Chapter 2

Molecular Structure and Bonding

Lecture 4
09/10/2009
Dr. Andrei Jitianu
Atkins • Overton • Rourke • Weller • Armstrong

Shriver & Atkins

Inorganic Chemistry
Fourth Edition

Chapter 2
Molecular Structure and Bonding

Copyright © 2006 by D. F. Shriver, P. W. Atkins, T. L. Overton,

J. P. Rourke, M. T. Weller, and F. A. Armstrong
 Outline
• Lewis structures
– The octet rule;
– The structure and bond properties;
– The VSEPR model;
• Valence-bond theory
– The hydrogen molecule;
– Homonuclear diatomic molecules;
– Polyatomic molecules;
• Molecular orbital theory
– An introduction in theory
– Homonuclear diatomic molecules;
– Heteronuclear diatomic molecules;
– Bond properties;
 Outline
• Lewis structures
– The octet rule;
– The structure and bond properties;
– The VSEPR model;
• Valence-bond theory
– The hydrogen molecule;
– Homonuclear diatomic molecules;
– Polyatomic molecules;
• Molecular orbital theory
– An introduction in theory
– Homonuclear diatomic molecules;
– Heteronuclear diatomic molecules;
– Bond properties;
 Lewis structures
• A covalent bond is formed when two
neighbouring atoms share an electron pair.
– Single bond – one shared electron pair
A:B or A-B
– Double bond – two shared electron pairs –
A::B or A=B
– Triple bond – three shared electron pairs –
A:::B or A≡B
An unshared of valence electrons on an atom (:A)
lone pair
 The octet rule

Key point:
• Atoms share electron pairs until
they have acquired an octet of
valence electrons.

Each atom shares electrons with

neighbouring atoms to achieve a total of
eight valence electrons (an ‘octet’)
The steps of constructing a Lewis structure:

1. Decide on number of electrons that are to be included in

the structure by adding together the numbers of all
valence electrons provided by the atoms.

2. Write the chemical symbols of the atoms in the

arrangement that shows which atoms are bonded
together.

3. Distribute the electrons in pairs so that there is one pair

of electrons forming a single bond between each pair of
atoms bonded together , and then supply electron pairs
(to form lone pairs or multiple bonds) until each atom
has an octet
Exercises
Write the structure of the BF4-
Tetrahedral
Write a Lewis structure for PF3 molecule

Trigonal pyramidal
Resonance
Key points:
• Resonance between Lewis structures lowers the
calculated energy of the molecule and
distributes the bonding character of electrons
over the molecules;

• Lewis structures with similar energies provide

the greatest resonance stabilization.
This Lewis structure indicates incorrectly that one O-O bond is different from the other.
In fact O-O bond from O3 is 128 pm between O-O which is 148 pm and O=O which is
121pm.
The concept resonance shows that the actual structure is a superposition, or average
of all feasible Lewis structures corresponding to a given atomic arrangement.
Resonance ………………………
• In quantum mechanical terms:

– The electron distribution of each structure is presented by a

wavefunction

– The actual wavefunction is the superposition of the individual

wavefunctions for each contributing structure.

ψ = ψ(O-O=O)+ψ(O=O-O)

- The overall wavefunction is written as a superposition with

equal contributions from both structures because the two
structures have identical energies
• The blended structure of two or more Lewis
structures is called a resonance hybrid.

– The resonance occurs between structures that differ

only in allocation of electrons;
– The resonance does not occur between structures
in which the atoms themselves lie in different
positions.
• Resonance effects:
1.Resonance averages the bond characteristics
over the molecules

2.The energy of resonance hybrid structure is

lower than that of any single contributing
structure.

The energy of O3 resonance hybrid is lower

than that of either individual structure
alone.
Resonance is important when several
structures with the same energy are
present.

For this case all the structures with the same

energy contribute equally to the overall
structure.

Structure with different energies may also

contribute to an overall resonance hybrid.
Higher energy
Formal Charge
Key points:
• The formal charge is the charge an atom
would have if electron pairs were shared
equally;
• Lewis structures with low formal charges
typically have the lowest energy.
The decision about the best arrangement of
electrons to give a Lewis structure with the
lowest energy can be estimated quantitatively
by formal charge, f , on each atom.

