however, gives the
E A B  E A  A . EB B
X AB  difference in the
96.49 electronegativities
and not the absolute
As the largest electronegativity difference on this scale between the most value assigned to a
electronegative element fluorine and the most electropositive element caesium particular element.
came out to be 3.3, Pauling assigned arbitrarily a whole number value 4.0 for
fluorine so that values of electronegativity of all elements remain positive. In
Table 1.10, the values of electronegativity of different elements are
represented in bold face as calculated by Pauling using the above formula for
differences in electronegativity.

Mulliken defined electronegativity as the mean value of first ionisation energy

and first electron affinity. Both quantities are given a positive value if loss of
electron involves absorption of energy and gain of electron involves release of
energy. Thus, electronegativity XA of atom A is given by the following
relationship:

(I )A  (E A )A
XA 
2

According to this relationship, a very electronegative element has a very high

ionisation energy. So, it will be difficult to remove its electrons. It also has a
very high electron affinity. Hence, a very stable species results when electrons
are added. The electronegativity values on Mulliken's scale are about 2.8
times those of Pauling's values. The trends in the variation of
electronegativities are, however, the same.

Table 1.12: Electronegativity values of elements

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18
IA IIA IIIB IVB VB VIB VIIB VIIIB IB IIB IIIA IVA VA VIA VIIA VIIIA
H HE
2.1 Pauling Scale
2.1 Allred-Rochow Scale
Li Be B C N O F Ne
1.10 1.5 2.0 2.5 3.0 3.5 4.0
1.15 1.50 2.0 2.5 3.05 3.5 4.1
Na Mg Al Si P S Cl Ar
0.9 1.2 1.5 1.8 2.1 2.5 3.0
1.1 1.25 1.45 1.74 2.05 2.45 2.85
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
0.8 1.0 1.3 1.5 1.6 1.6 1.5 1.8 1.8 1.8 1.9 1.6 1.6 1.8 2.0 2.4 2.8
0.9 1.05 1.2 1.3 1.45 1.55 1.6 1.65 1.7 1.75 1.75 1.65 1.8 2.0 2.2 2.5 2.75
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
0.8 1.0 1.2 1.4 1.6 1.8 1.9 2.2 2.2 2.2 1.9 1.7 1.7 1.8 1.9 2.1 2.5
0.9 1.0 1.1 1.2 1.25 1.3 1.35 1.4 1.45 1.35 1.4 1.46 1.5 1.7 1.8 2.0 2.2
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
0.7 0.9 1.1 1.3 1.5 1.7 1.9 2.2 2.22 2.2 2.4 1.9 1.8 1.8 1.9 2.0 2.2
0.85 0.95 1.1 1.25 1.35 1.4 1.45 1.5 1.55 1.45 1.4 1.45 1.45 1.55 1.65 1.75 1.90
Fr Ra Ac Unq Unq Unh Uns Uno Une

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
1.1 1.1 1.2 --- 1.2 --- 1.1 1.2 --- 1.2 1.2 1.2 1.1 1.2
1.82 1.82 1.82 --- --- 2.04 1.79 1.77 1.77 1.76 1.75 1.74 1.93 1.74
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
1.3 1.5 1.7 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3 1.3
1.80 --- 1.4 --- --- --- --- --- --- --- --- --- --- --- 31
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

According to Allred and Rochow, electronegativity is equated to the force of

It is very difficult to attraction between an atom and an electron separated by a distance equal to
measure electron
the covalent radius of the atom. Where Z* is the Slater's effective nuclear
affinity for all
elements. Therefore,
charge, e the electronic charge and r the covalent radius, a plot of Pauling
Mulliken’s method is electronegativities against Z*/r2 gives approximately straight line. Values of the
not universally slope and intercept indicate that on the Pauling scale, Allred-Rochow
applicable. electronegativities are given by the numerical relationship.

Z*
X A  3590  0.744, where value of r is in pm.
The force of attraction r2
is expressed
according to This method has an advantage in that it can be applied to a comparatively
Coulomb's law as, larger number of elements. Electronegativities of elements on Allred-Rochow
Z * e2 scale have been listed in Table 1.12.
F
r2
All the electronegativity scales give average values of electronegativities of
elements in different bonding environments. The larger the difference between
Hybridisation also
affects the electronegativities of two elements, the more polar will be the bond
electronegativity between these elements.
because of the lower
energy and hence, Periodicity in Electronegativity
greater electron
attracting power of s-
Electronegativity values of elements show a fairly discernible periodic trend
orbitals. Thus, hybrid throughout the periodic table. The trend is similar to that of ionisation energies.
orbitals having Thus, as expected electronegativity of elements increases sharply across a
greater s-character row of s and p-block elements, since the effective nuclear charge of these
possess higher elements is increasing sharply for example, from lithium to fluorine. However,
electronegativity. across a series of transition elements, the increase in electronegativity is much
An atom in sp
smaller. This is because the additional electron is being added to an inner
hybridised state will
be more shell which provides relatively good shielding for the outer electron from the
electronegative than nucleus.
the same atom in sp2
hybridised state On moving down a group of representative elements, for example, in the
which in turn will be lithium group, there is a general decrease in electronegativity. The decrease is
more electronegative relatively small except between the first two elements. The much greater
than the same atom electronegativity of lithium row elements correlates well with their small size.
2
in sp hybridised As expected, the elements of period 4 from gallium onwards, i.e., Ga, Ge, As,
state.
Se and Br have greater electronegativities than would be expected by
extrapolation from values for the first two elements in the respective groups.
This is due to the insertion of transition elements, because of which, the
effective nuclear charge of these elements is greater than that if the transition
elements were not there. Similarly, the presence of the lanthanoid elements is
responsible for greater electronegativities of the elements of 5d series than
would be expected by extrapolation from values of the elements of 3d and 4d
series.

Transition elements have fairly low values of electronegativity. It increases

from Sc to Cu with a fall at Mn and Zn. But, this increase in electronegativity is
much slower as the additional electron is being added to an inner shell which
provides relatively good shielding to the outer electrons from the nucleus.
Thereby the elements become slightly less metallic which is reflected in the
increasing positive electrode potentials of their ions M2+and M3+ (Table 1.11).
32
Unit 1 General Characteristics of Main Group Elements and Transition Elements

The periodic variation

of electronegativity
with atomic number
for the first six rows of
the periodic table is
shown below
Lanthanoids Fig. 1.9.
(f block)

Fig.1.11: Periodic Variation of Electronegativity with Atomic Number for the First
Six Rows of the Periodic Table

Electrode Potential
When a metal is placed in a solution of its ions a potential difference is set
up between the metal and the solution. This concept is illustrated in
Fig. 1.12.

Fig. 1.12: Single Electrode Cell (Half-cell).

The value of this potential difference for a particular metal depends upon
the particular metal, the concentration of the metal ions in solution and the
temperature. By convention, the potential difference set up in a 1M solution
of metal ions at 298K is called the standard electrode potential. Measuring
the standard electrode potentials is absolutely impossible. It has to be
measured against some reference electrode which is the hydrogen
electrode. This consists of hydrogen gas at one atmosphere pressure in
contact with a 1M solution of its ions at 298 K.

The values of some standard electrode potentials for the elements of first
transition series are given in Table 1.13. Electrode potential is a measure
of the electropositive character and the reactivity of the metals. You will find
that along a period, generally there is a decrease in electropositive
character and also the reactivity of metals also decreases. Table 1.13
contains the thermochemical parameters related to the transformation of
the solid metal atoms to M2+ ions in solution and their standard electrode
potentials. If you look at Table 1.7, you will see that all the elements of the
first transition series, except copper, have negative values and can react
with acids (H+) producing hydrogen. A plot of variation of the electrode
potential of the transition elements of 3d series is shown in Fig. 1.16. The 33
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

unique behaviour of Cu, having a positive E0, accounts for its inability to
liberate H2 from acids. Only oxidising acids (nitric and hot concentrated
sulphuric) react with Cu, the acids being reduced. The high energy to
transform Cu(s) to Cu2+ (aq) is not balanced by its hydration enthalpy. The
general trend towards less negative E0 values across the series is related
to the general increase in the sum of the first and second ionisation
enthalpies. It is interesting to note that the value of E 0 for Mn, Ni and Zn are
more negative than expected from the trend.

M3++3e M

M2++2e M

Atomic Number

Fig.1.13: Trends in electrode potentials of transition metals of 3d series.

Table 1.13: Thermochemical data (kJ mol-1) for the first row transition
Elements and the Standard Electrode Potentials for the
Reduction of M2+ to M.

Element (M) OH0 (M) Δ1H10 Δ1H02 ΔhydH0 (M2 ) E 0 /V

Ti 469 656 1309 -1866 -1.63

V 515 650 1414 -1895 -1.18

Cr 298 653 1592 -1925 -0.90
Mn 279 717 1509 -1862 -1.18
Fe 418 762 1561 -1998 -0.44
Co 427 758 1644 -2079 -0.28

Ni 431 736 1752 -2121 -0.25

Cu 339 745 1958 -2121 -0.34

Zn 130 906 1734 -2059 -0.76

Ti 469 656 1309 -1866 -1.63

V 515 650 1414 -1895 -1.18

Cr 298 653 1592 -1925 -0.90
Mn 279 717 1509 -1862 -1.18
Fe 418 762 1561 -1998 -0.44
Co 427 758 1644 -2079 -0.28

Ni 431 736 1752 -2121 -0.25

Cu 339 745 1958 -2121 -0.34

Zn 130 906 1734 -2059 -0.76

34
Unit 1 General Characteristics of Main Group Elements and Transition Elements

Oxidation States
The transition elements usually exist in several different oxidation states which
change in units of one, e.g. Fe3+ and Fe2+, Cu2+ and Cu+.

The oxidation states shown by the transition elements may be related to their
electronic structures which have been already discussed in section 1.2 of this
unit. Recalling the electronic configuration of the transition elements we
remember that Cr and Cu have additional stability when the d orbitals are
exactly half filled or completely filled (Table 1.14) in their ions.

Table 1.14: Oxidation states of transition elements (The solid dots show
common oxidation states, and the hollow dots show possible
but unlikely states)

Table 1.15: Oxidation states of transition elements of d-block (the most

common oxidation states are in bold type)

Sc Ti V Cr Mn Fe Co Ni Cu Zn
+3 +2 +1 +2 +2 +2 +2 +2 +1 +2
+3 +2 +3 +3 +3 +3 +3 +2
+4 +3 +4 +4 +4 +4
+4 +6 +6
+5 +6 +7
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
+3 +4 +3 +3 +4 +2 +3 +2 +1 +2
+5 +4 +6 +3 +4 +3 +2
+5 +7 +4 +6 +4 +3
+6 +5
+6
+7
+8
La Hf Ta W Re Os Ir Pt Au Hg
+3 +4 +4 +2 +3 +2 +2 +2 +1 +1
+5 +3 +4 +3 +3 +3 +3 +2
+4 +5 +4 +4 +4
+5 +6 +6 +6
+6 +7 +8
35
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

If you look at Table 1.14 then you will notice that there is a reduced tendency
of higher states towards the end of the series. This could be due to steady
increase in the effective nuclear charge along the series thus pulling the d
orbitals into the electron core and not making them readily available for
bonding. For example, the only oxidation state for Zn is Zn (+2) where no d
orbital is involved. On the other hand, early in the series, it is difficult to form
species that do not utilize the d electrons i.e., Sc(+2) is virtually unknown and
Ti(+5) is more stable than Ti(+2).

By looking at Table 1.15 you can very easily follow the trend in the oxidation
states as we go down the group. The trend in the stability of oxidation states
within the groups is different for the transition elements and the main group
elements (s and p block elements). For the main group elements, the higher
oxidation state becomes less stable going down a group because of inert
effect. However for the transition elements the stability of the higher oxidation
states increase going down a group.

