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KIM3204

STRUCTURAL IDENTIFICATION OF
CHEMICAL COMPOUNDS

CHAPTER 1: Infra-Red Spectroscopy (IR)


Chapter Overview:

In this Chapter, we will be discussing on:


- Fundamental aspect of IR and
instrumentation
- Infra-red absorption process
- Introduction to stretching and bending
- Bonding characteristics and absorption
- The use of IR Correlation chart
- Practice and more practice !
IR 1/6

INDEX OF HYDROGEN DEFICIENCY

and

THE BASIC THEORY OF


INFRARED SPECTROSCOPY
WHAT CAN YOU LEARN FROM A
MOLECULAR FORMULA ?

YOU CAN DETERMINE THE NUMBER OF


RINGS AND / OR DOUBLE BONDS.
Saturated Hydrocarbons
CnH2n+2 GENERAL FORMULA

CH4 CH4
CH3CH3 C2H6
CH3CH2CH3 C3H8
CH3CH2CH2CH3 C4H10
CH3CH2CH2CH2CH3 C5H12

CH3 CH3
CH3 CH CH C CH3 C9H20
CH3 CH3
branched compounds
also follow the formula
FORMATION OF RINGS AND DOUBLE BONDS

-2H
C C C C
H H

H H
-4H
C C C C
H H

CH2 CH2
H2C -2H H2C CH2
CH2 H
H2C CH2 H H2C CH2
CH2 CH2

Formation of each ring or double bond causes the loss of 2H.


Index of Hydrogen Deficiency
CALCULATION METHOD

Determine the expected formula for a noncyclic,


saturated compound ( CnH2n+2 ) with the same
number of carbon atoms as your compound.

Correct the formula for heteroatoms (explained later)

Subtract the actual formula of your compound

The difference in Hs divided by 2 is the

Index of Hydrogen-deficiency
C5H8

C5H12 = ( CnH2n+2 )
C5H8
H4 Index = 4/2 = 2
Two Unsaturations
double bond and
ring in this example
Index of Hydrogen Deficiency
CORRECTIONS FOR ATOMS OTHER THAN HYDROGEN
O or S -- doesnt change H in calculated formula

+0 C-H
+O
C-O-H

N or P -- add one H to the calculated formula

C-H C-NH2
+1 +N,+H

F, Cl, Br, I -- subtract one H from calculated


formula
-1 C-H C-X
-H,+X
H
N
C4H5N

C4H10 = ( CnH2n+2 )
C4H11N add one H for N
C4H5 N
H6 Index = 6/2 = 3
two double bonds and
ring in this example
The index gives the number of
double bonds or
triple bonds or
rings in a molecule
one ring and the
equivalent of three
Benzene
double bonds gives
an index of 4

If index = 4, or more,
expect a benzene ring
PROBLEM A hydrocarbon has a molecular
formula of C6H8. It will react with
hydrogen and a palladium catalyst
to give a compound of formula
C6H12. Give a possible structure.

INDEX C6H14
-C6H8
H6 Index = 6/2 = 3

HYDROGENATION
Pd
C6H8 + 2 H2 C6H12
Hydrogenation shows only two double bonds.
Therefore, there must also be a ring.
A FEW POSSIBLE ANSWERS
CH3
CH3

H3C CH3

CH3

CH2CH3

..... there is still work required to fully solve the problem


INFRARED
SPECTROSCOPY
THE ELECTROMAGNETIC SPECTRUM
high Frequency (n) low
high Energy low

X-RAY ULTRAVIOLET INFRARED MICRO- RADIO FREQUENCY


WAVE

Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED

short Wavelength (l) long


Types of Energy Transitions in Each Region
of the Electromagnetic Spectrum

REGION ENERGY TRANSITIONS

X-ray Bond-breaking
UV/Visible Electronic
Infrared Vibrational
Microwave Rotational
Radio Frequency Nuclear and
(NMR) Electronic Spin
Simplified Infrared Spectrophotometer
NaCl
focusing plates
mirror
Detection Electronics
and Computer

Determines Frequencies
of Infrared Absorbed and
Infrared
plots them on a chart
Source

Infrared
Sample Spectrum

intensity of
Absorption absorption
peaks
frequency
(decreasing)
Infrared Spectroscopy (IR) Lab
Infrared Spectroscopy
1. Liquid Samples
a. 1 to 2 drops of liquid sample are placed between
two single crystals of sodium chloride (Salt Plates)
Note: NaCl plates are water soluble keep dry
2. Solid Samples Soluble in Acetone
a. Dissolve sample in acetone
b. Evaporate on Salt Plate
3. Solid Samples Not Soluble in Acetone
a. Make Potassium Bromide (KBR) pellet
4. Put Salt Plate sandwich in Plate Holder
5. Place Plate Holder into Beam Slot of IR Spectrometer
KETONE

