Answers

Chapter 11
Exercises

1 The smallest division is 1 so the uncertainty is ±0.5. Absolute uncertainty in number of moles =
(6/100) × 0.0100 = 0.0006
2 The missing diamond has a mass of between
9.87 and 9.97 g. Number of moles = 0.0100 ± 0.0006 mol

The found diamond has a mass between 9.9 21 (a) ∆T = 43.2 − 21.2°C = 22.0°C
and 10.3 g. absolute uncertainty = (±)0.2°C
As the ranges overlap, it could be the missing (b) % uncertainty = 0.2/22.0 × 100% ≈ 1%
diamond.
(c) ∆H = −4.18 × 22.0/0.500 = −184 kJ mol−1
3 (a) 4 × 10−2 g (b) 2.22 × 102 cm3 (d) 1%
(c) 3.0 × 10−2 g (e) Absolute uncertainty = 1/100 × 184 =
(±) 2 kJ mol−1
(d) 3 × 10 or 3.0 × 10 °C (unspecified)
(f) Experimental value for ∆H = −184 (±) 2 kJ
4 (a) 4 (b) unspecified mol−1
(c) 3 (d) 4 The literature value is outside this range.
5 A 6 A 7 D 8 A The random errors involved in reading
the thermometer do not account for this
9 A 10 D 11 C difference.
12 The average value = 49.0 s There are systematic errors. The
The uncertainty in the measurements is given assumptions on which the calculation is
as ±0.1 s but the results show that there is based are not strictly valid. Some of the heat
additional uncertainty, suggesting that the value of reaction passes into the surroundings and
could be anywhere between 48.8 and 49.2 s. So the other uncertainties in the measurements
the value could be quoted as 49.0 s ± 0.2 s. cannot be ignored. It should also be noted
that the standard value for ΔH refers to
13 Note that the correct solution to this question standard conditions of 298 K and 100 kPa.
is not one of the possible answers listed.
The temperature change expressed to the 22 B
appropriate precision is 2.050 ± 0.050 K. 23 The scale of the graph does not allow us to
14 D 15 B 16 B 17 C distinguish whether A or B is the best answer
and both are acceptable.
18 A 19 C
24 B
20 Number of moles = concentration ×
volume/1000 25 Concentration of chromium (from graph for
absorbance of 0.215) = 3.34 µg dm−3
= 1.00 × 10.0/1000 = 0.0100 mol
% uncertainty in concentration = (0.05/1.00) × 26 B 27 C 28 C
100 = 5% 29 A (the spectrum on the left) corresponds to
% uncertainty in volume = (0.1/10.0) × 100 = 1% CH3CH2CHO
% uncertainty in number of moles = 5% + 1% = B (the spectrum on the right) corresponds to
6% CH3COCH3
1
 Similarities 40 C–H bond
Both have a molecular ion corresponding to 58. 41 CH3OCH3
Differences
42 C 43 A
A has peaks corresponding to 29 (CH3CH2+) and
28 (loss of CH3CH2). 44 (a) 2 (b) 1
B has a peak corresponding to 43 (loss of CH3). (c) 1 (d) 2

45 The H atoms are in three different environments

30 (a) Mass / charge Fragment
so there will be three peaks in the 1H NMR
15 CH3+ spectrum with integrated areas in the ratio
29 C2H5+ 3:2:1.

43 C3H7+ (loss of CH3) 46 (a) CH3COCH2CH3

58 C4H10+
(b) Type of Chemical No. of H Splitting
hydrogen atom shift / ppm atoms pattern
(b) CH3CH2CH2CH3
CH3CO 2.2–2.7 3 1
31 Molecule Corresponding saturated IHD
COCH2CH3 2.2–2.7 2 4
non-cyclic molecule
C6H6 C6H14 4 CH2CH3 0.9–1.0 3 3
CH3COCH3 C3H8O 2
47

of peaks

Splitting
C7H6O2 C7H16O 5

No. of H
Number

pattern
atoms
Chemical
C2H3Cl C2H5Cl 1 Compound
shift / ppm
C4H9N C4H9NH2 1
C6H12O6 C6H14O6 1 CH3CHO 2 2.2–2.7 3 2
32 B 33 D 34 B 9.4–10.0 1 4
35 (a) Empirical formula CH2O. Molecular formula CH3COCH3 1 2.1 6 1
C2H4O2.
48 Possible structures: CH3CH2COOH,
(b) IHD = 1 CH3COOCH3, HCOOCH2CH3.
(c) O The peak at 8.0 ppm corresponds to
R–COOH. There is no splitting as there are no
CH3 C OH hydrogen atoms bonded to neighbouring carbon
36 atoms.
The peak at 1.3 ppm corresponds to a CH3
group. The peak is split into a triplet because
symmetric stretch asymmetric stretch symmetric bend
IR active IR active IR active
there is a neighbouring CH2 group.
The peak at 4.3 ppm corresponds to the
37 B R–CH2–COO group. The peak is split into a
38 The polarity (of bond or molecule) changes as quartet as there is a neighbouring CH3 group.
the bonds are bent or stretched. Molecular structure: CH3CH2COOH

39 Hex-1-ene shows an absorption in the range 49 X-ray crystallography.

1610–1680 cm−1 due to the presence of the
50 Monochromatic means all the X-rays have the
C=C bond.
same wavelength.