Formal charge f = V – L – (1/2)P

V- number of valence electrons

L- number of lone pair of electrons
P- number of shared electrons
 The formal charge is the difference between the number of valence electrons in the
free atom and the number that the atom has in the molecule, assuming it owns one
electron of each shared pair and both electrons of any lone pair.

A representation of the calculation of formal charge. The lines show the bonding electrons and lone
pair electrons are apportioned to each atom (a.) In a diatomic molecule A-B and (b.) in a triatomic
molecule A=B-C. The formal charge on each atom is the difference between the number of
electrons obtained in this way and the number in the free, neutral atom.
Oxidation State

Key points:
• Oxidation numbers are assigned by applying a set
of rules;

• The oxidation number ω (omega) is a

parameter obtained by exaggerating the ionic
character of a bond.

• Oxidation state is the physical state of the

element corresponding to its oxidation
number
Hypervalence
Key point:
• Hypervalence and octet expansion occur for
elements following Period 2.

• The elements of Period 2 from Li to Ne obey the

octet rule, but the elements of later periods show
deviations from it.
 10 e- in the valence shell 12 e- in the valence shell

A P atom can accommodate more than eight electrons if it uses its vacant 3d orbitals;
In PCl5 with its five pairs of bonding electrons, at least one of 3d orbital must be used in
addition to the four 3s and 3p orbitals of the valence shell.
 Outline
• Lewis structures
– The octet rule;
– The structure and bond properties;
– The VSEPR model;
• Valence-bond theory
– The hydrogen molecule;
– Homonuclear diatomic molecules;
– Polyatomic molecules;
• Molecular orbital theory
– An introduction in theory
– Homonuclear diatomic molecules;
– Heteronuclear diatomic molecules;
 Structure and bond properties
a. Bond length

Key points:
• The equilibrium bond length in a molecule is the
separation of the centers of the two bonded atoms;

• Covalent radii vary through the periodic table in

much the same way as metallic and ionic radii.
The equilibrium bond length in a molecule
is the separation of the centers of the two
bonded atoms.
»X-Ray data on solids;
»IR and Microwave spectroscopy;

• The contribution of an atom to a covalent

bond is called the covalent radius of the
element.
 Bond length

Covalent radii

A covalent radius expresses the closeness of approach of bonded atoms.

The closeness of approach of nonbonded atoms in neighbouring
molecules that are in contact is expressed in terms of the van
der Waals radius of an element;
- the internuclear separation when the valence shells of the two atoms
are in nonbonding contact
b. Bond strength

Key points:
• The strength of a bond is measured
by its dissociation enthalpy;
• Mean bond enthalpies are used to
make estimates of reaction enthalpies
Thermodynamic measure of the strength of an
AB bond - bond dissociation enthalpy
∆Hϴ(A-B)

AB(g) →A(g)+B(g) standard reaction enthalpy

The mean bond enthalpy, B, is the average

bond dissociation enthalpy taken over a
series of A-B bonds in different molecules.
Mean bond enthalpy, can be used to estimate reaction enthalpies.
d. Electronegativity and bond enthalpy
Key point:
• The Pauling scale of electronegativity is useful for
estimating bond enthalpies and for assessing the
polarities of bonds.

Pauling definition: power of an atom of the element to

attract electrons to itself when it is a part of a compound.

The original concept related the electronegativity with the

energetics of bond formation
 A2(g)+B2(g) →2AB(g)

∆E-excess of energy of the A-B bond over the average

energy of A-A and B-B bonds can be attributed to the
presence of ionic contributions to the covalent bonding.

|χP(A)-χP(B)|=0.102(∆E/kJ mol-1)1/2

Where ∆E=B(A-B)-1/2{B(A-A)+B(B-B)}

B(A-B) is the mean A-B bond enthalpy.

• Binary compounds with ∆χ>1.7 - ionic

 CsF- ∆χ=3.19; χmean=2.38 –ionic

F2 - ∆χ=0; χmean=3.98
Cs - ∆χ=0; χmean=0.79

Ex: χMg=1.31; χO=3.44

A Ketelaar triangle, showing how a plot of

average electronegativity against
electronegativity difference can be used to
classify the bond type for binary compounds