This question is about the three organic compounds involved in the following reaction.

C2H4O2 + C2H6O → C4H8O2 + H2O

W X Y

(a) The infrared spectra of all three compounds showed several absorptions. Describe what happens
on a molecular level when molecules absorb infrared radiation.
(3)

(b) Use the following information about their infrared spectra to deduce which bonds are present in
the three compounds.

–1
All three compounds showed an absorption close to 1200 cm .

–1
There were broad absorptions in both W and X. The one in W was centred around 3000 cm , and
–1
in X around 3400 cm .
–1
Compounds W and Y showed absorptions close to 1700 cm .

bonds in W

bonds in X

bonds in Y
(3)

1
(c) The H NMR spectra of the three compounds were available. State what can be deduced from each
of the following.

(i) The presence of two peaks in the spectrum of W.

(1)

(ii) The presence of a triplet and a quartet, with areas in the ratio 3:2, respectively, in the spectra
of both X and Y.
(1)

(d) Use your answers to (b) and (c) to deduce the structures of the three compounds.

Y
(3)

(e) The infrared spectrum of compound Z, an isomer of Y, is shown below.

 1 0 0

8 0

T r a n s m i 6t t 0a n c e / %

4 0

2 0

3 0 0 0 2 0 0 0
W a v e n u – 1m b e r / c m

(i) Estimate the wavenumber values of the three most prominent absorptions in this spectrum
and suggest which bonds are responsible for them.

absorption 1

absorption 2 .

absorption 3
(3)

(ii) Deduce the structure of Z.

(Total 15 marks)

(a) bond angles change/bonds bend;

bond lengths change/bonds stretch;
If neither scored, allow [1] for bonds vibrate.
bond polarity changes; 3
(b) W: C––O, C==O, O––H;
X: C––O, O––H;
Y: C––O, C ==O; 3

(c) (i) two different chemical environments for hydrogens/two different

‘types’ of proton/OWTTE; 1
(ii) CH3 and CH2 next to each other/CH3CH2/ethyl group; 1
(d) W: CH3COOH
X: CH3CH2OH;
Accept C2H5OH.
Y: CH3COOCH2CH3; 3
Accept CH3COOC2H5.
If displayed formulas attempted, penalize missing H atoms once only.

–1
(e) (i) 3000 – 2900 (cm ) C––H;
–1
1750 – 1700 (cm ) C==O;
–1
1150 – 1200 (cm ) C––O; 3
Above can be in any order as long as bond linked with correct
wave number.
(ii) CH3CH2COOCH3; 1
Accept C2H5COOCH3 and HCOOCH(CH3)2 and
CH3COCH2OCH3 .
If displayed formula attempted, penalize missing H atoms
unless already penalized in (d).
[15]
An organic compound with three carbon atoms has two structural isomers A and B with the same functional
–1
group. The infrared spectrum of the compound shows a broad absorption at about 3350 cm .

(a) The mass spectra of the two isomers A and B are as follows.

1 0 0

8 0
R e la tiv e In te n s ity

6 0

4 0

2 0

0
1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0
m / z
I s o m e r A
 1 0 0

8 0
R e la tiv e In te n s ity

6 0

4 0

2 0

0
1 0 1 5 2 0 2 5 3 0 3 5 4 0 4 5 5 0 5 5 6 0
m / z
I s o m e r B

(i) Deduce, giving a reason, the molecular formula of the organic compound.
(1)

(ii) Deduce the formula of the fragmentation ion responsible for the peak at each of these m/z
values.

isomer A 29

31

isomer B 30

45
(4)

1
(b) The H NMR spectra of isomers A and B are shown below.
 I s o m e r A

6 5 4 3 2 1 0
c h e m i δc / a l s h i f t p p m

I s o m e r B

6 5 4 3 2 1 0
c h e m i δc / a l s h i f t p p m

(i) State the formula and function of the compound responsible for the peak at 0 ppm.
(2)

(ii) Explain what information about the isomers can be obtained from the number of peaks and
area under each peak.
(2)
 (iii) Deduce the structural formulas of isomers A and B and give the ratio of peak areas in each
case.
(4)

(iv) Draw the structural formula of a third isomer C that has the same molecular formula as
isomers A and B but a different functional group. Give the ratio of peak areas in isomer C.
(2)
(Total 15 marks)

(a) (i) C3H8O, peak at 60 due to molecular ion/molar mass 60; 1

(ii) isomer A
29 C 2 H 5+ ;
+ +
31 CH2OH /CH3O ;
isomer B
+ +
30 CHOH /CH2O ;
+ +
45 CH3 -CHOH /C2H5O ; 4
If + charge missing, penalize once only.
(b) (i) Si(CH3)4/SiC4H12;
used as reference standard; 2
(ii) number of peaks
different chemical environments occupied by the protons/H atoms;
area under each peak
number/ratio of H atoms/protons in each particular chemical
environment; 2
(iii) isomer A
CH3CH2CH2OH;
ratio:
3 : 2 : 2 : 1;
isomer B
(CH3)2CHOH;
ratio:
 6 : 1 : 1; 4
(iv) CH3OCH2CH3;
3 : 2 : 3; 2
[15]

Compounds A and B are alcohols with the molecular formula C3H8O. The following information was obtained
from a mass spectrum of each alcohol.

A: peaks at m/z = 29, 31, 60

B: peaks at m/z = 45, 60

(a) Deduce the formula of the species responsible for the peak at m/z = 60.
(1)

(b) Deduce the formula of the species with m/z = 31.

(1)

(c) Deduce the structure of each alcohol.

Structure of A

Structure of B
(2)
(Total 4 marks)

+
(a) C3H8O ; 1
+
Accept more detailed formula such as CH3CH2CH2OH .
+ +
(b) CH3O / CH2OH ; 1
 For (a) and (b), if charge is missing penalize once only.
(c) (A) CH3CH2CH2OH;
Accept more detailed formula.
(B) CH3CH(OH)CH3; 2
Accept more detailed formula.
Hydrogen(s) missing, penalize once only.
Award [1] if both structures correct but the wrong way round.
[4]