MISS CHOHANS NOTES ON ANALYSIS UNIT 2 EDEXCEL

ANALYSIS

 Mass spectrometry Measuring the Mr of an

organic molecule
 If a molecule is put through a mass
spectrometer it will often break up and give a
series of peaks caused by the fragments.
 The peak with the largest m/z, however, will
be due to the complete molecule and will be
equal to the Mr of the molecule.
 This peak is called the parent ion or molecular
ion

Fragmentation
+.
Molecular ion formed: M → [M] + e– The molecule loses
When organic molecules are passed through a mass
an electron and becomes both an ion and a free radical
spectrometer, it detects both the whole molecule and
fragments of the molecule.

Several peaks in the mass spectrum occur due to

fragmentation. The Molecular ion fragments due to This process produces an ion and a free radical. The
covalent bonds breaking: ion is responsible for the peak

+. + .
[M] → X + Y

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

+
CH3CH2CHO → [CH3CH2CHO] . + e– m/z 58

Equations for formation of fragment ions from molecular

ions

+. + .
[CH3CH2CHO] → [CHO] + CH2CH3 m/z 29

+. + .
[CH3CH2CHO] → [CH3CH2] + CHO m/z 29
MISS CHOHANS NOTES ON ANALYSIS UNIT 2 EDEXCEL

Equation for formation molecular ion

+.
CH3COCH3 → [CH3COCH3] + e– m/z 58

Equations for formation of fragment ions from molecular ions

+. + .
[CH3COCH3 ] → [CH3CO] + CH3 m/z 43

It is not possible for propanone to fragment to give a peak at

29 so the fragmentation patterns can distinguish between
the structural isomers of propanone and propanal

INFRA-RED SPECTROSCOPY

 Organic molecules absorb infra-red light.

 The reason for this is that the electromagnetic radiation in the infra-red region causes bonds to vibrate.
 Each bond vibrates at a particular frequency and absorbs the light at that frequency.
 This means that by looking at which frequencies are absorbed, it is possible to determine which bonds are
present.

 In infra-red spectroscopy a range of frequencies are passed through a compound and the intensity of the
light emerging is detected.
 The infra-red spectrum shows the amount of light being absorbed at particular frequencies.
 The frequency is usually expressed as the wave number which is the reciprocal of the wavelength in units of
cm-1.

The table below gives information about infrared absorption.

Bond Type of compound Absorption Intensity

C-H Alkanes, alkenes, aldehydes 2840 to 3095 Medium - strong
C=C Alkenes 1610 to 1680 Medium
C=O Aldehydes and ketones 1680 to 1750 Strong
(C-O) (Alcohols) 1000 to 1300 Strong
C-Cl 700 to 800 Strong
O-H “free” 3850 to 3670 Strong
Hydrogen bonded in alcohols 3230 to 3550 Strong [Broad]
Hydrogen bonded in carboxylic acids 2500 to 3300 Medium [Broad]
N-H amines 3100 to 3500 Strong
MISS CHOHANS NOTES ON ANALYSIS UNIT 2 EDEXCEL

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 e.g. an alcohol from an absorption peak of the O–H bond, or C=O
stretching absorption in aldehydes and ketones
MISS CHOHANS NOTES ON ANALYSIS UNIT 2 EDEXCEL

Molecules which change their polarity as they vibrate can absorb infrared radiation. E.g. C-H, C=O, O-H

Molecules such as H2 , O2 and N2 cannot change their polarity as they vibrate so can absorb infrared radiation and don’t
register on an infra red spectrum
 MISS CHOHANS NOTES ON ANALYSIS UNIT 2 EDEXCEL

The absorption of infra-red radiation by bonds in this type of spectroscopy is the same absorption that bonds in CO 2 , methane
and water vapour in the atmosphere do that cause them to be greenhouse gases.

H2O, CO2 , CH4 and NO molecules absorb IR radiation and are greenhouse gases, whilst O 2 and N2 are not.