To illustrate this trend, let us first look at Group 6. It is composed of Cr, Mo

and W. We have seen that chromium in +6 oxidation state as in K 2CrO4 is a
good oxidizing agent forming Cr3+ as the product. This means that in many
instances Cr(+3) is more stable than Cr(+6). In contrast, molybdenum and
tungsten in +6 oxidation state in K2MoO4 and K2WO4 are not easily reduced.
This implies that lower oxidation states, e.g., Mo(+3) and W(+3) are not as
easy to form as Cr(+3), making the +6 oxidation state more stable. Thus the
stability of the +6 state for Group 6 elements will be W 6+>Mo6+>Cr6+. We find
the same trend in Group 4 which is composed of Ti, Zr and Hf. For all the
three elements, most stable oxidation state is +4. However Ti(+2) and Ti(+3)
can be formed from Ti(+4) by the use of good reducing agent but lower
oxidation states of Zr and Hf are extremely difficult to prepare. Table 1.16
shows how various oxidation states of some elements of period 4 tend to react
with respect to oxidation and reduction.

Going from left to right across period 4, M2+(aq) ions are known for the last
seven elements from V to Cu and M3+(aq) ions are known for the first seven
elements from Sc and Co. Thus, there is an overall increase in stability of
M2+(aq) with respect to oxidation as one moves across the series. However, in
the case of iron, Fe2+(aq) is less stable than Fe3+(aq) because of the extra
stability associated with half-filled (d5) orbitals in the case of Fe3+(aq). Sc
could have an oxidation state of (+2) if both s electrons are used for bonding
and (+3) when two s and one d electrons are involved. Ti has an oxidation
state (+2) when both s electrons are used for bonding, (+3) when two s and
one d electrons are used and (+4) when two s and two d electrons are used.
Similarly, V shows oxidation states of (+2), (+3), (+4) and (+5). In the case of
Cr, by using the single s electron for bonding, we get an oxidation state of
(+1): hence by using varying numbers of d electrons oxidation states of (+2),
(+3), (+4), (+5) and (+6) are possible. Mn has oxidation states (+2), (+3), (+4),
(+5) (+6) and (+7). In case of the first transition series the lowest oxidation
state displayed is tha number of s electrons and the highest oxidation state is
36
the number of s and d electrons.
Unit 1 General Characteristics of Main Group Elements and Transition Elements

The highest oxidation states are often stabilized in the oxide and fluoride
compounds, e.g., MnO4, CrO24 , VO2 , VF5 , etc. In these compounds O2 and
F are difficult to be oxidized by the central metal because O and F are strong
oxidizing agents.

Table 1.16: Reactivity of some oxidation states of first transition series

elements in aqueous solution

Reducing agents ⟶ Most stable ⟵ Oxidising agents

3+
 Sc 

Ti2+, Ti3+ Ti4+ 

2+ 3+ 4+ 5+
V ,V V V (slightly)

Cr2+ Cr3+ Cr6+

2+ 3+ 4+ 7+
 Mn Mn , Mn , Mn

Fe2+ Fe3+ 
2+ 3+
 Co Co
2+
 Ni 
2+ 2+
Cu Cu 

Once the d5 configuration is exceeded, i.e. in the last five elements, the
tendency for all the d electrons to participate in bonding decreases. Thus, Fe
has a maximum oxidation state of (+6). However, the second and third
elements in this group attain a maximum oxidation state of (+8) in RuO4 and
OsO4. Can you guess why this difference between Fe and the other two
When we say that
elements Ru and Os? Well, the reason is the increased size of the atoms.The compounds are
oxidation states form a regular ‘pyramid’ as shown in Table 1.14. The stable, it is meant that
oxidation number of all elements in the elemental state is zero. In addition, they exist at room
several of the elements have zero-valent and other low valent states in temperature, are not
complexes. Low oxidation states occur particularly with  bonding ligands such oxidized by the air,
as carbon monoxide and dipyridyl. The higher oxidation states are displayed are not hydrolysed by
water vapour and do
with electronegative elements like oxygen and fluorine. Compounds in higher
not disproportionate
oxidation states are oxidizing in nature and covalent while those in lower or decompose at
oxidation states are reducing and ionic. Similar but not identical pyramids of normal temperatures.
oxidation states are found in the second and third rows of transition elements. Within each of the

SAQ 7
a) Explain briefly in the space provided below, the existence of OsO 4 in
terms of trends in oxidation states.

b) What are the basic requirements for stabilization of high and low oxidation
states of transition metals.

c) Describe and account for the trends in the ionic radii and the stability of
high oxidation states upon moving from the second to the third row of the
transition series.
37
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

1.3 STABILITY OF VARIOUS OXIDATION

STATES FOR Mn, Fe AND Cu
Latimer Diagrams

Latimer diagrams, also called reduction potential diagrams, show the different
species of an element in varying oxidation states and are widely used to
ascertain relative stabilities of different oxidation states. Arrows are put
between different species and standard potentials involving two immediate
species are written over the arrows. The oxidation state of the element
concerned is specified under each species which may differ by one or more
electrons. The species with the highest oxidation state is placed at the
extreme left and the one with the lowest at the right extreme. The first point to
understand here is how to construct a Latimer diagram? You have to
remember that in a Latimer diagram, oxidation members decrease from left to
right, then the numerical values of the standard potentials (E 0) in volts are
written above the line joining the species involved in the particular couple.
Typically standard conditions are taken in either strong acid ([H+] =1 M, pH 0)
or strong base ([OH]) =1M, pH 14).

Latimer diagram for manganese (in 1 M acidic solution at 25 ºC ) in oxidation

states from +7 to 0 is shown below:
- 2- 3- 3 2
MnO4 MnO4 MnO4 MnO2 Mn Mn

0.564V
 
0.274V
 
4.27V
 
0.95V
 
1.51V
 
1.18V
 Mn
7 6 5 4 3 2

The Latimer diagram has in it all the standard potentials for redox reactions of
the element Mn, See the last part which connects Mn2+ and Mn which gives
the potential for the half-cell reaction:

Mn2 (aq )  2e  Mn(s ) E10/ 2  1.18 V

Next look at the point which connects Mn4+and Mn3+ which basically represents
the reaction:

MnO2 (s )  4H (aq )  e   Mn3  (aq )  2H2O (l ) E10/ 2   0.95 V

After this, let us see how to calculate the standard potential for non-adjacent
species from the Latimer diagram. Remember that the standard potential
values (E0) are not additive. They have to be converted to
ΔG0 (   n F E0 ) values which are additive. We can calculate values for multi-
electron reactions by first adding ΔG0 (   n F E 0 ) values and then dividing by
the total number of electrons. Example, for conversion of MnO 4 to Mn2  the
Oxygen atom is
standard potential will be:
assigned an oxidation
state of -2 and the 1(0.56)  1(0.274)  1(4.27)  1(0.95)  1(1.51)
hydrogen atoms an E0   1.51V
5
oxidation state of +1.

38 5 electrons are involved in this oxidation number change.

Unit 1 General Characteristics of Main Group Elements and Transition Elements

It is possible to predict whether a species will disproportionate into a lower and

a higher oxidation state from an inspection of the Latimer diagram covering the
redox species. If the potential to the right of the species is higher than the
The highest oxidation
potential on the left, then the species will undergo disproportionation. Let us
state is listed on the
take the following case: left and the reduction
electrode potentials
M2 xvolt
M yvolt
M(s)
are listed between
each species and the
The disproportionation reaction will be as:
next reduced form,
with the lowest
2M (aq) M(s )  M2 (aq) oxidation state
appearing on the
We have right. If the potential
on the right of a
M+ (aq)+e→ M(s); E0 = y volt (right hand side)
species is higher than
M2+ (aq)+e→ M+(aq); E0= x volt (left hand side) the potential on the
left then the species
If we now subtract the left hand side (half reaction) from the right hand side would undergo
(half reaction) of the Latimer diagram we get the disproportionation reaction disproportionation.
whose standard potential is given by:

E0 = y – x

When (y - x) is positive i.e. when the potential to the right of the redox species
(of the Latimer diagram) is higher than that to the left, we have E 0 > 0. This
means ΔG0  0 and so the reaction is spontaneous i.e. the species will
disproportionate.

Latimer diagram for Iron (in acid solution)

SAQ 7
Find the standard potential for the three-electron reduction of MnO -4 to MnO2(s)
where the three-electron reduction for Mn is given as in section 1.5.

1.4 SUMMARY
In this unit you have studied that periodic trends of properties like atomic radii,
ionisation energy, electronegativity electrode potential and oxidation states of
main group elements & transition elements. These atomic properties are
related to the electronic configuration of the atoms of elements. These vary in
a more or less regular way that is to say exhibit periodicity as we go across a
period of the periodic table. Therefore, these atomic properties are also called
periodic properties. Also the …………… have been discussed. 39
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

1.5 TERMINAL QUESTIONS

1. a) How does atomic size vary in a group and in a period? Give reasons
for the variation.

b) Arrange H, H+ and H- in order of increasing atomic radius.

2. What are isoelectronic ions? How does their size vary with the change of
atomic number?

3. Which is the Larger member of each of the following pairs of ions? Give
reasons.

i) TI+ or TI3+ ii) N3 or F; iii) O2 or S2; iv) Na+ or K+; v) Ca2+ or Zn2+

4. Why is the second ionisation energy of sodium higher than that of

magnesium?

5. Among the elements Li, K, Ca,S and Ne, which ones have the lowest and
highest first ionisation energy?

6. Among the elements of the second period, i.e., Li, Be, B, C, N, O, F, pick
out:

i) the element with the highest first ionisation energy

ii) the element with the highest electronegativity

iii) the element with the largest atomic radius

iv) the most reactive nonmetal

v) the most reactive metal

7. Explain why the electronegativity values of noble gases are zero while
those of halogens are the highest in each period.

8. Across the periodic table, the effective nuclear charge increases. Explain
why the ionization energies of the first four second-period elements are in
the order Li < Be > B < C.

1.6 ANSWERS
Self Assessment Questions

The radius of an atom 1. a) 1s2 2s 2 2p6 3s2 3p4

can be defined as the
distance from the b) i) 4s23d5 ii) 5s24d10 iii) 4s23d10 iv) 5s14d8 v) 4s23d2 vi) 5s24d4
centre of the nucleus
to the point where the
c) i) Mn2+ ii) Ir3+ iii) Ni2+ iv) Mo2+ v) Ti2+ vi) Fe3+ vii) Pt2+ viii) Nb3+
electron density is
2. (i) rSi–C = rSi + rC or rSi = rSi–C  rC
virtually zero.
or rSi = 193  77 = 116 pm

(ii) The interatomic distance in Br2 is 228 pm, what is the radius of Br?
40
Unit 1 General Characteristics of Main Group Elements and Transition Elements

3. In the elements of period 2, i.e., from Li to Ne the value of effective

nuclear charge increases by 0.65 units whereas in the elements of 3d
series it increases by 0.15 units from one element to another. In other
words in the elements of period 2, it increases more steeply.

4. a) i) Na; ii) Br; iii) I; iv) S; v) Cl; vi) Li

b) N3 > 0 > F > Ne > Na+ > Mg2+ > Al3+ > Si4+

5. (i) Calcium (ii) Titanium (iii) Molybdenum (iv) Osmium

b) Due to lanthanoid contraction. Because of the filling in of 4f orbitals in

the lanthanoids.

