STRUCTURAL IDENTIFICATION OF
CHEMICAL COMPOUNDS
and
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
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
C-H C-NH2
+1 +N,+H
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
Nuclear
Vibrational
Ultraviolet Visible magnetic
infrared
resonance
2.5 mm 15 mm 1m 5m
200 nm 400 nm 800 nm
BLUE RED
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
WAVELENGTH (cm-1)
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
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
MATHEMATICAL DESCRIPTION
OF THE
VIBRATION IN A BOND
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)
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
infrared beam
C C
+ + O d+
O
- - d-