CHE 622 Physical Methods in Inorganic Chemistry (3 credits)

Credits 3
Type (Core, optional/general) Core
Semester in which course is taught 2
Pre-requisite CHE 621
Aims and learning objectives:
Students will gain an understanding as well as acquire skills of the various physical
methods available in Inorganic Chemistry. They will then be able to apply their
knowledge of these methods to characterize inorganic and organometallic compounds.

Intended Learning Outcomes

With the benefit of material learnt in CHE621, after completing CHE622 the student
is expected to have gained a sound understanding of the chemical and physical
processes upon which each of the following physical methods are used. The student
should also be able to apply knowledge acquired to successfully use data obtained by
each technique, to characterize inorganic and organometallic compounds.

1. Infrared Spectroscopy
2. Raman Spectroscopy
3. Nuclear Magnetic Resonance (NMR) of inorganic compounds
4. Electron Paramagnetic Resonance (EPR) spectroscopy
5. Nuclear Quadrapole resonance spectroscopy
6. Mossbauer spectroscopy
7. Mass spectroscopy of Inorganic compounds
8. Optical Techniques
a. ORD
b. CD
(i) Absolute configuration of chiral inorganic complexes
(ii) Ligand conformations

Course Synopsis
Electronic absorption spectroscopy: crystal field and charge transfer bands; vibrational
and rotational spectroscopy: Infrared, Raman and Microwave. Nuclear Magnetic
Resonance of inorganic compounds. Electron paramagnetic resonance spectroscopy;
Nuclear Quadruple resonance spectroscopy; Mossbauer spectroscopy. Mass
spectroscopy of inorganic compounds. Optical activity of inorganic complexes:
ORD, CD, absolute configuration of chiral complexes, ligand conformation.

Assessment: Continuous assessment (50%) and final examination (50%)

Recommended Textbook:
1. Structural Methods in Inorganic Chemistry, 3rd edition, by E.A.V. Ebsworth,
D.W.H. Rankin, and S. Cradock – Blackwell Scientific Publications, 1998
2. Physical Methods for Chemists, 2nd edition, by R.S. Drago – Saunders College
Publishing, 1992
 Infrared Spectroscopy

1. Introduction

2. Bonds as springs (Basic physical Principles)

3. Signal characteristics – wavenumber

4. IR spectra for hydrocarbons

5. Signal characteristics – intensity

6. Signal characteristics – shape

7. Symmetric and asymmetric stretching

8. IR signals for carbonyl compounds

9. IR spectra practice
 1. Introduction

Shine certain frequencies of IR radiation on a molecule  absorption

Absorbed E causes the bonds to stretch

The stretching of bond is like oscillation of a spring. Energy is needed to stretch and
compress the spring

When IR radiation (consisting of various wavelengths) interacts with a molecule, some of

the frequencies are absorbed and others are transmitted without absorption

Which frequencies are absorbed? Observe the absorption “fingerprint” of the

compound-IR spectrum

100%

%
T
r
a
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s
0%

Wavenumber
 Relating wavenumber to wavelength and frequency (of the light absorbed)

Definition: wavenumber = 1/λ(in cm) = ύ

But ν =c/λ = c.ύ

Thus frequency of radiation, v ( and therefore E) is directly proportional to the

wavenumber ύ.

Radiation absorbed at high wavenumbers is high energy radiation (and vice versa)

100%
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ύ :4000 cm-1 ύ :500cm-1

ν : 1.20 x 1014 s-1 ν : 1.50 x 1013 s-1
 D F
i i
a n
g R g
n e e R
o g r e
s i p g
t o r i
I n i o
c n n
t

Signals on this side are diagnostic of a Difficult to assign each peak but
certain functional group the shape gives a fingerprint of
the molecule as a whole
Bonds as Springs (Review of some basic classical physics concepts)
Consider a chemical bond to be a spring so C-H bond can be
modelled as a spring with C atom on one end and H atom on
the other..

If the spring obeys Hooke’s Law, then the stretching

vibration is comparable to the oscillation of a mass
attached to a spring

Basic mechanics of a spring;

Consider a box of mass m attached to a spring that is

anchored on a body with infinite mass.

Assume the box is sitting on the floor but has no friction

Now if we pull the box to the right, spring
stretches and the box assumes a new position.
The new position of the box is further from
the wall by Δx

To move the box to the new position requires a

force F and keeping it at that position will
require overcoming the force of the spring, Fs

Hooke’s Law,
The restraining force (force of the spring), Fs = -kx, where k is the force
constant and x is the displacement from the original position

But knowing that F =ma  Fs = -kx = ma

But remember a is a derivative of speed (or a second

derivative of position)
 So,

Fs = -kx = ma = m. (d2x/dt2)

Now, consider what happens after letting

the box go after stretching the spring by Δx:

Because of the restraining spring force Fs , the box will accelerate back
towards its original position. Fs will take the box back beyond its original
position and cause the spring to compress, thus building up potential
energy to push the box back to the stretching position.

The complete movement from the stretched position to the compressed position
and back to the stretched position is a complete oscillation. The time that it takes
for one complete oscillation is called the period, and its measured in seconds.
The number of oscillations per second define the frequency of the vibration, v

Algebraic manipulation  v =1/2π. k/m

So, the variables that affect frequency are k and m;

In terms of molecules, it means that

• a strong bond (large k) will vibrate at a higher frequency (v).
• assuming they are bonded to the same “backbone”, a heavier atom
will vibrate at a lower frequency than a lighter one.

The frequency can also be defined as the number pf oscillations per

second and it is dependent on;

• strength of the bond

• mass of the atom
In expressing the frequency as; v =1/2π. k/m, we are assuming that the vibration involves
movement of only one atom attached to a rigid stationary body

In reality, when two atoms are bonded to each other, both move. The dynamics
involved are therefore slightly different from those described above.

So, the frequency of vibration is no longer dependent on the mass of one atom, but both

v =1/2π. k/μ , where μ = (m1m2)/(m1+m2)

Consider reduced mass for the systems ;

H-C, C-C, C=C and the implications for the frequency of vibration of the bonds