6. a) Atom having [He]2s2 2p3 configuration will have the highest first
ionisation energy because this is the smallest atom having exactly
half filled p subshell.

b) i) Na < P < N < Ne

7. For the the three-electron reduction of MnO-4 (aq ) to MnO2(s),

1(0.564)  1(0.274)  1(4.27)

E0   1.70 V
3

Terminal Questions
1. a) Atomic size generally decreases across a period and Increases down
a group in the periodic table. Across a period as the atomic number
increases, effective nuclear charge also increases, whereas the
number of shells remains the same. As a result of this, the electrons
are pulled in and the size of the atom decreases. On the other hand,
when we move down a group, the effective nuclear charge remains
almost the same, but the number of shells increases from one
element to the next in the group. Therefore, the electrons become
farther from the nucleus and the size generally increases.

b) H+ < H < H

2. Ions having equal number of electrons are called isoelectronic ions. In a

series of isoelectronic ions, size decreases from anion to cation. The
higher is the charge on the anion, the larger is its size. For a cation, the
higher the charge, the smaller is its size.

3. i) Tl+ ii) N3 iii) S2 iv) K+ v) Ca2+

4. The second ionisation energy of sodium is higher than that of magnesium

because the removal of a second electron from the former, the stable core
of 8 electrons is to be disrupted. Therefore, more energy has to be
supplied. In the latter case, removal of second electron leaves behind a
stable core.

5. Among the elements, Li, K, Ca, S and Ne, K and Ne have the lowest and
the highest first ionisation energies.

6. i) F ii) F iii) Li iv) F iv) Li 41

Block 1 Main Group Elements, Transition Elements and Structure of Molecules

7. Since noble gases have a stable electronic configuration, they have no

tendency to attract the bond pair to themselves. Therefore, their
electronegativity is zero. On the other hand, halogens are only one
electron short of noble gas configuration. So, they have a very high
tendency of attracting the bond pair to themselves. Therefore, their
electronegativity values are the highest in the respective periods.

8. The ionization energies of the first four second-period elements are in the
order Li < Be > B < C. The Be has a doublet in its outermost valence shell,
so its ionization energy is more than B, where the outermost electron can
be removed much more easily.

42
Unit 2 The Structures of Molecules

UNIT 2

THE STRUCTURE OF
MOLECULES

Structure
2.1 Introduction 2.5 Geometric and Optical
Isomers
Expected Learning Outcomes
2.6 Summary
2.2. VSEPR (Along with Point
Groups) 2.7 Terminal Questions
2.3 Walsh Diagram (Triatomic and 2.8 Answers
Penta-atomic Molecules), d-
2.9 Further Reading
p Bond
2.4 Bent’s Rule and Energetics of
Hybridization

2.1 INTRODUCTION
In the previous unit you have learnt about the periodic trends of main group
elements and transition elements along with their electronic configuration.
Also the stability of various oxidation states for Mn, Fe and Cu along with
Latimer diagrams were discussed there. In your previous courses of
chemistry you must have been introduced to various semiquantitative models
in order to interpret the structures pertaining to molecules. Models of
molecular structure as such have been developed utilizing valence bond and
molecular orbital theory. In this unit you will be introduced to how to describe
the shapes of molecules with the help of the Valence Shell Electron Pair
Repulsion (VSEPR) Theory. Thereafter you will be learning about Walsh
diagrams and d-p bond. We will also discuss Bent’s rule and the energetics
of hybridization before we discuss geometric and optical isomers.

Expected Learning Outcomes

After studying this unit you should be able to:
 describe the postulates of valence shell electron pair repulsion theory;
 predict the shapes of molecules (along with point groups) on the basis of
valence shell electron pair repulsion theory;
43
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

 describe Walsh Diagram for triatomic and penta-atomic molecules;

The atoms in a
molecule combine in  understand d-p bond;
such a manner that
each atom has a  discuss Bent’s rule and energetics of hybridization; and
definite position
relative to other  describe geometric and optical isomers.
atoms and give rise to
the specific three- 2.2 VALENCE SHELL ELECTRON PAIR
dimensional structure
of a molecule called REPULSION (VSEPR)
the molecular
geometry. The The Valence Shell Electron Pair Repulsion (VSEPR) theory provides a way
molecular geometry or is an approach that allows us to predict the probable structure for the
can be determined molecules. Let us now discuss about the postulates of VSEPR theory.
experimentally.
The first postulate states that bonding and nonbonding electron pairs in the
The VSEPR theory valence shell of the central atom in a molecule arrange themselves in space in
was put forth by such a way that they minimize their mutual repulsion. The second one states
Sidgwick and Powell that the repulsion between two lone pairs of electrons in a molecule is greater
in 1940 and was later than that between a bond pair and a lone pair which in turn is greater than that
refined and extended between two bond pairs. The order of repulsive force between different
by Nyholm and
possibilities is given below:
Gillespie in 1957.
VSEPR theory lone pair - lone pair > lone pair - bond pair > bond pair - bond pair
accounts for the
geometric Table 2.1: The basic arrangement of electron pairs according to VSEPR model
arrangements of Number of Predicted geometry
electron pairs around electron pairs
a central atom in
terms of the
2
electrostatic repulsion
Linear
between electron
pairs.
3

Trigonal planar

Tetrahedral
5

Trigonal bipyramidal

Octahedral
44
Unit 2 The Structures of Molecules

In case of molecules with the central atom having one or more pairs of lone
The positions of the
pair electrons in addition to the bond pairs of electrons, we have to use both bond pairs define the
the postulates. The first postulate decides the location of the electron pairs shape of the molecule
(bond pair and lone pair) around the central atom. In other words it determines although bond angle
the electron pair geometry. As per the second postulate the electron pair values depend on the
geometry changes as there is difference in the extent of repulsion between the number of both the
bond pairs and lone
lone pairs and bond pairs etc. Thereby, the final molecular geometry i.e. the
pairs around the
location of atoms around the central atom is arrived at.
central atom.
For example, in ammonia the central atom (N) contains a total of four
electron pairs (three bond pairs and one lone pair) predicts tetrahedral It may be noted that
geometry. We can predict that the three bond pairs will occupy three corners in molecules with
of a tetrahedron centred on the nitrogen atom while the lone pair orbital will trigonal bipyramidal
point towards the fourth corner of the tetrahedron. But due to the difference in arrangement, there
the repulsive force between bond pair─bond pair and lone pair─ bond pair, the are two types of
bonds, namely
NH3 molecule does not have a tetrahedral shape instead it takes a pyramidal
equatorial (e) and
shape (107o bond angle) or a trigonal pyramid to be more accurate. axial (a). The angle
between two
Table 2.2: Molecular geometries of molecules with a total of 5 and 6 electron
equatorial bonds is
pairs with different combinations of lone pairs and bond pairs o
120 while that
No. of electron pairs Molecular Molecular shape between an axial and
Total Bond Lone geometry Examples an equatorial bond is
o
pairs pairs 90 .

5 5 0 trigonal PCl5,
bipyramidal SnCl 5

5 4 1 see-saw TeCl4,
IF4 , SF4

5 3 2 T-shaped ClF3, BrF3

5 2 3 Linear XeF2,
ICl 2

6 6 0 Octahedral SF6, PF6

6 5 1 square IF5, SbF52

pyramidal

6 4 2 square BrF4 ,
planar XeF4

45
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

Now let us understand how to apply the VSEPR model systematically.

1. You should firstly from the electronic configuration of the elements, write
down the Lewis structure. For example, in the carbon dioxide molecule,
there will be a total of 16 valence electrons to distribute among three atoms
(Fig. 2.1):

Fig 2.1: Lewis structure of carbon dioxide molecule.

Here you should note that both Fig. 2.1(a) and (b) are valid Lewis
structures. So, we cannot predict the bond angle from the Lewis structure.

2. A structure should now be considered which lets all the electron pairs in the
valence shell of the central atom(s) get as far away from each other as
possible. This helps the molecule to achieve the lowest energy and you can
predict which basic shape the molecule would adopt by the relation
between number of electron pairs and arrangement as shown in Table 2.1.
Next, you have to find out which location corresponds to atoms and then
predict the shape of the molecule from Table 2.2.

Table 2.3: The description of molecular shapes

Shape Examples

Linear HCN, CO2

Angular (bent) H2O,O3

Trigonal planar BF3 , SO3 , CO32-

Trigonal Pyramidal NH3,SO32-

Tetrahedral CH4,SO24-

Square planar XeF4

Square pyramidal Sb(Ph)5

Trigonal bipyramidal PCl 5 (g), SOF4

Octahedral SF6 , PCl -6

- bonds are dealt by ignoring the  bonds at first. For example, in carbon
dioxide two  bonds form on opposite sides of the carbon atom.
Hybridization of the carbon 2s and 2pz orbitals gives sp hybrid orbitals with
a bond angle of 180o.

3. Deciding on the number of  bonds next,  bonds are added so that the
molecule gets completed. In carbon dioxide, px and py orbitals on the
carbon atom were unused by the  system and are available for the
46 formation of  bonds.
Unit 2 The Structures of Molecules

+
O
+
+
F
C 3v
c) d)

Br Br
Br

Al o Al
90
Br
Br Br
e) (f)

Fig. 2.2: Some simple molecular structures in which all electrons on the central
atom form bonding pairs: (a) trimethylborane (b) carbonyl chloride
(phosgene (c) phosphorous oxyfluoride (d) phosphorus pentachloride
(e) Phosphorus tetrachloride (f) aluminum bromide dimer.

The molecular orbitals approach undoubtedly justifies these structures but the
VSPER rules can be applied directly and in a much easier way to approach a
new structure. Now let us predict the structures of some inorganic compounds
after drawing their Lewis structure and applying VSEPR rules. Also we will
have to keep in mind the symmetry and point group associated with it.

Trimethylborane: The Lewis structure of (CH3)3B will place six electrons in the
valence shell of the boron atom. To minimise repulsion, the methyl groups
should be located at the corners of an equilateral triangle. This results in sp2
hybridization for the boron atom as shown in Fig. 2.2 a. The resulting point
group is D3h.

Phosgene: A Lewis structure for OCCl2 has eight electrons about the carbon,
but one pair forms the  bond of the double bond, so sp2, hybridization will be
the most stable as shown in Fig. 2.2 b.

Phosphorus oxyfluoride: Two Lewis structures can be drawn for the OPF3
molecule.

Fig. 2.3: Lewis structure of OPF3 molecule. 47

Block 1 Main Group Elements, Transition Elements and Structure of Molecules

 bonds from sp3 tetrahedral orbitals form between the central phosphorus
atom and each of the three fluorine atoms and one oxygen atom. The
symmetry gives A fifth bond, d-p bond forms by the overlap of one of the 3d
orbitals of phosphorus atom with a 2p orbital on the oxygen (Fig 2.2c) atom
which leads to more stabilisation. The symmetry gives C3v point group.

Phosphorus pentachloride: A Lewis structure for the PCl5 molecule requires

ten electrons in the valence shell of the phosphorus atom forming five 
bonds. Five bonds in three dimensions cannot be oriented in such a way that
all are equidistant from one another. The trigonal bipyramidal (Fig. 2.2d) and
square pyramidal arrangements minimize repulsions in such cases. Other than
coordination compounds, most of the five-coordinate molecule form trigonal
bipyramidal structure. The structure of the PCl5 molecule is shown in Fig. 2.2d
(sp3 hybrid). The bonds are of two types: axial, the linear Cl-P-Cl system; and
equatorial, the three P bonds forming a trigonal plane. The symmetry gives D3h
point group.

Aluminium bromide (D2h). We would expect a trigonal planar structure with

120o bond angles for the molecule AlBr3. This does not match with the
experimentally obtained aluminium bromide which is a dimer. The dimer
Al2Br6 contains four bonds per aluminum atom. This happens as the aluminum
atom behaves like a Lewis acid and accepts a lone pair in its unused p orbital
and rehybidize from sp2 to sp3. The structure of Al2Br6 molecule is shown in
Fig. 2.2 f where the average bond angle is 90o inside the ring.

