63 (a) H2O(s) → H2O(l) 74 C 75 D 76 B

ΔHreaction = –286 – (–292) = +6 kJ mol

⊖ −1
77 When ∆G = –30 kJ mol−1
ΔHreaction
⊖

(b) T = –30 kJ mol−1 = –123 – (T1 × –128 × 10−3) kJ mol−1

ΔS⊖reaction
6000 93 = (T1 × 128 × 10−3)
= = 273 K
22.0 T1 = 727 K
64 A 65 D 66 B When ∆G = +30 kJ mol−1
+30 kJ mol−1 = –123 – (T2 × – 128 × 10−3) kJ mol−1
67 (a) ∆H is positive as heat is needed to break up
the carbonate ion. 153 = (T2 × 128 × 10−3)
(b) ∆S is positive as there is an increase in the T2 = 1195 K
amount of gas produced. 78 When ∆G = –30 kJ mol−1
(c) At low temperature: ∆G = ∆H and so is –30 kJ mol−1 = –93 – (T1 × –198 × 10−3) kJ mol−1
positive.
63 = (T1 × 198 × 10−3)
At high temperature: ∆G = –T∆S and so is
T1 = 318 K
negative.
When ∆G = +30 kJ mol−1
The reaction is not spontaneous at low
temperature but becomes spontaneous at +30 kJ mol−1 = –93 – (T2 × –198 × 10−3) kJ mol−1
high temperatures. 123 = (T2 × 198 × 10−3)

68 D 69 C T2 = 621 K

70 ∆Greaction = (–604 + –394) – (–1129) = 131 kJ mol−1

As ∆Greaction is very positive, the reaction is not
Practice questions
spontaneous under standard conditions. This
accounts for the stability of calcium carbonate in
For advice on how to interpret the marking below
the form of limestone, chalk and marble.
please see Chapter 1.
71 ΔH⊖reaction = 178 kJ mol−1
1 D 2 D 3 A 4 C
ΔS⊖reaction = 160.8 J K−1 mol−1
ΔG⊖reaction = +178 – (2000 × 160.8 × 10−3) kJ mol−1 5 B 6 C 7 B 8 B

= –144 kJ mol−1 9 (a) amount of energy required to break bonds of

reactants
72 B
3 × 414 + 358 + 463 + 1.5 × 498 (kJ mol−1)
1
73 (a) 2C(graphite) + 3H2(g) + 2O2(g) → C2H5OH(l) = 2810 (kJ mol−1) [1]
(b) ΔS reaction = +161 – (2 × 5.7) – (3 × 63.5) –
⊖
amount of energy released during bond
(12 × 102.5) formation of products
= –98 J K−1 mol−1 4 × 463 + 2 × 804 (kJ mol−1) = 3460 (kJ
(c) ΔGreaction = –278 – (500 × –98 × 10−3) mol−1) [1]
= –229 kJ mol −1 ∆H = 2810 – 3460 = –650 (kJ mol ) −1
[1]
(d) The reaction is spontaneous as ∆G is Award [3] for correct final answer. Award [2]
negative. for (+)650.
(e) At high temperature: ∆G = –T∆S and so (b) (i) m(methanol) = 80.557 – 80.034 =
is positive. The reaction will stop being 0.523 (g) [1]
spontaneous at higher temperature.
4
 0.523 g ∆T = 48.2 (°C) [1]
n(methanol) =
32.05 g mol−1 Allow in the range 47 to 49 (°C). Award
= 0.0163 (mol) [1] [2] for correct final answer. Allow ECF if
Award [2] for correct final answer. Tfinal or Tinitial correct.
(ii) ∆T = 26.4 – 21.5 = 4.9 (K) [1] (ii) temperature decreases at uniform
rate (when above room temperature) /
q = (mc∆T =) 20.000 × 4.18 × 4.9 (J) or
OWTTE [1]
20.000 × 4.18 × 4.9 × 10−3 (kJ) [1]
(iii) 10.1 (kJ) [1]
= 410 J or 0.41 kJ [1]
Allow in the range 9.9 to 10.2 (kJ).
Award [3] for correct final answer.
410 (J) (c) Complete colour change shows all the
(iii) ∆H⊖c = – or
0.0163 (mol) copper has reacted, so n(Zn) = n(CuSO4)
0.41 (kJ) 1.00 × 50.0
– [1] = = 0.0500 (mol) [1]
0.0163 (mol) 1000
= –25153 J mol−1 or –25 kJ mol−1 [1] (d) –201 kJ mol−1 [1]

Award [2] for correct final answer. Award Allow in the range –197 to –206 (kJ mol−1).
[1] for (+)25 (kJ mol –1). Value must be negative to award mark.

