4.2.
4 Modern Analytical Techniques
Infrared spectroscopy
Complicated spectra can be obtained than
Certain bonds in a molecule absorb infra-red radiation at provide information about the types of bonds
characteristic frequencies causing the covalent bonds to present in a molecule
vibrate
ABOVE 1500 cm-1 – “Functional group identification”
BELOW 1500 cm-1 – “Fingerprinting”
Complicated and contains many
signals – picking out functional group
signals difficult.
This part of the spectrum is unique for
every compound, and so can be used
as a "fingerprint".
A computer will compare the IR
e.g. C=O 1640 - 1750 cm-1
spectra against a database of known
O-H (acid) 2500 - 3300 cm-1 pure compounds to identify the
compound
Use an IR absorption table provided in exam
to deduce presence or absence of particular
bonds or functional groups Use spectra to identify particular functional groups limited to data
presented in wavenumber form e.g. an alcohol from an absorption peak
Bond Wavenumbe of the O–H bond.
r
C-O 1000-1300
Spectra for
C=O 1640-1750 butanal
C-H 2850 -3100
O
O-H 2500-3300 H3C CH2 CH2 C
Carboxylic acids Very broad H
N-H 3200-3500
2000 1500
O-H 3200- 3550 C=O
Alcohols, phenols broad 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
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
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The ‘Greenhouse Effect’
Carbon dioxide (CO2), methane (CH4) and Infrared radiation is absorbed by
water vapour (H2O) are all greenhouse gases. C=O, O–H and C–H bonds in H2O, CO2
(They trap the Earth’s radiated infra red energy and CH4.
in the atmosphere). These absorptions contribute to
global warming
Water is the main greenhouse gas (but is
natural), followed by carbon dioxide and
methane. The ‘Greenhouse Effect’ of a given gas is
dependent both on its atmospheric concentration
and its ability to absorb infrared radiation and
also its residence time. (Time it stays in
atmosphere)
Concentrations of carbon dioxide in the atmosphere have risen The Earth is thought to be getting
significantly in recent years due to increasing burning of fossil fuels. warmer, and many scientists
Carbon dioxide is a particularly effective greenhouse gas and its believe it is due to increasing
increase is thought to be largely responsible for global warming. amounts of greenhouse gases in
the atmosphere.
Modern breathalysers measure ethanol in the breath by analysis using infrared spectroscopy,
Infrared spectroscopy can be used to monitor gases causing air pollution (e.g. CO and NO from car
emissions)
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Mass spectrometry
Measuring the Mr of an organic molecule Spectra for C4H10
If a molecule is put through a mass spectrometer Mass spectrum for butane
it will often break up and give a series of peaks
caused by the fragments. The peak with the 43
Molecular ion
largest m/z, however, will be due to the complete
C4H10+
molecule and will be equal to the Mr of the
molecule. This peak is called the parent ion or 29
molecular ion
58
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.
Equation for formation molecular ion
Mass spectrum for butane
C4H10 [C4H10]+. + e– m/z 58
43
Equations for formation of fragment ions from molecular ions
[C4H10]+. [CH3CH2CH2]+ + .CH3 m/z 43
29 C4H10 = 58
[C4H10]+. [CH3CH2]+ + .CH2CH3 m/z 29
Equation for formation molecular ion
Mass spectrum for butanone
CH3CH2COCH3 [CH3CH2COCH3]+. + e– m/z 72
The high peak 43
at 43 due to [CH3CO]+ Equations for formation of fragment ions from molecular ions
stability of acyl
group [CH3CH2COCH3]+. [CH3CH2CO]+ + .CH3 m/z 57
29 [CH3CH2CO]+ [CH3CH2COCH3]+. [CH3CO]+ + .CH2CH3 m/z 43
+.
[CH3CH2]+ 57 [CH3CH2COCH3] [CH3CH2COCH3]+. [CH3CH2]+ + .COCH3 m/z 29
72
A mass spectrum is essentially a fingerprint for the
molecule that can be identified by computer using a
spectral database.
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