When there are five electron pairs around the central atom for cases like
InCl 52  , where the square pyramidal has only very little extra energy than that
of the trigonal bipyramidal, then both the square pyramidal (as shown in
Fig. 2.4) as well as trigonal-bipyramidal arrangement may occur.

Fig. 2.4: lnCl 52 

The Table 2.2 shows various options of molecular geometries of molecules

with a total of 5 and 6 electron pairs with different combinations of lone pairs
and bond pairs.

Though the valence bond terms (Lewis structures, hybridization, etc.) have
been incorporated in the above examples, the beauty of the VSEPR method of
predicting structures for molecule is the application of the second postulate,
that is minimising the repulsion between electron pairs. Valence bond (VB)
hybridization schemes may be avoided for VSEPR although it is most readily
applied in a VB context. The VSEPR model is widely accepted as an
48 extremely powerful one for predicting structures of molecules.
Unit 2 The Structures of Molecules

Structures of Molecules Containing Lone Pairs of Electrons

Now we will specially look at the molecules containing lone (unshared)
electron pairs. We have to look at the differences between the bonding
electrons and the nonbonding electrons. Let us start with the example of the
H2O (water) molecule. H2O molecule in which the central oxygen atom is
bound to two hydrogen atoms and also contains two pairs of nonbonding
electrons. There are four pairs of electrons (2 bonding and 2 nonbonding).
Each of the four corners of the tetrahedron would have one electron pair. The
repulsive forces between lone pair─lone pair; lone pair─bond pair and bond
pair─bond pair electrons decide the shape of the water molecule. This
structure is bent shaped and not pure tetrahedral. The H–O–H bond angle in
water is 104.5° somewhat less than even the H─N─H angle of 107o in
ammonia.

In the second postulate of VSEPR you have learnt that the order of repulsive
energies is:

lone pair-lone pair > lone pair-bonding pair > bonding pair-bonding pair.

As the lone pair does not have the second nucleus, it is attracted only by its
own nucleus and thereby occupies a greater angular volume as shown in
Fig. 2.5 .

Fig. 2.5: (a) Four equivalent bonding electrons pairs, (b) Three bonding electron
pairs repelled by a nonbonding pair of electrons.

Fig. 2.6: The molecular structure of (a) methane (b) ammonia (c) water.

In Fig. 2.6, the isoelectronic series methane, CH4 (no lone pairs, bond angle
=109.5), ammonia, NH3 (one lone pair, bond angle = 107o); and water, H2O
(two lone pairs, bond angle = 104.5 o) have been shown.

So, if we follow the second postulate of VSEPR, we can state that lone pair
will always occupy a greater angular volume than bonding electrons. The
approximate molecular shape along with possible distortions can be predicted
only if we consider the lone pair. Next, let us discuss how to predict the
structures of more molecules, one by one. 49
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

Sulfur tetrafluoride: The molecule SF4 has ten electrons in the valence shell of
sulfur, four bonding pairs and one nonbonding pair. So, the geometry is
trigonal bipyramidal. Now, let us examine what is the position of the lone pair.
There are two possibilities of arranging the lone pair, either equatorially
or axially. The one with lone pair in the equatorial position is found to match
with the experimental derived structure as in Fig. 2.7b. The bonding pairs are
repelled by the lone pair and bent back forming a distorted structure called
see-saw.
F

F
o
S 130 179o
F

(a) (b)

Fig. 2.7: Sulfur tetrafluoride (Green spheres indicate S, orange spheres indicate
F). (a) Trigonal bipyramidal structure with equatorial lone pair. (b)
Experimentally determined structure of sulfur tetrafluoride.

If you examine the Fig. 2.7 a) you will see that the lone pair has three 90 o
interactions with the equatorial bonding pairs but only two 90o interactions with
the axial bonding pairs. The 120o interactions are not so important to decide
the structure as repulsive forces play a crucial role only at very small
distances. For all cases, lone pair always adopt positions which minimize 90o
interactions. The symmetry gives C2v point group.

Dichloroiodate(I) anion. The ICl-2 anion has two bond pairs and three lone
pairs. The three lone pairs occupy the three equatorial positions to minimise
repulsion and avoid distortion as shown in Fig. 2.8. I has 7 electrons +2
electrons (from 2Cl) + 1 electron (ionic charge) = 10 electrons, which gives 5
pairs. The symmetry gives Dh point group.

Fig. 2.8: The structure of the dichloroiodate(I) anion.

Pentafluorotellurate(IV) anion: In the TeF5- ion the tellurium atom has twelve
electrons that is, 6 pairs in its valence shell. So, five bonding pairs and one
nonbonding pair of electrons form the octahedron as shown in Fig. 2.9 a. But
50 the experimentally determined structure is different. The resulting structure is a
Unit 2 The Structures of Molecules

square pyramid with the tellurium atom 40 pm below the plane of the fluorine
atoms (Fig. 2.9b). The symmetry gives C4v point group.

Fig. 2.9: (a) The predicted pentafluorotellurate(IV) anion. (b) Experimentally

determined structure. [From Mastin, S.H.; Ryan, R. R.; Asprey, L.B.
Inorg. Chem. 1970, 9, 2100-2103.]

Phosphorous trihalides: The bond angles in phosphorus trihalide molecules

are PF3=97.7o, PCl3=100.30, PBr3=101.0o, PI3=102o. The more electronegative
fluorine atom attracts the bonding electron pairs away from the phosphorus
nucleus and allows the lone pair to expand. As a result the F-P-F angle
decreases. So, more the electronegativity of the substituent, lesser the bond
angle. In the same line, the fluorides have smaller bond angles than the
hydrides (NF3=102.3o, NH3=107.2o, OF2=103.1o, OH2=104.5o). Gillespie has
discussed the effect of substituent electronegativity and pointed out. The The behavior of the
symmetry gives C3v point group. doubly bonded
oxygen atom is in
Carbonylfluoride: Fluorine and oxygen atoms have similar electronegativity several ways similar
and size. There are no lone pairs on the carbon atom, C (4 electrons) + O to that of a lone pair.
(1electrons) +2 F (2 electrons), so three pairs of electron and a  bond is
there. Predicted geometry of the molecule is planar with approximately 120o
bond angles (Fig. 2.10 a). Though it is planar but the geometry is much
distorted from a symmetrical trigonal arrangement (Fig. 2.10b). The oxygen
atom is doubly bonded to the carbon and the C=O bond length (120 pm) is
somewhat less than that of C-F (135 pm) giving rise to more van der Waals
repulsion for the oxygen atom. More important in the present case is the fact
that the double bond contains two pairs of electrons and so will require more
space than a single bonding pair. The symmetry gives C3v point group.

Fig. 2.10: (a) Possible structure of OCF2. Arrows indicate small distortions
resulting from electronegativity and size effects. (b) Actual molecular
structure of OCF2. 51
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

Also this is seen in other compounds with double bonds. In the OSF4 molecule
the doubly bonded oxygen atom occupies equatorial position, thereby binding
the fluorine atoms somewhat from the other two equatorial and the two axial
positions (2.11b). Further examples are listed in Table 2.4. In Fig. 2.11, the
comparison of OSF4 (Fig. 2.11b) with that for SF4 (Fig. 2.11a) is given There is
a major difference between these two: there is a cylindrically symmetrical lone
pair in SF4 but the  bond in O=SF4 has a greater electron density in one plane
than another.
F F
F F

S O S

F F
F F

o o
179 178.5
Axial FSF Angle
o
(idealized = 180 )

o o
Equatorial FSF angle 103 110
o
(idealized = 120 )

a) b)
Fig. 2.11: Molecular structures of (a) sulfur tetrafluoride and (b) thionyl
tetrafluoride.

Table 2.4: Bond angles in molecules

Molecules containing X-Y-X Molecules with lone X-Y-X

doubly bonded oxygen pairs of electrons

O=CF2 108o : GeF2 94o  4o

o o
O2SF2 96 : SF2 98

O=PCl3 103,3o : PCl3 100, 3o

o o
O=SF4 110, 178.5 : SF4 103. 179

O=IF5 82, 89o :IF5 82o

Next let us apply VSEPR model to the molecular structure of XeF 6. So the
VSEPR model predicts that there are six bonding pairs and one lone pair i.e.
Xe:8, 6F:6, which means 14 electrons in total. So seven pairs of electrons.
Therefore a structure based on seven-coordination is thought of. It was
predicted that there may be three possibilities for XeF6. A distorted
pentagonal bipyramid, a distorted octahedron, or a distorted trigonal prism.
The lone pair should occupy a definite geometric position and a volume as
great as or greater than a bonding pair. Three neutral fluoride molecules IF 7,
ReF7, and OsF7 with seven bonding pairs are known. All three have
approximate D5h symmetry, and the structure is a distorted pentagonal
bipyramid (Fig. 2.12).
F

F
F
I F
F
F

52 Fig. 2.12: Molecular structure of iodine heptafluoride.

Unit 2 The Structures of Molecules

The gaseous XeF6 molecule was predicted to have a slightly distorted

octahedron. But strangely the lone pair occupied less space than the bonding
pairs. Fig. 2.13 is the best solution to its structure which is to be a distorted
octahedron in which the lone pair extends either through a face (C3v
symmetry) or through an edge (C2v symmetry).

(a) (b)

Fig. 2.13: Possible molecular structures of xenon hexafluoride: (a) lone pair Bonding pairs to
emerging face of the octahedron; (b) lone pair emerging through edge electronegative
of octahedron, [Source; Gavin, R. M., Jr.; Bartell, L.S. J. chem.. Phys. substituents occupy
1968, 48,2466.] less space than
Several conformations of the dynamic molecule exists. In either of the two those to more
electropositive
models shown in Fig. 2.13, the Xe-F bonds near the lone pair appear to be
substituents. To the
somewhat lengthened and distorted away from the lone. But this distortion is above Drago
less than would have been expected on the basis of the VSEPR model. All suggested the
other hexafluorides such as SF6 and UF6 are perfectly octahedral. So this following empirical
prediction of the XeF6 structure was successful in explaining its distortion. rule which
rationalizes the very
Raman spectroscopy indicates that the IF6 anion, like XeF6 , has lower o
small angles (~ 90 )
symmetry than octahedral. Anions such as in phosphine, arsine,
SbX36  , TeX26  (X  Cl,Br, or I), and BrF6 have been found to have perfectly hydrogen sulfide,
etc., and which is
octahedral structures on the basis of X-ray crystallography. These have the compatible with the
stereochemically inactive lone pair. Raman and infrared spectroscopy have energetics of
indicated, however, that these ions may be either nonoctahedral or extremely hybridization.
susceptible to deformation. So all the anions which are isoelectronic with XeF 6
have confusing structures.

It is of importance to note that XeF6 molecule donate a fluoride ion and form
the XeF5 cation, which is isoelectronic and isostructural with IF5. This matches
with that predicted from theory.

Alkaline halide molecules, MX2 exist only in the gas phase. Solids are ionic
lattices (example CaF2). Most of them are linear, but some, such as SrF2 and
BaF2 are bent. But ionic bonding in these molecules is not under the VSEPR
theory. Electrostatic repulsion of the negative anions should also favor a 180 o
bond angle. At present, there is no simple explanation of these difficulties, but
the phenomenon has been treated by means of Walsh diagrams which has
been discussed in the next section.

Some important points which we should remember:

 Repulsions are of the order LP-LP>LP-BP> BP-BP.
a. When lone pairs are present, the bond angles are smaller than
predicted by rule 1. 53
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

b. Lone pairs choose the largest site, e.g., equatorial in trigonal

bipyramid.

c. If all sites are equal, lone pairs will be trans to each other.

 Double bonds occupy more space than single bonds.

