Fall 2005

Chapter 2: IR Spectroscopy
Spectroscopic Process
IR Absorption Process
Uses of IR
Covalent bonds
Vibrational Modes
Absorption Trends

CHMBD 449 Organic Spectral

Analysis
1

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
Remember, most interesting molecules are not diatomic, and
mechanical or electronic factors in the rest of the structure may
effect an IR band
From a molecular point of view (discounting phase, temperature or
other experimental effects) there are 10 factors that contribute to the
position, intensity and appearance of IR bands
1. Symmetry
2. Mechanical Coupling
3. Fermi Resonance
4. Hydrogen Bonding
5. Ring Strain
6. Electronic Effects
7. Constitutional Isomerism
8. Stereoisomerism
9. Conformational Isomerism
10. Tautomerism (Dynamic Isomerism)
2

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
7. Constitutional Isomers
Obvious in most cases molecules with identical molecular
formulas with different connectivity implies a different set
of covalent bonds and interactions and therefore different
IR

Important to note that permutations of the substitution

pattern (i.e. ortho- meta- or para-) on an aromatic system
are also constitutional isomers IR is a powerful tool for
analysis

Variations of heterocyclic structures within the same

N
molecular formula
can also
be discerned by IR
N
N

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
8. Stereoisomerism - enantiomers and diastereomers
Enantiomers (optical isomers) pure enantiomers do not
differ in the arrangement of atoms and bonds relative to
the rest of the molecule identical IR spectra

Diastereomers - (geometric isomers) will have different

changes in dipole moment for given sets of vibration

Consider cis- and trans- alkenes; the stretching modes of

dibromoethylene are given as an example:
Br

Br

change in
710 cm-1

Br

Br
change in
840 cm-1

symmetric

asymmetric

Br

Br

no change in
Br IR inactive

change in
895 cm-1
Br

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
9. Conformational Isomerism
In open chain compounds the barrier to rotation is small,
and most often IR are observed of the energetically
favored form
X

X
H

YX

H
H

gauche
(staggered)

trans
(staggered)

H
H

HH

cis
(eclipsed)

Likewise in cyclic systems, the lowest energy conformer(s)

will be the one observed

These conformers will change depending on solvent,

temperature and phase, and can be observed in the IR
5

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
9. Conformational Isomerism
Sometimes, there is a stabilizing interaction that may allow
observation of a second band for an additional stable
conformer
Example: -halogenated ketones the lone e- pairs of the
carbonyl oxygen are deflected strengthening the bond;
these structures
are
H purported to Hbe either cis- or gauche
O
X

R
H

cis
(eclipsed)

O
H

R
X

gauche
(staggered)

Again for cyclic systems, bands may be observed for each

energy minima
O
O
Cl
H
equitorial
CO = 1745 cm-1

H
Cl
axial
CO = 1725 cm-1

IR Spectroscopy
I.

Introduction
G. The IR Spectrum Factors that affect group frequencies
10. Tautomerism (Dynamic Isomerism)
Carbonyl compounds with -hydrogens exist as an
equilibrium between keto- and enol forms
O

O
CH3

H
CH2

In most cases, the keto form is favored; however in cases

where the equilibrium has an appreciable fraction of enol
(or the enol form is actually favored) those additional IR
bands are observed
O

keto tautomer
CO = 1723 (symmetric stretch)
= 1706 (asymmetric stretch)

enol tautomer
CO = 1622 (H- bonded)
CO = 3200-2400 (H- bonded)

IR Spectroscopy
Instrumentation and Experimental Aspects
A. The IR Spectrometer Dispersive and Fourier Transform
1. Dispersive IR Spectrometers
All spectrometers consist of four basic parts that are
coupled with all four parts of the spectroscopic process irradiation, absorption-excitation, re-emission-relaxation and
detection.
excited state

AbsorptionExcitation:
Spectrometer
needs to
contain the
sample

h
n
tio
xa
la
Re

Energy

II.

rest state

h h h

Detection-reemission :
Spectrometer needs to detect
the photons emitted by the
sample and ascertain their
energy

rest state

Irradiation: Spectrometer
needs to generate photons

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
1. Dispersive IR Spectrometers
Those four parts are:
1. Source/Monochromator
2. Sample cell
3. Detector/Amplifier
4. Output

Dispersive IR spectrometers were the first IR instruments,

however their simplicity and longevity allows them to
continue in service for most routine organic analyses
their speed and resolution is adequate

For the most part, their design is austere and relies on

simple mechanics and optics to generate a spectrum, very
similar to simply rotating a glass prism to see different
bands of visible light

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
1. Dispersive IR Spectrometers
Here is a general schematic:

10

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
1. Dispersive IR Spectrometers
Source is a heated nichrome wire which produces a broad
band continuum of IR light (as heat)
The beam is directed through both the sample and a
reference cell
A rapidly rotating sector (beam chopper) continuously
switches between directing the two beams to a diffraction
grating

