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Introduction
Spectroscopy is a collective name for the various techniques that use the
interaction between molecules and electromagnetic radiation to elucidate the
structure of molecules. Spectroscopic methods are fundamental to the study of
Chemistry, Molecular Biology, Medicine and Astrophysics.
This booklet covers the following techniques:-
Describe how infrared spectroscopy (i.r.) can be used for the elucidation
of molecular structure;
Interpret infrared spectra for salicylic acid and simple compounds
containing a limited range of functional groups (hydroxyl, carbonyl,
carboxylic acid and ester) given relevant information.
B) Mass Spectrometry
Describe how mass spectrometry (m.s.) can be used for the elucidation
of molecular structure;
Interpret mass spectra (molecular ion and significance of the
fragmentation pattern) for salicylic acid and simple compounds containing
a limited range of functional groups (hydroxyl, carbonyl, carboxylic acid
and ester) given relevant information.
Calculations
1) c =
2) Wavenumber = 1/ (cm)
Theory
c.f.
spring
oscillations
Functional group
Alcohols
Absorbance (cm-1)
3200 3600 / strong and broad*
OH
Carboxylic acids
C=O
Aldehydes / ketones /
carboxylic acids/ esters
C-O
C-H
displayed
formula
i.r. spectrum
Absorption / cm-1
displayed
formula
i.r. spectrum
Absorption / cm-1
i.r. spectrum
Absorption / cm-1
1750
1250
3000
NB: This Alcohol is oxidised to compound 4)b) when heated under distillation
with acidified potassium dichromate and 4)c) when heated to reflux with
acidified potassium dichromate.
Clue?
Bond / (Functional group)
Displayed Formula of 4a
Absorption / cm-1
Absorption / cm-1
4)c) i.r. spectrum of the compound with molecular formula C 3H6O2 formed
when compound 4a is heated to reflux with acidified potassium
dichromate
Absorption / cm-1
5)a) i.r. spectrum of an isomer of 4a which forms the same product 5)b)
whether it is heated to distil or reflux with acidified potassium
dichromate
Absorption / cm-1
Absorption / cm-1
displayed
formula
i.r. spectrum
Absorption / cm-1
7) Aspirin (CH3COOC6H4COOH)
i.r. spectrum
Absorption / cm-1
2900 v. broad
1750
1700
1200
B) Mass Spectrometry
AS-level
A2-level
The atoms or molecules are ionised by bombarding with high energy
electrons:-
e.g. CH3COCH3 +
[CH3COCH3]
M+
2e
Usually, the resulting molecular ion has such high energy that it splits up
into a smaller ion and an uncharged molecule (fragmentation)
+
e.g. [CH3COCH3]
M+m/e = 58
or
[CH3COCH3]
58
[CH3CO]
CH3
43
CH3CO
[CH3]
15
The following peaks are often seen in the fragmentation patterns of mass
spectra the highlighted peaks usually provide very useful clues in
determining the structure of a molecule
fragment
m/e
CH3
15
CH3CH2 or CHO
29
CH2NH2
30
CH2OH
31
CH3CO or C3H7
43
CONH2
44
COOH
45
C6H5
77
C6H5CH2
91
C6H5CO
105
mass spectrum
m/z
58
43
15
Formula
m/z lost
Group lost
2) Propanal (CH3CH2CHO)
displayed
formula
mass spectrum
m/z
58
57
29
Formula
m/z lost
Group lost
O
C
H
O
H
mass spectrum
m/z
136
105
77
Formula
m/z lost
Group lost
mass spectrum
m/z
88
73
43
29
15
Formula
m/z lost
Group lost
displayed
formula
mass spectrum
m/z
Formula
m/z lost
Group lost
138
*
120
92
6) Aspirin (CH3COOC6H4COOH)
mass spectrum
m/z
180
138
120
43
Formula
m/z lost
Group lost
7) ethanamide (CH3CONH2)
displayed
formula
mass spectrum
m/z
59
44
43
Formula
m/z lost
Group lost
displayed
formula
mass spectrum
m/z
151
109
108
43
Formula
m/z lost
Group lost
Theory
When such nuclei are placed in a large magnetic field they will become
aligned with or against the direction of the external field.
The nuclei lined up with the field are slightly more stable (lower energy)
than those that oppose the external field.
If the sample is irradiated with a pulse of radio waves, the nuclei in the
lower energy state may be promoted to the higher energy state (the tiny
bar magnets flip from being aligned with to against the external field).
The excited nuclei will then return to the ground state releasing fixed
quanta of energy which will be detected.
The energy gap depends on the chemical environment of the nuclei and can be
used to deduce the exact structure of the molecule.
Ethanal has two proton types, so produces 2 signals in the n.m.r. spectrum .
The important features of the spectrum are: The number of peaks number of proton types
The integration how many protons of each type
The chemical shift () what are the proton types
The following table can be used to link the chemical shift to the proton type (chemical
environment of H atom):type of proton
0.8 - 1.4
1.8 - 2.2
RCH2Hal
3.2 - 4.6
3.2 - 3.5
ROH (alcohol)
1.0 - 6.0
RC6H4H (arenes)
6.0 - 9.0
RC6H4CH3 (methylarene)
2.2 - 2.4
RCONHR (amides)
7.0 - 10.0
RCHO (aldehydes)
9.7 - 9.8
9.0 - 12.0
RC6H4OH (phenols)
variable
RNHR (amines)
variable
1) propanone (CH3COCH3)
displayed
formula
nmr spectrum
Proton
integration
Ha
2) propanal (CH3CH2CHO)
inference
/ ppm
inference
displayed
formula
nmr spectrum
Proton
integration
inference
/ ppm
Ha
9.7
Hb
2.4
Hc
1.1
inference
Ha
Ha
Ha
Hb
Hc
Hb
Hc
Hc
nmr spectrum
Proton
integration
inference
/ ppm
Ha
2.1
Hb
4.1
Hc
1.2
inference
displayed
formula
nmr spectrum
Proton
integration
inference
/ ppm
Ha
8.0
Hb
7.6
Hc
7.0
inference
5) Aspirin (CH3COOC6H4COOH)
H
H
H
H
nmr spectrum
Proton
integration
inference
/ ppm
Ha
11.3
Hb
4x1
7-8
Hc
2.1
inference
Proton
integration
Ha
9.7
Hb
9.1
Hc
7.4
Hd
6.7
He
2.0
Structure
inference
/ ppm
inference
a) IR spectroscopy
Absorption / cm-1
b) Nmr spectroscopy
Proton
integration
inference
/ ppm
inference
c) Mass Spectrometry
m/z
Formula
m/z lost
Group lost
b) nmr spectrum
c) mass spectrum
45
60