Answers

Chapter 5
Exercises

1 B 2 B 3 A 11 q = mc∆T

4 D 5 C q = 150.00 g × 4.18 J g−1 K−1 × (31.5 – 25.0) K

q 100 = 4075.5 J = 4100 J (to 2 s.f.)
6 q = mc∆T, so ∆T = = = 7.25 °C
mc 100 × 0.138 0.0500 g
n(P) =
T = 25.0 + 7.25 = 32.3 °C 30.97 g mol−1
= 1.61 × 10−3 mol
7 A 8 A 9 C – 4100 J
ΔHc =
10 (a) ΔT = 36.50 – 25.85 = 10.65 °C (or K) 1.61 × 10−3 mol
= – 2525 × 103 J mol−1
q = mc∆T
= – 2500 kJ mol−1
q = m(H2O) × c(H2O) × ∆T(H2O) + m(Cu) ×
The precision of the answer is limited by the
c(Cu) × ∆T(Cu)
precision of measurement of the temperature
= (200.00 g × 4.18 J g−1 K−1 × 10.65 K) + difference. The value is lower than the literature
(120.00 g × 0.385 J g−1 K−1 × 10.65 K) value owing to heat losses and incomplete
= 8900 J + 492 J combustion.
q = 9392 J 12 q = mc∆T
1.10 g
n(C6H12O6) = = 1000 g × 4.18 J g−1 K−1 × (70.0 – 20.0) K
180.18 g mol−1
= 6.11 × 10−3 mol = 209 kJ, for 1 mole of 1 mol dm−3 solution
∆H = –209 kJ mol−1
In calculating the enthalpy change of
combustion, ∆Hc, we have to recognize that 13 ∆T = 32.3 – 24.5 = 7.8 K
this is an exothermic reaction and that ∆Hc q = m(H2O) × c(H2O) × ∆T(H2O)
will therefore be a negative value. = 100.00 g × 4.18 J g−1 K−1 × 7.8 K
9392 J = 3300 J
∆Hc = – 
6.11 × 10–3 mol 50.00
n(NaOH) = × 0.950 = 0.0475 mol
= –1.54 × 106 J mol−1 1000
–3300 J
= –1540 kJ mol−1 ∆H = = 69 × 103 J mol−1
0.0475 mol
(b) = –69 kJ mol−1
C6H12O6(s) + 6O2(s)
Assumptions: no heat loss, c(solution) = c(water),
m(solution) = m(H2O), density(H2O) = 1.00
∆H = –1540 kJ mol –1
H

14 If the mass of the solution is taken as 105.04 g

(mass of water + mass of NH2Cl dissolved),
6CO2(g) + 6H2O(l) ∆H = +16.5 kJ mol–1.
If the mass of the solution is instead assumed to
be 100.00 g (mass of water only), ∆H = +15.7 kJ
Extent of reaction
mol–1.
q = mc∆T
= 100.00 g × 4.18 J g−1 K−1 × (21.79 – 25.55)
= –1570 J for 5.35 g
1
 q = 293.6 J per g 35 –486 kJ mol−1
n(NH4Cl) = 53.50 g mol−1 36 B 37 C
∆H = 293.6 J g × 53.50 g mol
−1 −1
38 C2H5OH(l) + 3O2(g) → 2CO2(g) + 3H2O(g)
= 15.7 kJ mol−1 H H
15 ∆H is change in enthalpy, the heat content of a H C C O H(l) + 3 × O=O(g) →
system. Enthalpy cannot be measured directly
H H
but enthalpy changes can be calculated for
2 × O=C=O(g) + 3 × H–O–H(g)
chemical reactions and physical processes
from measured temperature changes using the Bonds ∆H / kJ Bonds ∆H / kJ
equation q = mc∆T, where q is the heat change, broken mol−1 formed mol−1
m is the mass of the substance(s) changing C–C +346 4 C=O 4 × (–804)
temperature, c is the specific heat capacity of 3 O=O 3 × (+498) 6 H–O 6 × (–463)
the substance(s) changing temperature and ∆T
O–H +463
is the measured temperature change occurring
C–O +358
in the substance(s).
5 C–H 5 × (+414)
16 A Total +4731 –5994
17 ΔH = –394 kJ – (–283) kJ = –111 kJ
 ⊖