11

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
1. Dispersive IR Spectrometers
The diffraction grating slowly rotates, such that only one
narrow frequency band of IR light is at the proper angle to
reach the detector
A simple circuit compares the light from the sample and
reference and sends the difference to a chart recorder

12

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
1. Dispersive IR Spectrometers
On the older instruments the motor in the chart recorder
was synchronized (& calibrated) to the motor on the
diffraction grating
Because each spectrum is the result of the tabulation of
the spectroscopic process at each frequency individually, it
is said to record the spectrum in the frequency domain

13

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
1. Dispersive IR Spectrometers
Advantages simple, easy to maintain last the life of the
source and moving parts
Disadvantages to cover the entire IR band of interest to
chemists it is necessary to use two diffraction gratings
At high , the component frequencies are more spread out,
so the resulting spectra appear to have various regions
expanded or compressed
The limit to resolution is 2-4 cm-1

14

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
2. Fourier Transform IR Spectrometers
FT-IR is the modern state of the art for IR spectroscopy
The system is based on the Michelson interferometer
o Laser source IR light is separated by a beam splitter,
one component going to a fixed mirror, the other to a
moving one and are reflected back to the beam
splitter

The beam splitter recombines the two to a pattern of

constructive and destructive interferences known as an
interferogram a complex signal, but contains all of the
frequencies that make up the IR spectrum

15

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
2. Fourier Transform IR Spectrometers
The resulting signal is essentially a plot of intensity vs.
time
Such information if plotted would look like the following:

This is meaningless to a chemist we need this to be in the

frequency domain rather than time.

16

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
2. Fourier Transform IR Spectrometers
By applying a mathematical transform on the signal a
Fourier transform the resulting frequency domain
spectrum can be observed

FT-IRs give three theoretical advantages:

1. Fellgetts advantage every point in the
interferogram is information all wavelenghts are
represented
2. Jacquinots advantage the entire energy of the
source is used increasing signal-to-noise
3. Connes advantage frequency precision Dispersive
instruments can have errors in the ability to move
slits and gratings reproducibly FTIR is internally
17
referenced from its own beam

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

A. The IR Spectrometer Dispersive and Fourier Transform
2. Fourier Transform IR Spectrometers
Justiks advantage does it give me what I need
1. Single-beam instrument collect a background (air
has IR active molecules!)

2.

Fast all frequencies are scanned simultaneously

3.

No referencing!

4.

Computer based scaling and editing of the spectrum

to squeeze out the most data; spectra are
proportional (no stretching or squeezing of regions),
comparison with spectral libraries

Disadvantages expenisve relative to dispersive

instruments, and the components take more expertise and
service calls to replace
18

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

B. The IR Spectrometer Experimental aspects
1. Sample size typically the size of the beam mms mgs
2.

Non-destructive sample can be recovered with varying degrees

of difficulty

3.

Liquid samples the easiest IR spectra are those of neat liquid

samples
Solid samples are too dense for good IR spectra intermolecular coupling of vibrational states occurs and peaks
are greatly broadened

In the liquid state full 3-D motion is available, and these

effects are averaged out and diminished

The thickness of a sample can be decreased to reduce

these effects further
Thin film liquid samples are best!
19

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

B. The IR Spectrometer Experimental aspects
3. Liquid samples
Sample cell cannot possess covalent bonds (SiO2, or glass
is out)

The most common cell is a pair of large transparent

windows of inorganic salts

Most common:
NaCl cheap, transparent from 650 4000 cm-1, but
fragile
Less common AgCl, KBr, etc. if you need transparency
below 650, limit is practically 400
20

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

B. The IR Spectrometer Experimental aspects
4. Solution samples
One way solids can be handled is as a solution
Key is that the solvent picked will cover the least amount
of the spectrum as possible, as it will also be present
Common solvents typically are symmetrical, or have many
halogenated bonds low cm-1: CCl4, CHCl3, CH2Cl2, etc.
The cell in this case is two NaCl (or other) windows with a
spacer, the sample is loaded via a syringe into the cell:

21

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

B. The IR Spectrometer Experimental aspects
4. Solution samples
A newer method involves the use of a polyethylene matrix,
that will hold allow a solution sample to evaporate, leaving
small portions of the sample embedded in the matrix

The samples are liquid-like

The only interference is that of hydrocarbon

22

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

B. The IR Spectrometer Experimental aspects
5. Solid Samples
The most common treatment for solid samples is to mull
them with thick mineral oil (high MW hydrocarbon) Nujol

Just like with the polyethylene cards, the molecules of the

sample are held in suspension within the oil matrix

Again, the interference is that of hydrocarbon

23

IR Spectroscopy
II.

Instrumentation and Experimental Aspects

B. The IR Spectrometer Experimental aspects
5. Solid Samples
The connoisseurs method (with no organic interference) is
to press the solid with KBr into a pellet
Under high pressure the KBr liquefies and entraps
individual molecules of the sample in the matrix
These spectra are the only spectra of solids that are as
interference free as liquids

24