 If the central atom is in the third row or below in the periodic

table, the lone pair will occupy a stereochemically inactive s
orbital and the bonding will be through p orbitals and near 90o
bond angles if the substituent electronegativity is almost of the
value 2.5.

Though the VSEPR model has been well received by inorganic chemists as it
is quite accurate, but the theoretical basis is still not undisputed. Lastly let us
discuss the basic shapes for seven electron pairs around the central atom.
There may be several conformations due to similar energies in them which are
in dynamic equilibrium. In the p block pentagonal-bipyraphidal dominates (eg.
IF7). But XeF5 is planar with two lone pairs.

SAQ 1
From VSEPR, predict the structure of sulfur-hexafluoride and mention is the
symmetry.

SAQ 2
a) Predict the geometry of tetrachloroiodate(III) anion.

b) What are the shapes the ions of solid pentachloride? Now, what will be
the case for PCl 4 ?

2.3 WALSH DIAGRAM (TRIATOMIC AND PENTA-

ATOMIC MOLECULES),d-p BOND
Scientist tried for the modification of LCAO- MO methods so that geometry of
molecules may be predicted in a better way. Walsh diagrams is one of the
basis of such methods which correlate changes in the energies of molecular
orbitals between a reference geometry, which generally has high symmetry,
and a deformed structure consisting lower symmetry. Let us consider the BeH 2
molecule. (Fig. 2.14) and look at the energies of the bonding, nonbonding, and
antibonding orbitals in it. Since the molecule is bent, the first 2g orbital is
constructed from atomic wave functions that are symmetric (g) and hence on
bending there is an increase in overlap. So, the energy of the 2 g orbital
decreases a bit. In contrast, the energy of the 1u orbital increases on
bending. Since the wave function changes sign as shown by the shading, the
terminal hydrogen overlaps in a way that the wave functions becomes
54 negative. Moreover, the linear p orbital.
Unit 2 The Structures of Molecules

Fig. 2.14: Molecular orbital pictures and qualitative energies of linear and bent
AH2 molecules. Open and shaded areas represent differences in sign
(+ or -) of the wave functions. Changes in shape which increase in-
phase overlap lower the molecular orbital energy. [Source: Gimarch,
B.M.J. Am. Chem. Soc. 1971, 93, 593,].

in the bent molecule makes less overlap with the hydrogen atoms. Thus, the
energy of the 1 u orbital increases. BeH2 has a molecular orbital electron
configuration 2  g21 u2. As 1 u loses more energy than 2 g gains. So BeH2
gains energy. Thus, BeH2 is linear and not bent.

The Walsh diagram shown in Fig. 2.14 has limitations. It is accurate only for
molecules in which there is a large separation between the ns and np energy
levels of the central atom. If the ns-np separation is small (as in SrF2 and
BaF2), the 1u level (of Fig. 2.14) does not rise as rapidly as 2g falls, and the
molecule may be stabilized on bending. Note that in MF2 molecules of this
type, the 3g and 1u levels are unoccupied.

So at the end of this section, you must be understanding that electron-electron

repulsions are usually omitted in simple approximations. Also the overlap of
orbitals is most important in this approach. Even though the VSEPR model
and the LCAO-MO approach to stereochemistry are not aggreable in many
points, but these theories of bonding do suggest that when electron-nucleus
attractions are the most and repulsions between electrons are least it leads to
stable molecules.

Structure and Hybridization

Such common geometries and their associated hybridizations are given in
Fig. 2.15. Many additional hybridizations are possible for higher coordination
numbers which are not common. 55
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

We should not say that a certain structure is “caused” by a certain

hybridisation. Instead we should say that a particular structure has certain
hybridisation “associated” with it.

The possible structures may be classified in terms of the coordination number

of the central atom and the symmetry of the resulting molecule (Table 2.5). If
there are two groups about central atom, it will from angular (p2 orbitals, C2v
symmetry) or linear (sp hybrid, D symmetry) molecules. When three groups
are there, it will from pyramidal (p3, C3v) or trigonal planar (p3, D3h) molecules,
with four tetrahedral (sp3, Td) or square planar (dsp2, D4h) forms and five
groups generally form a trigonal bipyramidal (D3h). Sometimes a square
pyramidal (C4v) molecule also forms. Both are dsp3 hybrids, but involve
different orbitals (as shown in Table 2.5). Lastly with six groups, octahedral
molecule (d2sp3, Oh) forms.

Stereochemically active lone pairs additionally lower the symmetry (for

example BF3 is D3h; NF3 is C3v). Also, you should note that the hybridization of
the lone pairs(s) will be different from that of the bonding pairs.

Not all hybrid orbitals are identical in composition as they have different
percentages of s and p character which are oriented in the space. For trigonal
bipyramidal there are three strong equatorial bonds (sp2 trigonal orbitals) and
two weaker axial bond (dp linear orbitals). The square pyramidal hybridization
is approximately a square planar dsp2 set plus the pz orbital. As in the trigonal
bipyramidal hydrization, the lengths and strengths are different.

180o
120o
90o
90o

p2 p3 sp sp2
C2v C3v D D3h
h
8

1
109 2 o
90o

120o
90o

sp3 dsp3 d2sp3

Td D3h Oh

90o
90o
dsp2 dsp3
D4h C4v

Fig. 2.15:Geometries of some common hybrid and nonhybrid bonding

arrangements. Solid lines represent bonds formed from the orbitals on
the central atom  . The dashed lines are geometric lines added for
56 perspective.
Unit 2 The Structures of Molecules

The relation between hybridization and bond angle is simple for s-p hybrids.
For two or more equivalent orbitals, the percent s character (S) or percent p
character (P) is given by the relationship:
S P 1 … (2.1)
COS   
S 1 P

Table 2.5: Atomic orbitals involved in hybrid orbital formation

Hybridization Atomic orbitals
2 3
sp, sp , sp s  arbitrary p n
dsp 2 d 2 2  s  p x  py
x y
3
dsp (TBP) d  s  p x  py  pz
z2
3
dsp (SP) d  s  p x  p y  pz
x2  y 2

d 2sp 3 (TBP) d  d 2 p x  p y  pz
x2  y 2 z

where  is the angle between the equivalent orbitals and the s and p
characters are expressed as decimal fractions. In methane, for example,
0.25
COS    0.333;   109.5 o … (2.2)
 0.75

For example in sp3d, the set of hybrid orbitals into subsets of orbitals can be
resolved into the sp2 subset and the dp subset. If you take the case of the
water molecule, the bonding orbitals are in between pure p and sp3 hybrids.
You can apply Eq. 2.2 to each subset of equivalent orbitals for such
molecules. In water, for example, the bond angle is 104 .5o so

P 1
COS   0.250 
P
COS   P  0.80  80% character and 20% s character

So, if we calculate the net p character over all four orbitals on oxygen, it must
be 3.00 (=px + py + pz). Similarly the, total s character must be 1.00. As the
bonding orbitals contain more-p character, nonbonding orbitals (the two lone
pairs) have less p character proportionately. We must understand that purely
trigonal and tetrahedral hybridizations are probably restricted to molecules
such as BCl3 and CH4 where the central atom has identical substituents. With
five-coordination, most. compounds of nonmetals favour the trigonal
bipyramidal (TBP) structure which has the symmetry which gives D3h point
group. But square pyramidal (SP) (C4v) structures are also found in
coordination compounds. It is important to understand that few compounds do
change their structure continuously from TBP to SP as depicted in Fig. 2.16.

Fig. 2.16: Dynamic equilibrium between the TBP and SP structures for penta
coordinated coordination compounds. 57
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

SAQ 3
Explain why the water molecule is bent rather than linear with the help of
Walsh diagrams.

2.4 BENT’S RULE AND ENERGETICS OF

HYBRIDIZATION
You have already learnt the LCAO linear combination of atomic orbitals
method where the resulting hybrids are having energy which is a weighted
average of the energies of the participating atomic orbitals. Look at Fig. 2.17,
which shows when carbon forms four covalent bonds, although there is a
promotion energy from 1s 2 2 s 2 2 p 2  1s 2 2 s1 2 p 3 . The hybridization to the
valence state is altogether different.

Fig. 2.17: Promotion energy from 1s 2 2 s 2 2 p 2  1s 2 2 s1 2 p 3

In the phosphorus atom there is little initial promotion energy: The ground
state is trivalent, as is the valence state. Hybridization will cost energy as a
filled 3s orbital is raised in energy and half-filled 3p orbitals are lowered in
energy.

So one can find out the strength of the bonds by the magnitude of bond
energies from the energy of hybridization. This will help in deciding the
structure of molecules. Some lone pairs take the role of spherical,
nonstereochemically active orbitals and are not stereochemically active hybrid
orbitals. In the hydrides of the Group 15 and 16 elements, bond angles
considerably decreases as one moves from the first element in each group to
those that follow as shown in Table 2.6.

Table 2.6: Bond angles in the hydrides of Groups 15 and 16

NH3 = 107.2o PH3 = 93.8o AsH3 = 91.8o SbH3 = 91.3o

o o o o
OH2 = 104.5 SH2 = 92 SeH2 = 91 TeH2 = 89.5

As hybridization of the central phosphorus atom requires 600 kJ mol-1 of the

energy, the structure which utilizes pure p orbitals in bonding and allows the
lone pair “sink” into a pure s orbital is favoured. But both bonding and
nonbonding (VSEPR) electrons repel each other and do not favour this. So a
58 disorted tetrahedral structure results. In the case of the small sized elements
Unit 2 The Structures of Molecules

like N and O the steric effects come into play but not in the larger atoms, such
as those of P, As, Sb, S, Se, and Te. So for larger atoms the reduced
hybridization energy of more p character in the bonding orbitals are seen.

3
Fig. 2.18: sp hybridisation in bonding orbitals.

How the bond energy changes with hybridization is also very important to
decide which structure will be stable. The directed lobes of s-p hybrid overlap
more effectively than the undirected s orbitals, the two-lobed p orbitals, or the
diffuse d orbitals, whichever gives better overlap is preferred even at the cost
of higher promotion energies.

Table 2.7 shows effect of the differences in hybrid bond strengths by the bond
lengths in MXn molecules with both equatorial req and axial rax substituents.

Table 2:7: Equatorial req and axial rax bond lengths for different
substituents in MXn molecules.
req (pm) rax (pm)
PF5 153.4 157.7
PCl5 202 214
SbCl5 231 243
SF4 154 164
CIF3 159.8 169.8
BrF3 172.1 181.0

An sp3 hybrid orbital set is seen to be combination of pz d 2 hybrids and spxpy

z

hybrids. Two linear hybrid orbitals bond axially for and trigonal, equatorial
bonds for the sp2 type. The sp2 hybrid orbitals are shorter than the weaker
axial bonds. Experimental evidences have shown that when the
electronegativities of the substituents on the phosphorus atom differ, as in the
mixed chlorofluorides, PCl xF5 - x , and the alkyphosphorus fluorides, R xPF5 - x , the
more electronegative substituent occupies the axial position and the less
electronegative substituent the equatorial one. This is an example of Bent’s
rule, which states: More electronegative substituents “prefer” hybrid orbitals
having less s character, and more electropositive substituents “prefer” hybrid
orbitals having more s character. Although proposed as an empirical rule,
molecular orbital calculations also match in the chlorofluorides of phosphorus.

A second example of Bent’s rule is provided by the fluoromethanes. In CH2F2 the

F-C-F bond angle is less than 109.5o, indicating less than 25% s character, but
the H-C-H bond angle is larger and the C-H bond has more s character.
Similar results are observed for the bond angles in the other fluoromethanes. 59
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

This phenomenon is often termed “apicophilicity” as it explains which

substituent will occupy the typical orbital in TBP structures. It is well illustrated
in a series of oxysulfuranes. These, as well as related phosphoranes, provide
interesting insight into certain molecular rearrangements which you will learn
later in the second semester inorganic chemistry course of this M.Sc.
programme.