2
 The angle of diffraction depends on the C2H5+ and m/z = 29
wavelength. If the X-rays have different CHO+ and m/z = 29
wavelengths, different diffraction angles/pattern
CH3+ and m/z = 15 [2 max]
would be obtained. It would be impossible to
match the angles with the wavelengths. Penalize missing + sign once only.

51 Hydrogen atoms have a low electron density. 6 (a) (stretches/vibrations in) HBr involve change
in bond dipole / (stretches/vibrations in) Br2
52 The atoms must have a regular arrangement if do not involve change in bond dipole [1]
an ordered diffraction pattern is to be produced.
(b) (i) I: O–H
53 (a) C6H5CH3 II: C–H
(b) Hydrogen atoms do not appear because of III: C=O[3]
their low electron density Award [2] for C–H for I and O–H for II.
(c) The saturated non-cyclic compound is C7H16 (ii) m/z 102: molecular ion peak /
(CH3)3CCOOH+ / C5H10O+ / M+
IHD = 12(16 − 8) = 4 (the IHD of a benzene
m/z 57: (CH3)3C+ / (M–COOH)+ / C4H9+
ring = 4)
m/z 45: COOH+ [3]
Penalize missing + once only.
Practice questions (iii) (H of) COOH group [1]
(iv) nine hydrogens in the same
For advice on how to interpret the marking below environment / (CH3)3C– (group) [1]
please see Chapter 1. CH3 O

1 B 2 C 3 C 4 A (v) (CH3)3CCOOH / (CH3)3CCO2H / H3C C C OH [1]

CH3
5 (a) Compound:
(vi) no peak at 11.5 ppm in spectrum of
CH3–CH2–CHO isomer / different chemical shift values
Explanation: [1 max] four peaks (instead of two) / different
only this compound would give 3 peaks / number of peaks;
OWTTE Three of these peaks can be split in actual
only this compound has H atoms in 3 spectrum, so allow for this in answers if
different chemical environments / OWTTE exactly four peaks is not stated.
only this compound has protons in ratio different integration trace / different
3:2:1 in each environment / OWTTE areas under the peaks / integration trace
only this compound would give a peak in the would have a 3:2:2:3 peak area
9.4–10 ppm region / OWTTE [2 max] ratio [2 max]
(b) 2.5 ppm peak Do not award mark if incorrect peak area
CH3–CO–CH3 also has hydrogen atoms on ratios are given for the structure drawn
a carbon next to the >C=O group [2] in (v).

(c) (i) 1700–1750 cm−1 (>C=O)[1] 7 change in bond length / bond stretching /
(ii) 1610–1680 cm−1 (>C=C<) / asymmetric stretch
3200–3600 cm−1 (–O–H)[1] change in bond angle / bending (of molecule)
(d) C3H6O+ and m/z = 58 Allow [1 max] for only stating vibrations.

3
 induces molecular polarity / dipole moment / (bonded to the second carbon atom) /
OWTTE [3] (CH3)2CHCH2OH

8 (a) A: O–H the peak at 3.4 ppm is due to the

(H atoms in the) –CH2– group /
B: C=O
(CH3)2CHCH2OH
C: C–O
Accept explanations with suitable
Award [2] for three correct, [1] for two diagram. [3]
correct. [2]
(b) (i) butan-1-ol and butan-2-ol
(b) m/z = 74: C2H5COOH+ / C3H6O2+
74: M+ / C4H10O+ / CH3CH2CH2CH2OH+
m/z = 45: COOH +
and CH3CH2CH(OH)CH3+
m/z = 29: C2H5+ 59: C3H7O+ / (M – CH3)+ /
Penalize missing + charge once only. CH2CH2CH2OH+ and CH2CH(OH)CH3+ /
Do not award mark for m/z = 29: CHO+. [3] CH3CH2CH(OH)+
(c) –COOH[1] 45: C2H5O+ / (M – C2H5)+ / CH2CH2OH+
and CH(OH)CH3+
(d) CH3CH2COOH / CH3CH2CO2H
Accept explained answers instead of
More detailed structural formula may be given.[1]
formulas. [4]
9 (a) absence of peak between 3200 and 3600 (ii) butan-1-ol
cm−1 / above 3000 cm−1 / peak for OH
CH2OH+ / (M – C3H7)+
presence of peak between 1700 and 1750
Penalize missing + signs once only in
cm−1 / peak for C=O
parts (b)(i) and (ii). [2]
absence of peak between 1610 and 1680
(c) they all contain O–H
cm−1 / peak for C=C [2 max]
(b) H H they all contain C–H
O
they all contain C–O
H C C C
Award [1 max] for same functional groups/
H bonds. [2 max]
H H
Accept CH3CH2CHO. 11 D could be CH3CH2COOCH3 or
3:2:1 CH3COOCH2CH3
Ignore order. this is because there are 3 peaks / 3:2:3 ratio
ECF if structure is incorrect only if its NMR explanation of splitting into a singlet, a triplet and
spectrum contains three peaks. [2] a quartet

