FURTHER MASS SPECTROMETRY

A guide for A level students

KNOCKHARDY PUBLISHING

MASS SPECTROMETRY
INTRODUCTION This Powerpoint show is one of several produced to help students understand selected topics at AS and A2 level Chemistry. It is based on the requirements of the AQA and OCR specifications but is suitable for other examination boards. Individual students may use the material at home for revision purposes or it may be used for classroom teaching if an interactive white board is available. Accompanying notes on this, and the full range of AS and A2 topics, are available from the KNOCKHARDY SCIENCE WEBSITE at...

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MASS SPECTROMETRY
CONTENTS
Fragmentation of molecular ions - theory What a mass spectrum tells you Molecular ions Fragmentation Mass spectra of alkanes Mass spectra of halogenoalkanes

Mass spectra of aldehydes and ketones

Test questions Check list

MASS SPECTROMETRY
Before you start it would be helpful to
recall the basic principles of a mass spectrometer know the different types of functional group in organic chemsitry

MOLECULAR MASS DETERMINATION USING MASS SPECTROMETRY

Nowadays, mass spectrometry is used to identify unknown or new compounds.
IONISATION

MOLECULAR ION FRAGMENTION

When a molecule is ionised it forms a MOLECULAR ION which can also undergo FRAGMENTATION or REARRANGEMENT to produce particles of smaller mass. Only particles with a positive charge will be deflected and detected.

RE-ARRANGEMENT

FRAGMENTION

The resulting spectrum has many peaks. The final peak (M+) shows the molecular ion (highest m/z value) and indicates the molecular mass. The rest of the spectrum provides information about the structure.

THE MASS SPECTRUM

Spectra obtained for organic molecules have many peaks. Each peak is due to a particular fragment with a certain m/z value.

highest m/z value usually corresponds to the molecular ion its position provides information about the molecular mass of a substance the tallest peaks come from the most stable species

THE MASS SPECTRUM

Spectra obtained for organic molecules have many peaks. Each peak is due to a particular fragment with a certain m/z value.

highest m/z value usually corresponds to the molecular ion its position provides information about the molecular mass of a substance the tallest peaks come from the most stable species

Interpretation of thousands of spectra has shown that many classes of organic compound show characteristic fragmentation patterns due to their functional groups. It is possible to identify the type of compound from its spectrum by looking at the ...

position of peaks differences between major peaks

THE MASS SPECTRUM - THE MOLECULAR ION

In the spectrum of octane, a signal occurs at 114 due to the species C8H18+
The species due to the final signal is known as the molecular ion and is usually corresponds to the molecular mass of the compound.

Abundance %

60

80

100

40

molecular ion 114

20

.
10 20 30 40 50 60 70 80 90 100 110 120 130 140

m/z

THE MASS SPECTRUM - THE MOLECULAR ION

The small peak (M+1) at 115 due to the natural abundance (about 1%) of carbon-13. The height of this peak relative to that for the molecular ion depends on the number of carbon atoms in the molecule. The more carbons present, the larger the M+1 peak.

Abundance %

40

60

80

100

114
20

.
10 20 30 40 50 60 70 80 90 100 110 120 130 140

m/z

THE MASS SPECTRUM - FRAGMENTATION

The rest of the spectrum provides additional information of the molecules structure. Peaks appear due to characteristic fragments (e.g. 29 due to C2H5+) and differences between two peaks also indicates the loss of certain units (18 for H2O, 28 for CO).