Bent’s rule is also consistent with, and may provide alternative rationalization
for, Gillespie’s VSEPR model. Thus the Bent’s rule predication that highly
electronegative substituents will “attract” p character and reduce an
electronegative substituent. Strong, s-rich covalent bonds require a larger
volume in which to bond. Thus, doubly bonded, oxygen, despite the high
electronegativity of oxygen, seeks s-rich orbitals because of the shortness and
better overlap of the double bond. Again, the explanation, whether in purely
s-character terms (Bent’s rule) or in larger angular volume for a double bond
(VSEPR), predicts the correct structure.

SAQ 4
Apply the Bent’s rule to predict the pentacoordinated structure for any
coordination compound.

2.5 GEOMETRIC AND OPTICAL ISOMERS

A detailed classification of isomerism in metal complexes is given in Fig. 2.21.

Fig. 2.19: Classification of isomerism in metal complexes.

The two principal types of isomerism known among coordination compounds

are structural isomerism and stereoisomerism. Stereoisomerism can be further
subdivided as follows:

(i) Geometrical isomerism (ii) Optical isomerism

Let us discuss them one by one.

Stereoisomerism

Stereoisomers have similar metal ligand bonding sequence but the

arrangement of atoms in space is different. Stereoisomerism can be divided
60 into two kinds: geometrical and optical.
Unit 2 The Structures of Molecules

(i) Geometrical isomerism occurs when ligands can assume different

positions around the metal ion. For example, the compound [Pt(NH 3)2Cl2]
has a square planar structure. The two possible arrangements are shown
in Fig. 2.22

In the cis-isomer the two ammonia molecules are next (cis) or adjacent to
each other whereas in the trans-isomer the two ammonia molecules are
across (trans) to each other.

Fig. 2.20: cis- and trans- isomers of diamminedichloridoplatinum(II).

This type of isomerism is not possible for complexes with coordination

number 2 (linear molecule), 3 (trigonal planar) and 4 (tetrahedral
geometry).

For square planar complexes Ma4, Ma3b or Mab3 where a and b are
monodentate ligands, geometrical isomerism is not possible. However,
square planar complexes of the type Ma2b2, Ma2bc. Mabcd and M(AA)2,
M(AB)2where AA and AB represent symmetrical and unsymmetrical
bidentate ligands respectively  do give geometrical isomers. A few
examples are given below:
Type Compound Isomers

Ma2b2 [Pt(NH3)2Cl2]

Ma2bc [Pt(NH3)2Br Cl]

Mabcd [Pt(NH3)l)(C5H5N)]]

Fig. 2.21: Isomers of square planar complexes

Bridged binuclear planar complexes like [PtCl 2l 2 (Pet 3 ) ] may exist in three
isomeric forms as shown in Fig. 2.22:

Fig. 2.22: Isomers forms of [PtCl2l2 (Pet 3 ) ]

Six-coordinated octahedral complexes of the type Ma 4b2, Ma3b3, Ma3b2c,

Ma3bcd, Ma2b2cd, Ma2bcde, Mabcdef would all give geometrical isomers.
Systems with one or two bidentate ligands along with monodentate ones
would also give geometrical isomers. Thus we see that with octahedral 61
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

geometry a large number of isomers are possible; whether they can be

separated or not is a different question which depends on many factors.
As we increase the number of different ligands, the possible number of
isomers increases. For example, Ma2b2 type of complex would give only
two isomers cis- and trans-. Similarly for Ma3b3 type of complex we again
get two isomers facial (fac-) and meridional (mer-) isomers. In the former
(fac-) three ligands of one type form one triangular face of the octahedron
and the other three are on the opposite face, as shown in Fig. 2.23(a). In
the latter (mer-).one set of these ligands are arranged around an edge of
the octahedron whereas the other set occupies the opposite edge as
shown in Fig. 2.23(b).

Fig. 2.23: (a) facial and (b) meridional isomers of Ma3b3 complex.

I II III

IV V
Fig. 2.24: Geometrical isomers of Ma2b2cd complex.

When writing the geometrical isomers you must make sure that the
relative positions of the ligands must be different in each configuration and
it is not just a rotation of the molecule as a whole. The trick in writing
these configurations is that you fix the position of some ligands initially
and rotate the other ligands, then for the isomer write the configuration
with the changed positions of the ligands which were fixed earlier. For
example, in the above case we have fixed the cis position for the two
ligands ‘a’ and wrote all possible configurations as shown in Fig. 2.24 I, II
and III. Once that is over then we put the two ‘a’ ligands in trans-positions
and again rotate other ligands in all possible ways to get a different
configuration. Finally you must remember that there is no formula
available which can predict the number of possible isomers for any
particular compound and hence, you have to try writing down all possible
configurations in each and every case (which of course, requires a lot of
62 patience and practice).
Unit 2 The Structures of Molecules

(ii) Optical Isomerism: Two isomers which have almost identical physical and
chemical properties like melting point, boiling point, density, colour etc. but
differ in the way they rotate the plane-polarised light are called optical
isomers. Such optically active compounds exist in pairs and are known as
stereoisomers or enantiomers. These isomers are non-superimposable
mirror images of each other just like your right hand is the mirror image of
your left hand. Any molecule which contains either a-centre of symmetry
or a plane of symmetry will not show optical isomerism. Optical isomerism
is rarely observed in square planar complexes. Tetrahedral complexes of
the type [M(AB) 2 ] where (AB) is an unsymmetrical bidentate ligand give
optical isomers as shown in Fig. 2.25 especially where M = Be, B. It is customary to
symbolize a chelating
agent as a curved line
with the abbreviation
for the ligand in the
middle. Thus en could
be used to represent
NH2CH2-CH2NH2.

Fig. 2.25: Optical isomers of M(AB)2 complex.

However, optical iomerism is very common with octahedral complexes of

the type M(AA)3, M(AA)2ab, M(AA)a2b2, M(AA)(BB)a2 etc. A few typical
examples are shown in Fig. 2.26.

Fig. 2.26: Optical isomers of [Co(en) 3]3+.

This brings us to the end of this unit. However, after reading this section you
should be able to solve the following SAQ.

SAQ 5
A square-planar complex with formula [MABCD] can form three isomers.
These isomers are called “A trans to B” and so on. Draw and label the three
possible isomers.
63
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

2.6 SUMMARY
In this unit you have learnt about the postulates of valence shell electron pair
repulsion theory. Thereafter, you have learnt how to predicted the shapes of
molecules on the basis of this theory and you have also learnt about the point
group associated with these molecules. Thereafter, you have learnt about
Walsh diagram and you have specially applied it to triatomic and penta-atomic
molecules. Finally, the Bent’s rule and energetics of hybridization have been
discussed along with the geometric and optical isomers. So in this way in this
unit you have been learning how to predict the structure of molecules and in
the next unit you will be learning about phosphorus and nitrogen compounds.

2.7 TERMINAL QUESTIONS

1. Predict the geometry of the bromine trifluoride molecule.

2. Arrange the following species in the order of increasing bond-angle,

considering the repulsive forces due to lone pair: NO 2 ,NO2 and NO 2

3. What shapes can be predicted for a) SO3 b) SO32  c) 1F5 .

4. With the help of VSEPR rules predict the structure of 1Cl6 and IF6 ions.

5. What is the molecular structure of methylene sulfur tetrafluoride Give

reasons why the Feq-Feq angle has been reduced to 97o In CH2=SF4
molecule (Fig..).

6. Predict the reason why SeF62  ions is octahedral.

7. Predict the structure of the water molecule with the help of Walsh
diagrams.

8. In which of the following molecule there is a possibility of p-d bonding?

S4N4F4, S4H4N4, N  SF3, H3SiOSiH3, CH3N=C=S and Et3NO.

9. cis and trans isomers are possible for octahedral complexes with the
formula [MA4B2]. Draw and label the two possible isomers.

2.8 ANSWERS
Self Assessment Questions
1. Sulfur hexafluoride (Oh). Six sulfur-fluorine  bond require 12 electrons in
the valence shell. Six equivalent bonds require an octahedron and so
sulfur will be sp3d2 hybridized as shown in the Fig. below. The symmetry
gives Oh point group.

3 2
64 Sulfur hexafluoride with six sp d  bonds
Unit 2 The Structures of Molecules

2. a) It has ten electrons (I (7) + 2Cl (2) + 1 (ionic charge)). So forms 5 pairs.
The ICl -4 anion has four bonding pairs and two lone pairs. In an
undistorted octahedron, all six points are equivalent, and the lone pairs
could be in the adjacent or cis positions. To minimise lone pair-lone pair
repulsion, the trans structure is preferred. Lone pairs are not visible and
so square planar is the final geometry as shown in the figure (part c)
below:

Fig. The tetrachloroiodate(III) ion. (a) lone pairs cis to each other, (b) lone pairs
trans to each other. (c) Experimentally determined structure.

b) PCl4 and PCl6 .

PCl4 will have four bonds and will take up tetrahedral arrangement
giving symmetry of Td point group as shown in the Fig. 2.2e.

3. Walsh diagrams can be applied to the nonbonding and antibonding orbitals.

In the water molecule, H2O, with eight valence electrons, the MO
configuration will be 2  g21 u2 1 ux
2
1 ux
2
1 uy
2
. Because the formerly
nonbonding 1 ux orbital is greatly stabilized (3g) on bending, the water
molecule is bent rather than linear.

4. Take example of any compound given in Section 2.4 and explain.

5.

Terminal Questions

1. Bromine trifluoride (C2v): The BrF3 molecule has ten electrons in the
valence shell of the central atom,(Br:7 electrons, 3F:3 electrons) in this
case three bonding occupying equatorial positions. The distortion from lone
pair repulsion causes the axial fluorine atoms to be bent away from a linear
arrangement so that the molecule is a slightly “bent T” with bond angles of
86o 65
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

The molecular structure of bromine trifluoride.

2. NO2 < NO2 < : Nitrogen dioxide (C2v), nitrite ion (C2v), and nitryl ion (Dh).
The three species, NO2 ,NO-2 , and NO 2 , show the effect of steric repulsion of
bonding and nonbonding electrons. The Lewis structures are

+ 
+ O  O
O N O L.P. N 115 o
e N 134o
 + O
O
(a) (b) (c)

(a) The linear nitryl ion, NO 2 , (b) Nitrite ion, NO 2 .

The nitryl ion, NO 2 , CN has 5 electrons, 20 atoms give 2, one positive

charge, so six electrons, adopt a linear structure with two  bonds (a). The
nitrite ion, NO 2 , eight electrons will have one  bond (stereochemically
inactive), two  bonds, and one lone pair. Predicted geometry is to be
trigonal, with 120o angle and sp2 bond. Thus, it is similar to carbon dioxide.
The lone pair repulsion decreases the bond angle is found to be 115 o Fig.
(b).

The nitrogen dioxide molecule (7 electron) is a free radical, i.e., it contains

an unpaired electron. This single electron repels the bonding electrons less
and the bond angle increase from NO2+ to NO2 (Fig. 2.c).

