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6 Spectros PDF
6 Spectros PDF
NMR spectroscopy
NMR spectroscopy involves interaction of materials with the low- The radio waves used in
energy radiowave region of the electromagnetic spectrum proton nmr cause the
hydrogen nucleus to change
NMR spectroscopy is the same technology as that used in ‘magnetic its spin state.
resonance imaging’ (MRI) to obtain diagnostic information about
internal structures in body scanners e.g. scanning for brain disorders
Ha H b 3 Ha Hb Hc H d
a
a H Hd
H C C O C C C C
c aH Hc H
H Hb H H C Ha d
a 2 a
Ha
4sets of equivalent H’s:
Ethanol has 3 ratio 6:1:2:3
1
groups of different
O
hydrogen atoms
H3C C CH3 1 signal
a a
a b O c
CH3c H3C CH2 C O CH3
O
a b c
H3C CH2 C O C CH3
3 sets of equivalent H’s: ratio 3:2:3
c
CH3
Br
3 sets of equivalent H’s: ratio 3:2:9
a b c
H3C CH CH2 CH3 CH CH2 CH3
a b c d
3 sets of equivalent 4 sets of equivalent H’s: ratio 3:1:2:3
H’s: ratio 3:1:2
Solvents
This means that in the H NMR the
Samples are dissolved in solvents without any 1H atoms, e.g. CCl4, CDCl3.
solvent will not give any peaks
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Calibration and shift
H NMR shift
The δ depends on what other atoms/groups are near the
H – more electronegative groups gives a greater shift.
3
O
H3C CH2 C O CH3
δ ppm
H H O
H C C C
H H O H
2
δ ppm
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Spin-Spin coupling in H NMR
Nuclei in identical chemical
In high resolution H NMR each signal in the spectrum can be split into environments do not show
further lines due to inequivalent H’s on neighbouring C atoms. coupling amongst themselves!
ppm
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Infrared spectroscopy
C-O 1000-1300
Spectra for
O-H absorptions tend ethanoic acid
to be broad
O
Absorption or trough in
between 2500-3300 cm-1 range H3C C
indicates presence of O-H OH
bond in an acid
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 Spectra for C4H10
Fragmentation
Molecular ion formed: M → [M]+. + e–
When organic molecules are passed through a mass
spectrometer, it detects both the whole molecule and The molecule loses an electron and
fragments of the molecule. becomes both an ion and a free radical
Several peaks in the mass spectrum occur due to fragmentation. This process produces an ion
The Molecular ion fragments due to covalent bonds breaking: [M]+. → X+ + Y. and a free radical. The ion is
responsible for the peak
Relatively stable ions such as carbocations R+ such as CH3CH2+ and
acylium ions [R-C=O]+ are common. The more stable the ion, the greater
the peak intensity.
The peak with the highest mass/charge ratio will be normally due to the
original molecule that hasn’t fragmented (called the molecular ion) . As
the charge of the ion is +1 the mass/ charge ratio is equal to Mr.
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Chromatography
The mobile phase may be a liquid or a gas.
The stationary phase may be a solid (as in thin-
Chromatography is an analytical technique that separates
layer chromatography, TLC) or either a liquid or
components in a mixture between a mobile phase and a
solid on a solid support (as in gas
stationary phase
chromatography, GC)
Waste
column outlet
Basic gas-liquid chromatography will tell us how
many components there are in the mixture by the Carrier gas detector
number of peaks. It will also tell us the
abundance of each substance. The area under
each peak will be proportional to the abundance
of that component
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Bringing it all together
C H O
1. Work out empirical formula
66.63/12 11.18/1 22.19/16
Elemental analysis C 66.63% H 11.18% O 22.19%
=5.5525 =11.18 =1.386875
=4 =8 =1
3. Use IR spectra to identify main C8H16O2 could be an ester, carboxylic acid or combination of
bonds/functional group alcohol and carbonyl. Look for IR spectra for C=O and O-H
bonds
C-H
C=O
CH3
H3C C
4. Use NMR spectra to give details of carbon chain singlet of area 9
At δ =0.9 CH3
4 peaks – only 4 different environments. Means 3 CH3 groups
9
5 4 δ ppm 3 2 1
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