11.

Spectroscopy
Mass spectroscopy high resolution mass spectrometry can be used to determine the molecular formula of a compound from the accurate mass of the molecular ion For example, the following molecular formulas all have a rough Mr of 60, but a more precise Mr can give the molecular formula. e.g. Mr = 60.02112 molecular formula = C2H4O2 Mr = 60.05751 molecular formula = C3H8O Mr = 60.03235 molecular formula = CH4N2O
Example 1 A compound is found to have an accurate relative formula mass of 46.0417. It is thought to be either CH3CH2OH or H2NCH2NH2. Calculate the Mr of each compound to 4 decimal places to work out which one it is. High resolution mass spectroscopy can measure the mass to 5 d.p. This can help differentiate between compounds that appear to have similar Mr (to the nearest whole number) Accurate masses of atoms: H = 1.0078 C = 12.0000 O = 15.9949 N = 14.0031

CH3CH2OH = (12.0000 x 2) + (15.9949 x 1) + (1.0078 x6) = 46.0417 H2NCH2NH2. = (12.0000 x 1) + (14.0031 x 2) + (1.0078 x6) = 46.0530 Fragmentation When organic molecules are passed through a mass spectrometer, it detects both the whole molecule and fragments of the molecule Molecular ion formed: M [M]+. + e

The molecule loses an electron and becomes both an ion and a free radical

Several peaks in the mass spectrum occur due to fragmentation. Molecular ion fragments due to covalent bonds breaking: [M]+. X+ + Y. Relatively stable ions such as carbocations R+ and acylium ions [R-C=O]+ are common. The more stable the ion, the greater the peak intensity m/z fragment 15 CH3+ 29 CH3CH2+ 31 CH2OH+ 43 CH3CH2CH2+ (CH3)2CH+ CH3CO+ 57

This process produces an ion and a free radical. The ion is responsible for the peak The acyl group present in carbonyls, O esters acid + derivatives is a R C common stable ion

CH3CH2CO+

Mass spectrum for butane

43

The peak with the highest mass/charge ratio will be normally due to the original molecule that hasnt fragmented (called the molecular ion) . As the charge of the ion is +1 the mass/ charge ratio is equal to Mr. C4H10 [C4H10]+. + e m/z 58

29 58

+. + . C4H10 = 58 [C4H10] [CH3CH2CH2] + CH3 m/z 43

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

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

m/z 29

Mass spectrum for butanone CH3CH2COCH3 [CH3CH2COCH3]+. + e m/z 72

[CH3CH2COCH3]+. [CH3CH2CO]+ + .CH3 m/z 57 [CH3CH2COCH3]+. [CH3CO]+ + .CH2CH3 m/z 43 [CH3CH2COCH3]+. [CH3CH2]+ + .COCH3 m/z 29
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Infrared spectroscopy Certain groups in a molecule absorb infra-red radiation at characteristic frequencies
ABOVE 1500 cm-1 Functional group identification

Complicated spectra can be obtained than provide information about the types of bonds present in a molecule

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".

e.g. C=O 1680 1750 cm-1 O-H (acid) 2500- 3000 cm-1

Use an IR absorption table provided in exam to deduce presence or absence of particular bonds or functional groups

A computer will compare the IR spectra against a database of known pure compounds to identify the compound

use spectra to identify particular functional groups and to identify impurities, limited to data presented in wavenumber form

Spectra for butanal

O CH3 CH2 CH2 C H

C=O Spectra for ethanoic acid

O-H absorptions tend to be broad

O CH3 C O H

C=O rogue absorptions can also occur and are indicators of impurities

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NMR spectroscopy
Different types of NMR There are two main types of NMR 1. C13 NMR 2. H (proton) NMR Equivalent Carbon atoms. In a C13 NMR spectrum, there is one signal (peak) for each set of equivalent C atoms.
H
a

There is only around 1% C13 in organic molecules but modern NMR machines are sensitive enough to give a full spectra for C13 The C13 spectra is a simpler spectrum than the H NMR