3. a) Pyramidal b) Tetrahedral C) TBP or SP. Give explanation with total

electrons and symmetry

4. ICl6 : l(7)  6Cl- (7)  14, 7 pairs electrons distorted octahedral geometry.
sp3d3 hydbridisdation. Due to difference in sizes of F and Cl, the bond
angles and bond lengths are different in the two molecules.
5. The Feq-Feq angle has been reduced to 97o because the hydrogen atoms lie
in the CSF2 axial plane; we know that the  bond involving a p orbital on the
carbon atom must lie in the equatorial plane of the molecule. And the
resulting repulsion between the  electron and the electron pairs bonding
the equatorial fluorine atoms is dramatic.
F
H F

C S

H F
F
Axial FSF Angle
o o
(idealized = 180 ) 170

Equatorial FSF angle

o o
66 (idealized = 120 ) 97
Unit 2 The Structures of Molecules

6. Even though 7 electron pairs, the lone pair is stereochemically inert and in
the s- orbital.

7. Walsh diagrams can be applied to the nonbonding and antibonding orbitals.

In the water molecule, H2O, with eight valence electrons, the MO
configuration will be 2  g21 u2 1 ux
2
1 ux
2
1 uy
2
. Because the formerly
nonbonding 1 ux orbital is greatly stabilized (3a1) on bending, the water
molecule is bent rather than linear.

8. (i) S4N4F4 (ii) N  SF3 (iii) H3SiOSiH3

9. If two ligands in an octahedral complex are different from the other four,
giving an MA4B2 complex, two isomers are possible. The two B ligands can
be cis or trans. cis- and trans-[Co(NH3)4Cl2]Cl are examples of this type of
system:

67
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

UNIT 3
PHOSPHORUS-NITROGEN AND
SULFUR-NITROGEN
COMPOUNDS

Structure
3.1 Introduction 3.3 Sulphur-nitrogen Compounds
Expected Learning Outcomes Ring and Chain Compounds
S2N2, S4N4. (SN)x etc.
3.2 Phosphorus-nitrogen
Compounds 3.4 Summary
Synthesis 3.5 Terminal Questions

Structure 3.6 Answers

3.7 Further Reading
Bonding and Uses of Cyclo and
Linear Phosphonitrilic
Compounds

3.1 INTRODUCTION
In the previous unit you have learnt about the shapes of molecules with the
help of the Valence Shell Electron Pair Repulsion Theory (VSEPR). Also you
have learnt about Walsh diagrams and d-p bond, Bent’s rule and the
energetics of hybridization. Lastly, the geometric and optical isomers were
discussed. In this unit you will be introduced to phosphorus-nitrogen
compounds and sulphur-nitrogen compounds. It will involve the synthesis,
structure and bonding of a number of interesting compounds specially the ring
and chain compounds.

Expected Learning Outcomes

After studying this unit you should be able to:
 understand the synthesis and, structure of phosphorus-nitrogen
compounds; and
 discuss about the ring and chain Compounds of sulfur-nitrogen
68 compounds.
Unit 3 Phosphorus-nitrogen and Sulfur-nitrogen Compounds

3.2 PHOSPHORUS-NITROGEN COMPOUNDS

Extensive studies on the chemistry of compounds with P-N (single bond) as
well as P=N (double bond) has been done. Most of such compounds are
oligomeric or polymeric.

Bonding and Uses of Cyclo and Linear Phosphonitrilic

Compounds

Let us first look into how the phosphorus-nitrogen compounds were

discovered. It was known that phosphorus pentachloride react readily with
basic reagents like water or ammonia. Now, the reactions with water is as
shown in Eq. 3.1 and 3.2:

2 PCl5  H2O  OPCl3  2HCl … (3.1)

PCI5 + 4H2O  H3PO4 + 5HCI … (3.2)

Thereafter the scientists thought that with ammonia analogous products such
as HN=PCl3 and HN=P(NH2)3 would form. But the reactants and products
were found to be sensitive to moisture and it did not happen. Also, other side
products were formed. It is seen that if the less reactive conjugate acid of
ammonia is used, namely ammonium chloride is used then reaction with PCl5
proceeds at a moderate rate as shown in Eq. 3.3:
o
146 C Monomer Cl2P=N is
NH4 Cl  PCl5 PNCl2 … (3.3)
Refluxing CHCl2CHCl 2 analogous to organic
nitriles, R—C=N and
The products either cyclic or linear polymers of general formula [NPCl2]n which was called
are analogous to benzene, borazine, etc.,and so they are called phosphonitriles,
phosphonitrilic
phosphazenes. The major product of the reaction in Eq. 3.3 and the easiest to
chloride, etc.
separate is the trimer, n = 3. Smaller amounts of the tetramer and other
oligomers up to n = 8 have been characterized and higher polymers also exist.
While preparing analogous bromo compounds you have to add bromine
sufficiently so that phosphorus pentabromide if prepared in a similar way do
not decompose as shown in Eq. 3.4.

PBr5 ⇌ PBr3  Br2 … (3.4)

NH4Br
PBr5 [NPBr2 ]3  2HCl … (3.5)
excess Br2

Indirect fluorination of the chloride result in the:

[NPCl2]3 + 6NaF  [NPF2]3 + 6NaCl … (3.6)

Planar six-membered rings (Fig. 3.2) are formed as a result of formation of the
halide trimers. The bond angles are consistent with sp2 hybridization. The
nitrogen is sp2 hybridised and the phosphorus sp3 hybridized. In Fig. 3.1 it is
shown that two of the sp2 orbitals of nitrogen, containing one electron each,
are used for  bonding and the third contains a lone pair of electrons. This
results in one unhybridized pz orbital which has one electron. 69
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

2
Fig 3.1: sp orbitals of nitrogen.

Phosphorus uses four electrons in the four sp3 hybrid orbitals for  bonding.
So the fifth electron is in the d orbital. We can draw resonance structures
which are analogous - to those for benzene as shown in Fig. 3.2 a). So we
expect aromaticity in the ring. The actual structure is not so simple. The
phosphorous ring is planar, the P—N bond distances are equal and short. All
these alone with the stability of the compounds suggests delocalization. Even
though all the phosphazenes are not planar, they are still stable.  bonding in
cyclophosphazenes involves d and p orbitals and dp bonding have been
discussed in various ways. This is a major difference from the bonding in
benzene. The extent of delocalization and the nature of the aromaticity are still
debatable. In Fig. 3.2 b) is shown the molecular structure of P 3N3Cl6 as
determined by X-ray diffraction.

Fig. 3.2: Structure of trimeric phosphazene, P3N3Cl6; a) resonance structures;

b) molecular structure. [Source: Bullen, G.J.J. Chem. Soc (A) 1971,
1450.]

+ + + + + + +
+  + 

+   + + 


 + +   +

        +  +

C1 C2 C3 C4 C5 C5 C6 N1 P1 N2 P2 N3 P3 N1

(a) (b)

Fig. 3.3: Overlap of the orbitals in the (a) p-p  system in benzene (a) and the (b)
p-d  system in the phosphazene ring.

From Fig. 3.3 you can see that there is gerade symmetry of the d orbitals and
this gives rise to mismatch in the signs of the wave functions in the trimer. So
nodes arise as a result of which the stability of the delocalized molecular
orbital reduces. All this is shown in Fig. 3.3b.

Craig and Paddock suggested the model as shown in Fig. 3.4. The dxz orbital
of the phosphorus atom overlaps with the pz orbitals of the adjacent nitrogen
70 atoms as shown in Fig. 3.4a.
Unit 3 Phosphorus-nitrogen and Sulfur-nitrogen Compounds

As shown in Fig 3.4b, if the d orbital, which is perpendicular to the dxz,

overlaps with the pz orbitals of nitrogen, nodal surface results. The sp2
nonbonding orbital of nitrogen and the dxy and/or dx2y2 orbitals of phosphorus
can have in-plane  bonding as shown in Fig. 3.4 c and d.

Fig. 3.4: Theory of Craig and Paddock for  bonding in phosphazenes: a)

interaction of pz(N) and dxz(P); b) interaction of pz(N) and dyz(P); c)
2 2
interaction of sp (N) and dxy(P); d) interaction of sp (N) and dx2 - y2(P).
[Source: Corbridge, D.E.C. Phosphorus; Elsevier: Amsterdam, 1978; p
235.]

Let us now discuss the alternative view offered by Dewar and coworkers. Here
the dxz and dyz orbitals hybridize to give two orbitals which are directed toward
the adjacent nitrogen atoms as shown in Fig. 3.5. So three-centre bonds are
formed about each nitrogen. Delocalization over selected three-atom
segments of the ring with nodes after each such “island” is there in this model.
z-axis

a h 
h p p
p
a N N p
z
z z P
z N N N N
z-axis
P P P P
a b N
d d
 
a b
d d
 
(b)
(a)

Fig. 3.5: Theory of Dewar for  bonding in phosphazenes: a) the relation of the
orthogonal phosphorus da and db orbitals to the nitrogen pz orbitals as
seen perpendicular and parallel to the z axis, respectively; b) the three-
centre bond model for P3N3Cl3. [Source: Schmulbach, C.D. Prog. Inorg.
Chem. 1965, 4, 275.]

Both these models have been supported by evidence. Yet, there is another
model where d orbital participation is not important in the bonding in these
molecules.

Tetrameric phosphazenes have more flexible structures than those of the

trimers. The structure of (NPF2)4 is planar, while conformations (tub, boat,
chair, crown, saddle, and structures in between) are seen in others which may 71
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

not be predicted. Out of the two of isolated forms of the tetrameric

chlorophosphazenes (Fig. 3.6), the one with the chair arrangement is most
stable. The other form has a tub conformation. Even though the
corresponding organic compound, cyclooctatetraene, C8H8, is nonaromatic as
it is nonplanar with chair structure but these tetrameric phosphazenes with
chair structure are aromatic with extensive delocalization. This is really very
interesting.

Fig. 3.6: Structures of tetrameric phosphazene, P4N4Cl8: a) tub conformation; b)

chair conformation. [Source: (a) Hazekamp, R.: Migchelsen, T.; Vos,
Acta Crystallogr. 1962, 15, 539; structure (b) from Wagner, A.J.; Vos, A.
Acta Crystallogr, 1968, 24, 707]

Many other ring sizes have been synthesized. For example, all of the
crystallographic studies of (NPMe2)n {n = 3 -12) compounds have been studied
as shown in Eq. 3.7. The first cyclo-diphosphazene has been prepared:
(i - Pr) 2N
hv P N
-
[(i Pr) 2N] 2PN3 o N(i-Pr) 2 …(3.7)
(i - Pr) 2N
40 C N P
N(i-Pr) 2

which were expected to be too unstable for isolation because of ring strain.

Phosphazene Polymers

Polymers of phosphazenes can be prepared which may be advantageous and

better than carbon based polyolefins and polyesters. It is still in the developing
stage for commercial application. The phosphorus-chlorine bond is sensitive to
moisture and poses problem. The preparation of the polymers of trimeric
chlorophosphazene is done as shown in Eq. 3.8:

…(3.8)

When the above reaction is carried out carefully, we can avoid extensive
cross-linking to form the polymer (n = 15,000) which is soluble in organic
solvents. But chlorine atoms may undergo nucleophilic attack and
72 displacement:
Unit 3 Phosphorus-nitrogen and Sulfur-nitrogen Compounds

[PNCl2]n + 2nNaOR  [PN(OR)2]n + 2nNaCl … (3.9)

[PNCl2]n + 2nR2NH  [PN(NR2)2]n + 2nHCl …(3.10)

Different elastomers, plastics, films and fibres may be procured if you change
the nature of the side chain, R, These materials tend to be flexible at low
temperatures, and water and fire resistant. Water repellent fluoroalkoxy-
substituted polymers (R = CH2CF3) do not have any interaction with living
tissues and so are used successfully for the fabrication of artificial blood
vessels and prosthetic devices.

Phosphazenes are also useful medically as slow-release drugs. Inorganic

polymeric backbones are having useful electrical, optical, and thermal
properties. They find use as precursors to ceramies. By changing the
backbone of the polymer its properties may be changed.
CH3
OH

O N
O O CH N S NH

N P N P O N

NHCH 2COOEt OPh

(b)
(a)

HO OH

O N N
N P
CH 2CH 2NH 2
OPh
(c)

Fig. 3.7: Polymeric phosphazenes: a) steroid-bound; b) sulfadiazine-bound;

c) catcholamine-bound.