10 (a) (i) (2-)methylpropan-2-ol methyl propanoate / CH3CH2COOCH3 is correct

isomer because of higher chemical shift value of
the (H atoms in the three) –CH3 groups
singlet (3.6 instead of 2.0–2.5) [4]
are responsible for the peak at 1.3 ppm
the –OH hydrogen atom is responsible 12 (a) (i) 88
for the peak at 2.0 ppm Do not award mark if units are given.
Accept explanations with suitable C4H8O2+ [2]
diagram. [3] (ii) CH3CH2 /C2H5+ / CHO
+ +

(ii) (2-)methylpropan-1-ol Only penalize once for missing charge in

the first peak (at 0.9 ppm) is due to (a)(i) and (ii). [1]
the (H atoms in the) two –CH3 groups
4
 (iii) C2H3O2 produced has no charge / 3 Y1ave = Y2ave = 3
fragment produced after loss of C2H5 (−2×(−2)) + (−1 × 2) + 0 + (1 × 1) + (2 × (−1))
R =
from molecular ion has no charge 22 + 12 + 02 + 12 + 22
Accept fragment(s) too unstable, 4−2+1−2
= = 0.10
fragment breaks up etc. 10
Do not accept answers with reference to 4 Saturated hydrocarbons have the general
C/14C isotopes and peak at m/z = 61.
13 formula CnH2n+2
Do not accept C2H3O2+ / C3H7O+ does For CnHp:
not exist. [1] H atoms needed = 2n + 2 − p
(b) (i) A: C=O and B: C–O H2 molecules needed = IHD = 12(2n + 2 − p)
No mark if two bonds are given for For CnHpOq:
A or B. Oxygen forms two covalent bonds. Comparing
Ignore names if incorrect. [1] ethane, C2H6: C–H, to ethanol, C2H5OH: C–O–H,
(ii) ester we see that the presence of O has no impact on
Do not accept COO. [1] the IHD:
(c) (i) H O H H [1] IHD = 12(2n + 2 − p)
For CnHpOqNr:
H C C O C C H /
Nitrogen forms three covalent bonds. Comparing
H H H C–H to C–N–H, we see that the presence of
CH3CO2CH2CH3 one N increases the IHD by 1:
IHD = 12(2n + 2 − p + r)

(ii) [3] For CnHpOqNrXs:

peak area
Chemical

Splitting
Relative

pattern
shift /
Peak

A halogen, X, forms one bond, like hydrogen, so

ppm

can be treated in the same way:

IHD = 12(2n + 2 − p + r − s)
first 2.0 3 singlet
second 4.1 2 quartet 5 E = hν

third 0.9–1.0 3 triplet

E = 6.63 × 10−34 J s × 3.0 × 1014 s−1 = 2.0 ×
10−19 J
(iii) (quartet means) neighbouring C:
The energy of one mole of photons = 6.02 ×
has 3 H atoms [2] 1023 mol−1 × 2.0 × 10−19 J
= 120 kJ mol−1

6 1/l = 2100 cm−1 = 210 000 m−1

Challenge yourself
l = 1/210 000 m = 4.76 × 10−6 m
1 Y1ave = Y2ave = 3 3.00 × 108 m s−1
ν= = 6.30 × 1013 s−1
(−2×(−2)) + (−1×(−1)) + 0 + (1 × 1) + (2 × 2) 4.762 × 10−6 m
R =
(−2)2 + (−1)2 + 02 + 12 + 22 7 The answer to this question involves the
=1 derivation of the Bragg Equation, nλ = 2dsinθ,
2 Y1ave = Y2ave = 3 which is discussed in Chapter 12. A simple
derivation is provided in the worked solutions.
(−2 × 2) + (−1 × 1) + 0 + (1×(−1)) + (2×(−2))
R =
(−2)2 + (−1)2 + 02 + 12 + 22
= −1
5