A2 Chemistry UNIT 4.

9
Mass Spectrometry and Infra Red
1.

Consider the following reaction scheme:

ste p 1

C 2H 5B r

s te p 2

C 2H 5M gB r

C 2H 5C O O H

PC l5

r o o m te m p e r a tu re

C 3H 5O C l

A lC l3
benzene

C 9H

L iA lH 4 , d ry e th e r

A
(a)

10O

C 9H

12

(4)

Give the equation for the reaction between propanoic acid and phosphorus
pentachloride, making clear the structure of compound A.
(2)

(b)

Compound B reacts with 2,4-dinitrophenylhydrazine but not with ammoniacal

silver nitrate solution. Give the structural formula for compound B and explain why
B reacts with 2,4-dinitrophenylhydrazine but not with ammoniacal silver nitrate.
(3)

(c)

(i)

Give the structural formula for C.

(1)

(ii)

State why the ether solvent must be dry in the conversion of B to C.

(1)

(d)

The infrared spectra of B and of C are given below, together with a table of
infrared absorbencies. What is the evidence from these spectra for the conversion
of the functional group in B to that in C?
(3)

Com pound B:

T ra n s m itta n c e (% )

100

50

0
4000

3000

2000

1500

W avenum ber / cm
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1000

500

Com pound C :

T ra n s m itta n c e (% )

100

50

0
4000

3000

2000

1500

W avenum ber / cm

1000

500

Infra-red absorbencies.
Bond

Assignment

Wavenumbers/cm1

CH

Alkanes
Alkenes, arenes

28502950
30003100

C==C

Alkenes

16101680

Benzene ring

Arenes

14501650

C==O

Aldehydes, ketones,
amides, esters,
carboxylic
acids

16801750

O H

Free

35803670

Hydrogen bonded in
alcohols or phenols

32303550
25003300

Hydrogen bonded in
carboxylic acids
(e)

(i)

PCl5 is made by the action of excess chlorine gas on white phosphorus, P4.
Give an equation to represent this reaction.
(2)

(ii)

PCl5 decomposes on heating just above its sublimation temperature

PCl5(g) PCl3(g) + Cl2(g)
Explain whether or not this is a redox reaction.
(3)
(Total 25 marks)

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2.

This question concerns the three isomers A, B and C, each of which has a relative
molecular mass of 134.
O

C H

C H

C H

CH

C
H

C H

C H

C H 2O H

C
(a)

The mass spectrum of substance A is shown below. Identify the species

responsible for the peaks labelled 1, 2 and 3.
Peak
1 ......................................................................................................................
...
Peak
2 ......................................................................................................................
...
Peak
3 ......................................................................................................................
...
(3)

100

R e la t iv e in t e n s it y

80
60
1

40
20

0
25

(b)

m /e

75

100

125

The infra-red spectra of two of these substances were also measured.

(i)

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50

Use the table and the spectra below to identify which spectrum is that of
substance C.

Bond

Wavenumb
er/ cm1

CH (arenes)

3000-3100

Bond
OH (hydrogen
bonded)

Wavenumb
er/ cm1
3200-3570

CH
(alkanes)

2850-3000

OH (not hydrogen
bonded)

3580-3650

C==O

1680-1750

C==C (arenes)

1450-1600

The spectrum of substance C is spectrum

number ..........................................
(1)

(ii)

Give one reason for your choice.

......................................................................................................................
(1)

(iii)

Give one other reason why the other spectrum could not be that of
substance C.
......................................................................................................................
......................................................................................................................
(1)

100

R e la t iv e in t e n s ity

80
60
1

40
20

0
25

50

T ra n s m itta n c e

100

75

100

125

50

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m /e

4000

3000

2000
1500
W a v e n u m b e r /c m 1

1000

T ra n s m itta n c e

100

50

(c)

4000

3000

2000
1500
W a v e n u m b e r /c m 1

1000

State which of the substances A, B and C will react with the following reagents
and state what would be observed.
(i)

Bromine dissolved in hexane.

Substance(s) ...................................................................................................
..
Observation ....................................................................................................
..
(2)

(ii)

A warm ammoniacal solution of silver nitrate.

Substance(s) ...................................................................................................
..
Observation ....................................................................................................
..
(2)

(iii)

2,4-dinitrophenylhydrazine solution.
Substance(s) ...................................................................................................
..
Observation ....................................................................................................
..

(iv)
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Give the structural formula of the organic product(s) obtained in (c)(i).

5

(1)

(v)

Give the structural formula of the organic product(s) obtained in (c)(ii).

(1)
(Total 15 marks)

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ANSWERS
1.
(a)

C H 3CH 2C

O H + P C l5

C H 3C H 2C

C l + P O C l3 + H C l

structure of acid chloride showing at least expansion of COCl (1)

products (1)

O
C

(b)

C 2H

(1 )
2,4dnp reacts with carbonyl group (1)
this carbonyl compound is a ketone and cannot be oxidised
by/ cannot reduce ammoniacal silver nitrate (1)
This is consequential on B being shown as a ketone

O H
C 2H

C
(c)

(i)

(e)

H
(1)
This is consequential on a ketone being shown in (d)
The lithium aluminium hydride would react with any water (1)

1
1

B has absorption peak in region 1680 1750 showing carbonyl (1)

but peak in region of 3250 3550 is present ( not present in B)
showing alcohol group / allow broad peak if range omitted (1)
comparison between two spectra (1)

(ii)
(d)

(i)

(ii)

P4 + 10Cl2 4PCl5
Allow
P4 + PCl3 PCl5
for species (1) for balancing (1)
If start with P2 or P allow one mark for balanced equation

Oxidation number of phosphorus changes from 5 to 3 (1)

Oxidation number of chlorine changes from 1 to 0 (1)
Change of oxidation number is redox (1)

3
[25]

2.

(a)

(b)

Peak 1
m/e 77: C6H5+ (1)
Peak 2
m/e 105: C6H5CO+ (1)
Peak 3
m/e 134: C6H5COCH2CH3+ (1)
if + left off penalize only once

(i)

IR spectrum number 2

(ii)

Because of the broad peak at 3320cm1 caused by OH / because peak at

3320 is OH / because it does not have a peak at 1750 and is only one

without

(c)

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(iii)

The other has a peak at approx. 1700 cm1 caused by C=O

(i)

(brown) goes colourless 1

(ii)

silver mirror / black precipitate 1

2
7

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(iii)

A (1) and B (1) red/orange/yellow ppt 1

(iv)

C6H5CHBrCHBrCH2OH

(v)

C6H5CH2CH2COO but allow the carboxylic acid as product

consequential