(c) (i) bond enthalpies are average values/ 11 (a) energy required = C=C + H–H
differ (slightly) from one compound to = 614 + 436 = 1050
another (depending on the neighbouring
energy released = C–C + 2(C–H)
atoms) / methanol is liquid not gas in
= 346 + 2(414) = 1174 [1]
the reaction [1]
Allow full consideration of breaking all bonds
(ii) not all heat produced transferred to
and forming all the new bonds, which gives
water / heat lost to surroundings/
values of 2706 and 2830.
environment / OWTTE / incomplete
combustion (of methanol) / water forms energy required = C=C + H–H + 4(C–
as H2O(l) instead of H2O(g) [Do not allow H)/612 + 436 + 4(413)
just ‘heat is lost’] [1] and

10 (a) all heat is transferred to water/copper sulfate energy released = C–C + 6(C–H)/347 +
solution / no heat loss; 6(413);

specific heat capacity of zinc is zero/ ∆H = (1050 – 1174) or (2706 – 2830) =

negligible / no heat is absorbed by the zinc; –124 kJ mol−1 [1]

density of water/solution = 1.0 / density of (b) ∆H = –1411 + (–286) – (–1560) =

solution = density of water; –137 kJ mol−1 [1]

heat capacity of cup is zero / no heat is (c) the actual values for the specific bonds
absorbed by the cup; may be different to the average values / the
combustion values referred to the specific
specific heat capacity of solution = specific
compounds / OWTTE [1]
heat capacity of water;
(d) (i) –124 kJ mol−1 [1]
temperature uniform throughout solution;
(ii) average bond enthalpies do not apply
Award [1] each for any two. Accept
to the liquid state / OWTTE; [1]
‘energy’ instead of ‘heat’ [2]
the enthalpy of vaporization/
(b) (i) Tfinal = 73.0 (°C) [1]
condensation of cyclohexene and
Allow in the range 72 to 74 (°C). cyclohexane / OWTTE [2]

5
12 bonds broken: 4 × N–H, 1 × N–N, 1 × O=O 3 The temperature of the Bunsen flame is 5748 °C
= +2220 (kJ mol−1) [1]
4 The difference in the values is largely to due to
bonds formed: 1 × N≡N, 4 × O–H = –2797 the assumption that H2O is gaseous in the bond
(kJ mol−1) [1] enthalpy calculation (1), whereas it is actually
enthalpy change = 2797 + 2220 = formed as a liquid in combustion reactions (2).
–577 kJ mol−1 [1] (1) CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
Award [3] for correct final answer. ΔH = –891 kJ mol−1
13 reaction II (requires a shorter wavelength) [1] (2) CH4(g) + 2O2(g) → CO2(g) + 2H2O(g)
ΔH = –808 kJ mol−1
O2 has double bond/bond order 2 and O3
intermediate between double and single bonds/ (2) – (1) 2H2O(l) → 2H2O(g)
bond order of 112 [1] ΔH = 891 – 808 = +83 kJ mol−1
Do not accept stronger/weaker bonding without H2O(l) → H2O(g) ΔH = +41.5 kJ mol−1
justification for the second marking point. There are (on average) two hydrogen bonds
between each molecule so a hydrogen bond is
14 A 15 A 16 C 17 D
approximately 20 kJ mol−1.
18 B 19 B 20 B This assumes that all other molecular
21 (a) I is atomization/sublimation (of Mg) / interactions such as dipole–dipole and London
∆H ⊖atomization(Mg) / ∆H ⊖sublimation(Mg) [1] dispersion forces are negligible, which is an
approximation.
V is enthalpy change of formation of
(MgCl2) / ∆H⊖formation(MgCl2) [1] 5 Within the sheets of graphite the C=C bond
(b) Energy value for II is +242 [1] order is 1.33 and the coordination number is
3, and there are weak intermolecular forces
Energy value for III: is 738 + 1451 = 2189 [1]
between the layers. In diamond each carbon is
Energy value for IV is 2 × (–349) [1]
bonded to four other atoms by single covalent
∆H lat(MgCl2) = 642 + 148 + 243 + 2189 +
⊖
bonds and the C–C bond order is 1. The total
2 × (–349) = (+)2523 kJ [1] bonding is slightly stronger in graphite (higher
(c) theoretical value assumes ionic model [1] bond orders) and this makes it more stable.
experimental value greater due to 6 It has two unpaired electrons in the 2p sub-level.
(additional) covalent character [1]
7 With positive ions, there is generally a loose
(d) oxide has greater charge [1]
electrostatic attraction with the partially
oxide has smaller radius [1] negatively charged oxygen atoms of the water
Accept opposite arguments. molecules. Positive ions with higher charge
densities, such as d block ions, may form
complex ions with formal covalent coordinate
bonds with the water molecules. There is
Challenge yourself
increased covalent interaction between the Ag+
ions and the water molecules, which leads to
1 N2(g): N2(g) + O2(g) → 2NO(g) ΔH⊖c = 90 kJ mol−1
more exothermic hydration enthalpies.
2 The specific heat capacities depend on the
8 Sodium chloride is an ionic substance that
number of atoms in the unit mass. So c is
contains alternating sodium and chlorine ions.
approximately inversely proportional to the
When salt is added to water, the partial charges
relative atomic mass.
on the water molecule are attracted to the Na+