100

43

Abundance %

60

80

29

57

71

85 114

20

40

.
10 20 30 40 50 60 70 80 90 100 110 120 130 140

m/z

FRAGMENTATION PATTERNS ALKANES

The mass spectra of simple hydrocarbons have peaks at m/z values corresponding to the ions produced by breaking C-C bonds. Peaks can occur at ... m/z 15 CH3+ 29 C2H5+ 43 C3H7+ 57 C4H9+ 71 C5H11+ 85 C6H13+ etc.

the stability of the carbocation formed affects its abundance

the more stable the cation the higher the peak

the more alkyl groups attached to the carbocation the more stable it is most stable tertiary 3 > secondary 2 > primary 1 least stable

alkyl groups are electron releasing and stabilise the cation

FRAGMENTATION PATTERNS HALOGENOALKANES

Multiple peaks occur in the molecular ion region due to different halogen isotopes. There are two peaks for the molecular ion of C2H5Br, one for the molecule containing the isotope 79Br and the other for the one with the 81Br isotope. Because the two isotopes are of similar abundance, the peaks are of similar height.
100

Abundance %

20

40

60

80

molecular ion contains...79Br

81Br

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

FRAGMENTATION PATTERNS ALDEHYDES AND KETONES

Cleavage of bonds next to the carbonyl group (C=O) is a characteristic fragmentation of aldehydes and ketones. A common fragment is carbon monoxide (CO) but as it is a molecule and thus uncharged it will not produce a peak of its own. However, it will produce an m/z drop of 28 somewhere in the spectrum. The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group

the more stable the acylium ion RCO+, the more abundant it will be and the more abundant the species the taller its peak in the mass spectrum

FRAGMENTATION PATTERNS Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group.

O CH3 C
+

C4H9

MOLECULAR ION has m/z = 100

FRAGMENTATION PATTERNS Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group.

O CH3 C O C4H9 C+
m/z = 85

C4H9

MOLECULAR ION has m/z = 100

CH3

Breaking the bond between the methyl group and the carbonyl group produces two possible ions, depending on how the bond breaks. Two peaks at m/z values 15 and 85 will appear in the mass spectrum.

C4H9

CH3+
m/z = 15

FRAGMENTATION PATTERNS Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group.

O CH3 C
+

C4H9

MOLECULAR ION has m/z = 100

O
Breaking the bond between the butyl group and the carbonyl group produces two further ions, depending on how the bond breaks. Two peaks at m/z values 43 and 57 will appear in the mass spectrum.

CH3 C+
m/z = 43

C4H9

O CH3 C C4H9+
m/z = 57

FRAGMENTATION PATTERNS Aldehydes and ketones

The position of the carbonyl group influences the fragmentation pattern because the molecular ion fragments either side of the carbonyl group.

Example;

O CH3 C
+

C4H9

MOLECULAR ION has m/z = 100

O C4H9 C+
m/z = 85

O
CH3 CH3 C+
m/z = 43

C4H9

O CH3+
m/z = 15

C4H9

CH3 C

C4H9+
m/z = 57

A further peak occurs at m/z = 72 (100-28) due to loss of CO

IDENTIFY THE COMPOUNDS

IDENTIFY THE COMPOUND

Abundance %

80

100

43

29

40

60

122

124

20

79 81 0

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

IDENTIFY THE COMPOUND

Abundance %

80

100

43

29

40

60

122

124

20

79 81 0

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C3H7Br

IDENTIFY THE COMPOUND

100

105

Abundance %

80

77 51 120 43

40

60

20

28

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

IDENTIFY THE COMPOUND

100

105

Abundance %

80

77 51 120 43

40

60

20

28

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C6H5COCH3

IDENTIFY THE COMPOUND

Abundance %

100

60

80

105 106 51 77

40

57
43

20

28
0

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

IDENTIFY THE COMPOUND

Abundance %

100

60

80

105 106 51 77

40

57
43

20

28
0

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C6H5CHO

IDENTIFY THE COMPOUND

100

56 57 43

113

Abundance %

60

80

71

40

142
20

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

IDENTIFY THE COMPOUND

100

56 57 43

113

Abundance %

60

80

71

40

142
20

m/z
10 20 30 40 50 60 70 80 90 100 110 120 130 140

C10H22

REVISION CHECK

What should you be able to do?

Understand how mass spectrometry can be used to calculate molecular mass Recall the term molecular ion and understand what information it provides Interpret simple mass spectra

CAN YOU DO ALL OF THESE?

YES

NO

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WELL DONE!
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FURHER MASS SPECTROMETRY

The End

2004 JONATHAN HOPTON & KNOCKHARDY PUBLISHING