If one of the PCl2 groups in (PCl2N)3 is substituted by CCl group. It forms a

ring which gives a polymer with carbon in its backbones as shown in Eq. 3.11.
Cl

C Cl Cl
N N 120oC …(3.11)
Cl Cl C N P N P N
P P
Cl N Cl Cl Cl Cl
n

This polymer is the first example of a poly(carbophosphazene).

Linear Polyphosphazenes

The properties of linear poly phosphazenes may differ if the R groups in the
(R2P–N)n chain, are changed as shown in Eq. 3.12.

…(3.12)

73
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

By eliminating PCl5 from (NPCl2)3 synthetic polyphosphazenes are

synthesised. When all the PCl5 cannot be removed, cross-linked, insoluble
product result which is of no use. When (NPCl2)3 is heated above 230oC it
gives the polymer, where the degree of polymerization, n, can be ≥15,000.
So, molecular weights of the order of 2 million results. Nucleophiles such as
alkoxides, aryloxides, amines or organometallic reagents can react with this
polymer readily. This happens since in each molecule numerous chlorine
atoms may be substituted by organic or organometallic groups under
moderate reaction conditions, which generally do not make any cleavage of
the inorganic backbone. In this way there is unlimited scope of preparing
mixed substituent polymers which is shown in Fig. 3.8.
Single-Substituent Polymers

OR NHR
N P N P
OR
n
NHR n
Cl Cl
P RONa RNH2
N N NaCl HCl

Cl Cl
P P Cl
heat
Cl N Cl N P
25oC n = 15,000
catalyst Cl
n
Me3SiN = 15,000 Me3SiCl
RONa
NaCl

OR
N P
OR
n
R'ONa RNH2
NaCl HCl

OR OR

N P N P

OR' NHR
n n

Mixed-Substituent Polymers
Fig.: 3.8: Some synthetic routes for polyphosphazenes.

The inorganic backbone and the organic or organometallic side groups

determine the properties of these polymers. Whether the polyphosphazene will
be flexible, fire resistant, stable to oxidation and high energy radiation and in
some cases biocompatible will be determined by the backbone. Whether they
will be soluble, hydrolytically stable, and a wide range of optical, electrical, and
biological properties will be decided by side groups. The material properties
like crystallinity, liquid crystallinity, and glass transition temperature are
determined by the size and polarity of the side groups. So the polymers can be
74 designed in various ways.
Unit 3 Phosphorus-nitrogen and Sulfur-nitrogen Compounds

Fluoroalkoxy or aryloxy side groups in polyphosphazenes were used to

produce high performance elastomers. Ion-conducting materials which can be
fabricated into lightweight, thin-film rechargeable used lithium batteries were
used. Synthetic chemistry studies have recently given novel methods for the
preparation of poly (dichlorophosphazene) as following:
High temperatur e condensati on
O  PC 2  N  PC3           
 (NPCl2 )n …(3.13)

BCl catalysed in solution

(NPCl2 )3  
3
      polymer …(3.14)

PCl catalysed at room temperatur e

MeSi  N  PCl3  
5

 (Narrow molecular weight NPCl2 )n
…(3.15)
Direct synthesis of organophosphazene polymers without macromolecular
substitution:
200 o C
MeSi  N  PR2   (NPR2 )

There are many more methods whereby ring-opening polymerization from

cyctic trimers of substituted polyphosphazenes take place leading to
respective polymer. Phosphazene skeleton with other inorganic units make
hybrid units like when that cyclocarbo- and thiophosphazenes undergo ring-
opening polymerization to produce macromolecules such as Fig. 3.9, 3.10 and
3.91, which undergoes macromolecular substitution similar to (NPCl2)n. Hybrid
phosphazene-organosilicon polymers in which some of the properties of
phosphazenes have been combined with those of silicones have been
prepared.

Fig. 3.9

Fig. 3.10

Fig. 3.11

Phospham is, produced by the reaction a highly cross-linked polyphosphazene

(as shown in Fig. 3.12)

500oC
4NH 3(g) + 2P(red) 2PN 2H(s) + 5H 2 … (3.16)
75
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

HN

P N

Fig. 3.12: Phospham.

Other P–N Compounds

In the large and important class of compounds called phosphazenes we are

formally dealing with Pv and NIII. There are other P–N compounds that are
formally PIII–NIII types. In these the P–N bonds are all nominally single, but, of
course, partial double-bond character arises by N p–Pd donor bonding,
indicated as follows in resonance terms:

 

:
P N P N

The aminophosphanes, (R2N)nPX3n are monomeric, whereas groups are

bulky when the R and R aminophosphanes (R2N–P=NR are either monomers
or dimers Fig. 3.13. As shown in they from dimers with less bulky substituents.

Fig. 3.13: Dimer of aminophosphanes.

Compounds with larger rings, as shown in (Fig. 3.14) planar rings are found in
also formed. But the phosphorous atoms along with its substituents can adopt
either a cis or a trans relationship relative to the ring plane.

Fig. 3.14: P-N compounds with large rings.

76 Fig. 3.15: Three polycyclic types of P–N compounds.

Unit 3 Phosphorus-nitrogen and Sulfur-nitrogen Compounds

…(3.13)

Finally, there are polycyclic P–N compounds such as those shown in Fig. 3.15.
are of different types. (a) is an adamantine-type structure and (c) are isomers;
when R=Me, the adamantine structure is thermally stable. The situation
changes when R=Me2HC, then the structure shown in Fig. 3.15 a) converts to
structure shown in Fig. 3.15c on heating for 12 days at 157C.

SAQ 1
With the help of suitable diagrams discuss how the orbitals overlap in the
phosphazenes ring.

3.3 SULPHUR-NITROGEN COMPOUNDS

3.3.1 Ring and Chain Compounds
S2N2, S4N4. (SN)x etc.
Since last century compounds which contain sulfur–nitrogen rings have been
know although new ones have been prepared in the last decade. Lot of
interest is there among scientists in this field. The ammonolysis of sulfur
monochloride, S2Cl2, either in solution or in an inert solvent or heated over
solid ammonium chloride gives S4N4. The interesting compound tetrasulfur
tetranitride has been prepared by as shown in Eq. 3.14.
NH
S2Cl2 
3
 S 4N4  S8  NH4Cl …(3.14)

The product is a bright orange solid insoluble in water but soluble in some
organic solvents. Although the crystals are reasonably stable to attack by air,
they are explosively sensitive to shock or friction.

But in the cage structure (Fig. 3.16) the two pairs of nonbonding sulfur atoms
are at a distance of about 258 pm which is much less the sum of the van der
Waals radii (360 pm). The normal S-S bond length 206 pm. Thus there must
be some interaction must be between the transannular sulfur atoms which
cannot be expressed as a Lewis structure. The normal S—S bond length 206
pm, S—N bond distances are equal ( 162 pm). There must be extensive
delocalization (12 electrons) and not alternating distinct single and double
bonds as the ring. Cyclophosphazenes have resemblance to this but this is
more complicated.

We have seen that S2N2 and (SN)x can be prepared from S 4N4. Other neutral
binary sulfides may be obtained from it as well. When S4N4 is heated under
pressure in a solution of CS2 containing sulfur, S4N2 is formed. This molecule
has a "half-chair" conformation (Fig. 3.17). Others such as S5N6 and S11N2
have also been reported. 77
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

An even larger number of binary sulfur—nitrogen cations and anions are

known. Reduction of S4N4 (with metallic potassium or sodium azide) yields the
planar six-membered ring, S3N3 , (Fig. 3.18a). This is seems to be benzene
analogue. But if you count the electrons, you find there are ten electrons, so
the Hückel 4n + 2 rule is obeyed. So it is aromatic. But four of these electrons
reside in the antibonding orbitals. Thus, the S—N bond (Fig. 3.18b) becomes
weak.

Fig. 3.16: Eight-membered sulfur-nitrogen rings: (a) molecular structure of S4N4; (b)
diagrammatic structure of N4S4F4 which shows alternating bond lengths.

S(3) S(3')

S S(2)
N N N'

S S
S
S(1)
N

Fig. 3.17: Molecular structure of S4N2.

2a"g
antibonding
S electrons
2e"
N N
S S
N 1e" bonding
electrons
1a"g
(a) (b)

Fig. 3.18: a) Structure of S3N3 and b) qualitative molecular orbital diagram.

Tetrasulfur when reduced with tin(II) chloride produces tetrasulfur tetraimide,

S4(NH)4, isoelectronic with sulfur, S8 and in a similar way exists in a crown
configuration. S and NH are isoelectronic and thus a series of ring compounds,
Sx(NH)8x, have been produced which do not have N-N bonds that includes all
possible.

S4N4 can be oxidized. If treated with chlorine and then trithiazyl trichloride is
produced as in Eq. 3.15:

3S 4N4  6Cl2  4N3S 3Cl3 …(3.15)

78
Unit 3 Phosphorus-nitrogen and Sulfur-nitrogen Compounds

Fluoride may be formed from N3S3Cl3 as shown in Eq. 3.16.

Cl F

S S
N N AgF2 N N …(3.16)

S S S S
Cl N Cl F N F

N3S3Cl3 may be oxidised to sulfanuryl chloride.

Cl Cl O
S S
N N [O] N N …(3.17)
O Cl
S S S S
Cl N Cl Cl N O

SAQ 2
a) How is S3N3- prepared? Give its qualitative molecular diagram.

b) Give one example of eight-membered sulphur nitrogen ring along with its
molecular structures.

3.4 SUMMARY
In this unit you have learnt about the phosphorus-nitrogen compounds and
sulphur-nitrogen compounds. You have learnt about the bonding and uses of
cyclo and linear phosphonitrilic compounds. Thereafter you have learnt about
the synthesis, structure and bonding of a number of interesting compounds
specially the ring and chain compounds of sulphur-nitrogen compounds. This
brings us to the end of this block. In the next block you will be studying about
organometallic chemistry.

3.5 TERMINAL QUESTIONS

1. With suitable diagrams discuss the theory of Dewar for  bonding in
phosphazenes.

2. Give some synthetic routes for preparation of polyphosphazenes.

3. Predict whether the following species will exhibit inorganic aromaticity; a)

a) S 3 N3 b) S 4 N3 c) S5 N5 .

4. How do you prepared mixed-substituent polymers of phosphazenes? Give

suitable chemical equations.

3.6 ANSWERS
Self Assessment Questions
1. From Section 3.2, The two models(Craig & Paddock and Dewar models
with suitable diagrams (Fig. 3.3, 3.4 and 3.5) are to be discussed here. 79
Block 1 Main Group Elements, Transition Elements and Structure of Molecules

2. a) Reduction of S4N4 (with metallic potassium or sodium azide) yields the

planar six-membered ring, S3N3 , (Fig. 3.18a).

b) S4N4, Fig. 3.16 a

Terminal Questions

1. Dewar model: dxz and dyz orbitals hybridize to give two orbitals which are
directed toward the adjacent nitrogen atoms as shown in Fig. 3.5. So
three-centre bonds are formed about each nitrogen. Delocalization over
selected three-atom segments of the ring with nodes after each such
“island” is there in this model.

2. Take examples from the reactions given in Fig. 3.8.

3. a) S3N3 , (Fig. 3.18a). If you count the electrons, you find there are ten
electrons, so the Hückel 4n + 2 rule is obeyed. So it is aromatic. (Fig.
3.18b)

b) S 4 N3 , planar and there are ten electrons, so the Hückel 4n + 2 rule
is obeyed. So it is aromatic

c) S5 N5 , not planar and so not aromatic.

4. Eq. 3.11 to 3.15, give some examples.

80