ΔH⊖ = +4731 – 5994 kJ mol−1 = –1263 kJ mol−1

 

18 ΔH⊖ = –180.5 kJ + (+66.4 kJ) = –114.1 kJ

 
The calculated value is less exothermic than
19 ∆H⊖ = (2 × (–33.2 kJ mol–1)) + (+9.16 kJ mol–1) =
  the enthalpy of combustion in Table 13. This is
–57.24 kJ mol−1 because the bond enthalpy calculation assumes
all species are in the gaseous state: water and
20 B 21 C 22 D 23 D ethanol are liquids.
24 (a) 3C(graphite) + 3H2(g) + 12O2(g) → CH3COCH3(l) 39 (a) Step II, as bonds are formed.
ΔH f = –248 kJ mol
 ⊖ −1
O2 has a double bond. O3 has resonance
(b)
Under standard conditions of 298 K (25 °C)
(b) structures/delocalization with bonding
and 1.00 × 105 Pa. If the reaction involves intermediate between double and single
solutions these have a concentration of 1.00 bonds; the bond order is 1.5. The bonding
mol dm–3. in O2 is stronger therefore reaction I needs
25 +330 kJ mol−1 more energy.

26 –57.2 kJ mol−1 40 L × Ephoton = 498 kJ = 498 000 J

498 000
27 D Ephoton = J (= 8.272 × 10−19 J)
6.02 × 1023
28 2MgO(s) + C(s) → CO2(g) + 2Mg(s) λ = hc/Ephoton
6.02 × 1023
∆H⊖reaction = (–394) – 2(–602) = +810 kJ mol−1
 
= 6.63 × 10−34 × 3.00 × 108 ×
498 000
Such a highly endothermic reaction is unlikely to = 2.41 × 10−7 m
be feasible. = 241 nm
29 B 30 A 31 C Any radiation in the UV region with a wavelength
32 1 × C–C + 6 × C–H shorter than 241 nm breaks the O=O bond in
oxygen.
33 B
41 The oxygen double bond is stronger than the
34 –125 kJ mol−1 1.5 bond in ozone. Thus, less energy is required

2
 to dissociate O3 than O2. Longer wavelength 53 (a) ΔH⊖sol(KCl) = ΔH⊖lattice(KCl) + ΔH⊖hyd(K+) +
     

radiation of lower energy is needed to dissociate ΔH⊖hyd(Cl–)

 

O3. = +720 – 340 – 359 kJ mol−1

42 A 43 C 44 D = +21 kJ mol−1
45 (a) K2O(s) → 2K+(g) + O2−(g) ΔH⊖sol(KCl) = +17.22 kJ mol−1 (from data
(b)  

booklet)
(b) W = ΔH atom
⊖
(O), the enthalpy of atomization
21 − 17.22
of oxygen (which also corresponds to % accuracy = × 100% = 22%
1 17.22
2 E(O=O), the O=O bond enthalpy) The large inaccuracy is based on the
X = 2ΔH⊖i (K), 2 × the first ionization energy
 

calculated value being found by the

of potassium difference between two large values.
Y = ΔH⊖e1(O) + ΔH⊖e2(O), the sum of the first
   