4-Methyl-2-pentanone
C-H < 3000, C=O @ 1715 cm-1

100
100
%

T 80
80
R
A
N 60
S 60
M
I 40
T 40
T
A
N 20 CH3 O
20
C
E
0
CH3 CH CH2 C CH3
0

3500 3000 2500 2000 1500 1000 500

WAVELENGTH (cm-1)

https://youtu.be/S8R30EdcIT4?t=11 AN INFRARED SPECTRUM


THE UNIT USED ON AN IR SPECTRUM IS
WAVENUMBERS ( n )
n= wavenumbers (cm-1)
1
n= l(cm)
l = wavelength (cm)

c = speed of light
n = frequency = nc c = 3 x 1010 cm/sec
or

n (l)
=
1 c = c cm/sec = 1
l cm sec

wavenumbers are directly proportional to frequency


Molecular vibrations
Two major types :

STRETCHING
C C
BENDING C

bond is vibrating
C
stretching C
bending
both of these types are infrared active
( excited by infrared radiation )
BONDING CURVES
AND VIBRATIONS

MORSE CURVES
STRETCHING
BOND VIBRATIONAL ENERGY LEVELS

++ + + + oo +
++
e MORSE CURVE
n
e
r
g
y
zero point energy

rmin rmax
decreasing distance
ravg (average bond length) oscillate
BOND VIBRATIONAL ENERGY LEVELS
Bonds do not have a fixed distance.
They vibrate continually even at 0oK (absolute).
The frequency for a given bond is a constant.
Vibrations are quantized as levels.
The lowest level is called the zero point energy.

e
n bond
e dissociation
energy
r vibrational
g energy levels
y
zero point energy

rmin rmax
distance
ravg (average bond length)
Typical Infrared Absorption Regions
(stretching vibrations)

WAVELENGTH (mm)
2.5 4 5 5.5 6.1 6.5 15.4

O-H C-H C N C=O C=N C-Cl


Very C-O
N-H C C few C=C
C-N
X=C=Y bands C-C
(C,O,N,S) N=O N=O *

4000 2500 2000 1800 1650 1550 650


FREQUENCY (cm-1)
* nitro has
two bands
Infrared stretching absorptions
HARMONIC OSCILLATOR

MATHEMATICAL DESCRIPTION
OF THE
VIBRATION IN A BOND

. assumes a bond is like a spring


force
HOOKES LAW
constant
compress
K stretch

Dx

x0 x1
restoring
force = -F = K(Dx)

Molecule
as a
m1 m2 Hookes
Law
K device
THE MORSE CURVE APPROXIMATES
AN HARMONIC OSCILLATOR
HOOKES
LAW
Harmonic Oscillator

ACTUAL
MOLECULE
Morse Curve
(anharmonic)

Using Hookes Law and the


Simple Harmonic Oscillator
approximation, the following
equation can be derived to
describe the motion of a bond..
oscillate
THE EQUATION OF A n= frequency
SIMPLE HARMONIC in cm-1
OSCILLATOR
c = velocity of light
( 3 x 1010 cm/sec )
1 K
n =
2 pc m
K = force constant
in dynes/cm
where

m1 m2 C C > C C >C C
m = multiple bonds have higher Ks
m1 + m2
m = atomic masses
This equation describes the
vibrations of a bond. m = reduced mass
larger K,
higher frequency

1 K
n =
2 pc m larger atom masses,
lower frequency

constants increasing K

=
C=C > C=C > C-C
2150 1650 1200

increasing m

C-H > C-C > C-O > C-Cl > C-Br


3000 1200 1100 750 650
DIPOLE MOMENTS
DIPOLE MOMENTS
Only bonds which have significant dipole moments will
absorb infrared radiation.

Bonds which do not absorb infrared include:

Symmetrically substituted alkenes and alkynes


R R
R C C R
R R

Many types of C-C Bonds

Symmetric diatomic molecules


H-H Cl-Cl bond is vibrating
dipole moments
STRONG ABSORBERS

The carbonyl group is one


d-
O
of the strongest absorbers d+
C

Also O-H and C-O bonds O H C O

infrared beam
C C
+ + O d+
O
- - d-

oscillating dipoles couple and


energy is transferred
Infrared absorption and the greenhouse effect