SPECTROSCOPY - COMBINED TECHNIQUES

SPECTROSCOPY - COMBINED TECHNIQUES

Objectives:
Identify functional groups from IR spectra
Deduce formula mass from molecular ion peaks and parts of structures from fragmentation data

Use chemical, IR, MS and NMR data to deduce structures

Infra-red - The basics:

Different bonds in a molecule absorb IR and vibrate at different frequencies Infra-red spectra are complex due to the many different vibrations taking place in each molecule.

O-H in alcohol BUT bonds such as O-H and C=O can be confirmed because they have peaks in identifiable parts of the spectrum.

INFRA RED SPECTRA - INTERPRETATION

Vertical axis Horizontal axis

Absorbance Frequency

the stronger the absorbance the larger the peak wavenumber (waves per centimetre) / cm-1

FINGERPRINT REGION the messy bit

organic molecules have a lot of C-C and C-H bonds within their structure spectra obtained will have peaks in the 1400 cm-1 to 800 cm-1 range this is referred to as the fingerprint region and unique to a molecule

IR SPECTRUM OF A CARBONYL COMPOUND

carbonyl compounds show a sharp, strong absorption between 1700 and 1760 cm-1 this is due to the presence of the C=O bond

IR SPECTRUM OF AN ALCOHOL

alcohols show a broad absorption between 3200 and 3600 cm-1 this is due to the presence of the O-H bond

IR SPECTRUM OF A CARBOXYLIC ACID

carboxylic acids show a VERY broad absorption between 2500 and 3300 cm-1 this is due to the presence of the O-H bond they also show a strong absorption around 1700 cm-1 this is due to the presence of the C=O bond

IR SPECTRUM OF AN ESTER

esters show a strong absorption between 1750 cm-1 and 1730 cm-1 this is due to the presence of the C=O bond - Note this gives a similar result to ketones/aldehydes so you may need to use other evidence e.g. chemical

IR SPECTRUM OF AN AMINE

amines show an strong absorption between 3200 and 3500 cm-1 this is due to the presence of the N-H bond [ - note the double trough can be distinguished from O-H in an alcohol]

FUNCTIONAL GROUP?
95 90 85 80 75 70 65 60

%T

55 50 45 40 35 30 25 20 15 10 4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm-1)

Peak at 3300 cm-1 due to O-H in alcohols

FUNCTIONAL GROUP?
95 90 85 80 75 70 65 60

%T

55 50 45 40 35 30 25 20 15 10 4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm-1)

Very broad peak at 2800- 3200 cm-1 due to O-H in carboxylic acids Peak at 1700cm-1 due to C=O

Possibly -COOH

FUNCTIONAL GROUP?
95 90 85 80 75 70 65 60

%T

55 50 45 40 35 30 25 20 15 10 4000 3500 3000 2500 2000 1500 1000 500

Wavenumbers (cm-1)

Peak at 1700cm-1 due to C=O

Could be ketone, aldehyde or ester

Mass spectroscopy - the basics: Molecules are bombarded with electrons

This causes positive ions to form of different mass as the molecule fragments
These are detected and a spectrum results based on the ions masses (given as an m/z value)

When a molecule is ionised it forms a MOLECULAR ION

IONISATION

MOLECULAR ION FRAGMENTION

The molecular ion can fragment to produce particles of smaller mass. 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.

RE-ARRANGEMENT

FRAGMENTION

butane

C4H10 [C4H10]+. + e
m/z 58

CH3CH2CH2CH3
[CH3CH2CH2]+
43

[C4H10]+. [CH3CH2CH2]+ + .CH3

m/z 43

[C4H10]+. [CH3CH2]+ + .CH2CH3

m/z 29

Peak with greatest m/z value = MOLECULAR ION

[CH3CH2]+
29

[C4H10]+.
58

Other peaks due to molecular ion breaking into fragments

70 80 90 100 110

10

20

30

40

50 m/z

60

Using the m/z value of the molecular ion

The m/z value of the M+ ion = formula mass of the molecule

For example..

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 gives 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

butanone

CH3CH2COCH3

43

Mr = 72
29 72 57 10 20 30 40 50 m/z 60 70

80

90

100

110

methyl butanoate CH3CH2CH2COOCH3

43

Mr = 102
71 59 29 87

102 10 20 30 40 50 m/z 60 70 80 90 100 110

Using the m/z value of the molecular ion

The m/z value of the molecular ion is useful for finding the molecular formula given empirical formulae data

e.g. A compound has empirical formula of C2H4O The parent ion has an m/z value of 88 What is its molecular formula?

Answer: C4H8O2

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 more stable the ion the higher the peak the more alkyl groups attached to the ion the more stable it is (i.e. more branches = greater stability)

butane

C4H10 [C4H10]+. + e
m/z 58

CH3CH2CH2CH3
[CH3CH2CH2]+
43

[C4H10]+. [CH3CH2CH2]+ + .CH3

m/z 43

[C4H10]+. [CH3CH2]+ + .CH2CH3

m/z 29

[CH3CH2]+
29

[C4H10]+.
58

10

20

30

40

50 m/z

60

70

80

90

100

110

FRAGMENTATION PATTERNS ALDEHYDES AND KETONES Breaking of bonds next to the carbonyl group (C=O) is a typical fragmentation of aldehydes and ketones.

A common fragment is carbon monoxide (CO) - it will produce an m/z drop of 28 somewhere in the spectrum

the more stable the acylium ion RCO+, 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

butanone

CH3CH2COCH3

43

29 72

57 10 20 30 40 50 m/z 60 70

80

90

100

110

Abundance %

80

100

105

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

methyl butanoate CH3CH2CH2COOCH3

43

71

59 29 87

102 10 20 30 40 50 m/z 60 70 80 90 100 110

methyl butanoate CH3CH2CH2COOCH3

Which peaks would be absent if this was ethyl propanoate?

43

71

59 29 87

102 10 20 30 40 50 m/z 60 70 80 90 100 110

COMBINED TECHNIQUES Use I.R to find functional groups Use MS to find molecular formula with empirical formula data and clues about carbon skeleton Use C13 NMR for information on number and types of carbon environments Use proton NMR for information about numbers and types of proton and the environments they are in