54 B 55 C 56 A 57 D
and second electron affinities of oxygen
Z = ΔH⊖f (K2O(s)), the standard enthalpy of
 
58 (a) ∆S is negative. The number of moles of gas
formation of K2O(s) decreases from reactants to products.
ΔH⊖latt(K2O) = 361 + 2(89.2) + 2(419) + 12(498)
(c)  
∆S is negative. Three moles of solid and
(b)
+ (–141) + 753 four moles of gas change into one mole of
= +2238 kJ mol−1 solid and four moles of gas. There is a small
decrease in disorder.
46 B
∆S is positive. A solid reactant is being
(c)
47 They decrease down Group 17 as the ionic converted into an aqueous solution so there
radius of the halide ion increases. is a large increase in disorder.
48 Consider first the effect of increased ionic charge 59
(Na+/Mg2+ and Cl−/O2−). The charge of both the Gas
positive and negative ions is doubled. This leads
to a quadrupled increase in the lattice energy.
This effect is further enhanced by the decrease
S

in ionic radius of the Mg2+ compared to Na+ due

Liquid
to the increased nuclear charge of the metal
and the decreased ionic radius of the oxide ion Solid
because of a decrease in the number of energy
T
levels occupied.
60 N2(g) + 3H2(g)  → 2NH3(g)
49 C 50 A
191 3 × 131 2 × 193 S⊖ / J K−1 mol−1
 

51 Bonding in AgBr is stronger because Ag has+

smaller ionic radius and more covalent character, ΔS⊖reaction = 2 × 193 – (191 + (3 × 131))
 

which makes bonding stronger than that based = –198 J K−1 mol−1
on the ionic model.
61 C(graphite) + 2H2(g)  → CH4(g)
52 They have similar ionic radii but the enthalpy 5.7 2 × 131 186 S⊖ / J K−1 mol−1
 

of hydration of the F− ion is significantly more ΔS⊖reaction = 186 – (5.7 + (2 × 131)) = –82 J K−1 mol−1
 

exothermic. This suggests that there is an

When adding figures, the figure with the smallest
additional interaction to the electrostatic
number of decimal places determines the
attraction between the charged ion and the polar
precision.
molecules. F− ions form hydrogen bonds with the
water. 62 C
3
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  ⊖

T=
(b) –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)
∆S is positive as there is an increase in the
(b) T2 = 1195 K
amount of gas produced. 78 When ∆G = –30 kJ mol−1
At low temperature: ∆G = ∆H and so is
(c)
–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]
ΔS reaction = +161 – (2 × 5.7) – (3 × 63.5) –
(b)  ⊖
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
ΔGreaction = –278 – (500 × –98 × 10−3)
(c) mol−1)[1]
= –229 kJ mol−1 ∆H = 2810 – 3460 = –650 (kJ mol−1)[1]
The reaction is spontaneous as ∆G is
(d) Award [3] for correct final answer. Award [2]
negative. for (+)650.
At high temperature: ∆G = –T∆S and so
(e) (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.
∆T = 26.4 – 21.5 = 4.9 (K)
(ii) [1] temperature decreases at uniform
(ii)
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]
10.1 (kJ)
(iii) [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) Complete colour change shows all the
(c)
∆H⊖c = –
(iii)  
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
 –201 kJ mol−1
(d) [1]
= –25153 J mol−1 or –25 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
not all heat produced transferred to
(ii)
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 ∆H = –1411 + (–286) – (–1560) =

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

heat capacity of cup is zero / no heat is the actual values for the specific bonds
(c)
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;
average bond enthalpies do not apply
(ii)
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
Energy value for II is +242
(b) [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
theoretical value assumes ionic model
(c) [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
oxide has greater charge
(d) [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+

6
and Cl− ions. The water molecules work their  9 When Kc = 1, ΔG⊖reaction = 0
 

way into the crystal structure and between the When Kc > 1, ΔG⊖reaction < 0
 

individual ions, surrounding them and slowly

When Kc < 1, ΔG⊖reaction < 0
 

dissolving the salt – but as we have seen the

Possible function: ΔG⊖reaction = –A ln Kc where A is
 

enthalpy change is very small. The aqueous

a constant with units kJ mol−1.
solution is more disordered and so has a higher
entropy, as discussed later in the chapter. The precise relationship discussed in Chapter 7
is ΔG⊖reaction = –RT ln Kc