Spectroscopy and Chromatography
Spectroscopy and Chromatography
Spectroscopy and Chromatography
NMR spectroscopy
NMR spectroscopy involves interaction of materials with the lowenergy radiowave region of the electromagnetic spectrum
Ha H b
Hb
a H
O
H
Ha
Hb
Hc
H d
Hc
aH
H C Ha
2
1
O
H3C
CH2
O
C O C
CH3
O
b
CH2 C
CH3c
H3C
Ha
Ethanol has 3
groups of different
hydrogen atoms
Hd
H3C
1 signal
a
c
CH3
CH3
CH3
Br
H3C
CH CH2
3 sets of equivalent
Hs: ratio 3:1:2
CH3
CH
CH2
CH3
Solvents
Samples are dissolved in solvents without any 1H atoms, e.g. CCl4, CDCl3.
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CH3
H3C
Si
CH3
CH3
tetramethylsilane
10
H NMR shift
The depends on what other atoms/groups are near the
H more electronegative groups gives a greater shift.
3
H3C
CH2
O
C
CH3
ppm
3
O
C
O
ppm
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In high resolution H NMR each signal in the spectrum can be split into
further lines due to inequivalent Hs on neighbouring C atoms.
Splitting of peak = number of inequivalent Hs on neighbouring C atoms + 1
signal
singlet
doublet
triplet
quartet
quintet
number of
neighbouring
inequivalent
H atoms
H3C
CH2
O
C
CH3
appearance
Split number
of peaks
relative size
1:1
1:2:1
1:3:3:1
a
H
1:4:6:4:1
C O
a H
b H
H c
c
b
ppm
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Infrared spectroscopy
Complicated spectra can be obtained than
provide information about the types of bonds
present in a molecule
Bond
Wavenumber
C-O
1000-1300
C=O
1640-1750
C-H
2850 -3100
O-H
Carboxylic acids
2500-3300
Very broad
N-H
3200-3500
O-H
Acohols, phenols
3200- 3550
broad
Spectra for
butanal
O
H3C CH2 CH2 C
2000
1500
C=O
Absorption or trough in between 1640-1750 cm-1 range indicates
presence of C=O bond
Always quote the wave number range from the data sheet
Spectra for
ethanoic acid
O
Absorption or trough in
between 2500-3300 cm-1 range
indicates presence of O-H
bond in an acid
H3C
C
OH
C=O
Modern breathalysers measure ethanol in the breath by analysis using infrared spectroscopy
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Mass spectrometry
Measuring the Mr of an organic molecule
Molecular ion
C4H10+
29
58
Fragmentation
M [M]+. + e
C4H10 [C4H10]+. + e
43
29
C4H10 = 58
m/z 29
CH3CH2COCH3 [CH3CH2COCH3]+. + e
m/z 72
stability of acyl
group
29
[CH3CH2]+
m/z 58
72
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Chromatography
The mobile phase may be a liquid or a gas.
The stationary phase may be a solid (as in thinlayer chromatography, TLC) or either a liquid or
solid on a solid support (as in gas
chromatography, GC)
Sample in
Flow
control
oven
display
Waste
outlet
column
Carrier gas
detector
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66.63/12
=5.5525
=4
11.18/1
=11.18
22.19/16
=1.386875
=8
=1
C-H
C=O
CH3
H3C
singlet of area 9
At =0.9
Means 3 CH3 groups
C
H
CH3
9
Peak at 1.2
shows R-CH3
Area 3 means CH3
Triplet means next
to a CH2
CH3
H 2
ppm
CH3
H3C C
O
CH2 C
CH2
CH3
CH3
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