O
b CH3

H
b c

O C H

C H

C H

H a H C H

H c C O C

H d C H

a
H
H C H

b
C

c
C H

d
C H H

Ca O Ca O

a
H C H H

bCH 3

3 peaks 1,2 dinitrobenzene

4 peaks 1,3 dinitrobenzene 1,4 dinitrobenzene

4 peaks

2 peaks

NO 2
1 2 2 3 peaks 4 peaks 2 peaks 2 2 1
a H3C a

CH3 Cb Cl CH3
c d

a CH b

c d e

NO 2

2 peaks

NO2
5 peaks

Equivalent Hydrogen atoms. In an H NMR spectrum, there is one signal for each set of equivalent H atoms. 3
a H

In addition the intensity (integration value) of each signal is proportional to the number of equivalent H atoms it represents.
Ha C Hb C H C Ha Ha Hc C Hc H d C H Hd

aH

2 Ethanol has 3 groups of different hydrogen atoms 1

4sets of equivalent Hs: ratio 6:1:2:3

O H3C
a

CH3

1 signal
a

H3C

CH2

O C

c CH3

H3C
c

CH2

O C

CH3

O C CH3

CH3
c

3 sets of equivalent Hs: ratio 3:2:3

3 sets of equivalent Hs: ratio 3:2:9

a

Br CH3
a

H3C

CH CH2

CH
b

CH2
c

CH3
d

3 sets of equivalent Hs: ratio 3:1:2

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4 sets of equivalent Hs: ratio 3:1:2:3

Solvents Samples are dissolved in solvents free of 1H atoms, e.g. CCl4, CDCl3. This means that in the H NMR the solvent will not give any peaks

The same solvent is used in C13 NMR and in this case there will be one peak due to the solvent that will appear on the spectrum. However, it is known where this peak is so it can be ignored. In the exam it is likely this peak will not occur on the spectra Calibration and shift A small amount of TMS (tetramethylsilane) is added to the sample to calibrate the spectrum It is used because: its signal is away from all the others it only gives one signal it is non-toxic it is inert it has a low boiling point so is easy to remove The same calibration compound is used for both H and C NMR

CH3 CH3 Si CH3 CH3

The spectra are recorded on a scale known as the chemical shift (), which is how much the field is shifted from the field for TMS compared to the field for TMS.
7 6 5 4 3 2 1 0

The is a measure in parts per million (ppm) of how far the magnetic field required for absorption is shifted away from that for TMS. H NMR shift

10

chemical shift (ppm)

The depends on what other atoms/groups are near the H more electronegative groups gives a greater shift. 3
H3C CH2 O C O CH3

3
H H C H H C H C O H O

4
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C13 NMR shift

H H C H

O C O

H C H

H C H

H C H H

5-40 50-90

160-185

20-40

Spin-Spin coupling in H Nmr Each signal in the spectrum can be split into further lines due to inequivalent Hs on neighbouring C atoms. Number of lines = number of inequivalent Hs on neighbouring C atoms + 1
signal singlet doublet triplet quartet

Nuclei in identical chemical environments do not show coupling amongst themselves!

H3C
appearance

O b CH2 C

CH3

The peak due to group a will be a triplet as it is next to b (a carbon with 2 Hs)
1 2 3 4

number of lines number of neighbouring inequivalent H atoms relative size

The peak due to group b will be a quartet as it is next to a (a carbon with 3Hs) The peak due to group c will be a singlet as it is next to a carbon with no Hs)

1:1

1:2:1

1:3:3:1

a
H

H C

O C O

H C

H C H c H

a H c b

b H

The peak due to group c will be a triplet as it is next to a carbon with 2 Hs Shift 0.7-1.2 Integration trace 3 The peak due to group b will be a quartet as it is next to a carbon with 3 Hs Shift 3.7 -4.1 Integration trace 2 5

The peak due to group a will be a singlet as it is next to a carbon with 0 Hs Shift 2.1-2.6 Integration trace 3

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Chromatography Gas-liquid chromatography can be used to separate mixtures of volatile liquids Separation by column chromatography depends on the balance between solubility in the moving phase and retention in the stationary phase The time taken for a particular compound to travel through the column to the detector is known as its retention time. This can be used to identify a substance It is also possible for gas-liquid chromatography machine to be connected to a mass spectrometer, IR or NMR machine enabling all the components to be identified in a mixture In gas-liquid chromatography, the mobile phase is a gas such as helium and the stationary phase is a high boiling point liquid absorbed onto a solid.

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