c Point marked on x-axis where the graphs become −3

horizontal. [1] [carboxylic acid] = 0.8855 × 110 −3 = 0.1417 [1]

6.0000 × 110
d As [N2O4] at higher temperature is lower then the −3

equilibrium has moved to the left. [1] [alcohol] = 0.8855 × 110 −3 = 0.1417 [1]
6.0000 × 110
Higher temperatures favour the direction which [carboxylic acid ]][[ alcohol ]
absorbs heat/endothermic direction. [1] h Reaction quotient =
[ester ][
][ water ]
Therefore endothermic direction is to the left and = 0. 1417 × 0. 1417 = 1.326 × 10 [1] −4
so the dimerisation of NO2 must be exothermic. [1] 8.245 × 18.36
i As the reaction quotient is not equal to the
15 PCl3(g) + Cl2(g) ⇌ PCl5(g)
equilibrium constant then the mixture has not
To produce 1.5 mol of PCl5 then 1.5 mol of PCl3
reached equilibrium. [1]
and 1.5 mol of Cl2 must have been used.
So moles at equilibrium are
PCl3 = 1.5 and Cl2 = 0.5 [1]
Chapter 8: Acids and bases
Exercise 8.1
Equil. conc. of PCl3 1.5 = 0.775 , and of Cl2 0.5 = 0.225, Conjugate acid Conjugate base
2 2
and of PCl5 1 . 5 = 0.775 [1] a HClO4 ClO4–
2 b H2SO4 HSO4–
[ PCl 5 ] 0.75
Kc = = = 4 mol−1 dm3 [1] c HCl Cl–
][Cl 2 ] 0.75 ×0..25
[ PCl 3 ][ d HNO3 NO3–
16 a n(ester) = m as density = mass then e HNO2 NO2–
Mr volume
f H2S HS–
densityy × vvolume 0.932 × 4.000
n(ester) = = g HSO3 –
SO32–
Mr 74.09
= 5.032 × 10−2 mol [1] h H2PO4– HPO42–
i HCN CN–
00 × 2.00 = 0.111 mol [1]
b n(water) = 1.00 +
j NH4 NH3
18.02
c n(HCl) = volume × concentration = k H2CO3 HCO3–
2.00 × 10−3 × 1.00 = 2.00 × 10−3 mol [1] l HCO3 –
CO32–

d n(H+) = n(OH−) = vol × conc = m HPO42– PO43–

28.50 × 10−3 × 0.100 = 2.85 × 10−3 mol [1] n H2O OH–

0 NH3 NH2–
e moles of acid produced = n(acid)final − n(acid)initial
= 2.85 × 10−3 − 2.00 × 10−3 = 0.85 × 10−3 mol [1] Table A8.1
f as acid and alcohol are 1 :1, 2 a H2SO4(aq) + HNO3(aq) → H2NO3+(aq) + HSO4–(aq)
n(alcohol) = 0.85 × 10−3 mol [1] Acid 1 Base 2 Acid 2 Base 1
n(ester)used = n(water)used = n(acid)produced
as all ratios are 1 :1
n(ester & water)remaining = n(ester & water)originally b NH3(aq) + H2O(l) → NH4+(aq) + OH–(aq)
− n(ester & water)used n(ester)remaining Base 1 Acid 2 Acid 1 Base 2
= 5.032 × 10−2 − 0.85 × 10−3 = 0.04947 mol [1]
n(water)remaining = 0.111 − 0.85 × 10−3
= 0.1102 mol [1] c HSO4–(aq) + H2O(l) → H3O+(aq) + SO42–(aq)
Acid 1 Base 2 Acid 2 Base 1
g conc = n
V
[ester] = 0.04947−3 = 8.245 [1]
00 × 110
6.00 d H2PO4–(aq) + HCO3–(aq) → HPO42–(aq) + H2CO3(aq)
[water] = 0.1102 −3 = 18.36 [1] Acid 1 Base 2 Base 1 Acid 2
00 × 110
6.00

44

Answers.indd 44 2/20/2017 6:01:20 PM

 Exercise 8.2 f H2SO4 + 2KOH → K2SO4 + 2H2O
1 a A Lewis acid is a substance that can accept a lone g HCl + NH3 → NH4Cl
pair of electrons and a Lewis base is a substance HCl + NH4OH → NH4Cl + H2O is also correct.
that can donate a lone pair of electrons. h 2CH3COOH + Ba(OH)2 →
b coordinate bond (CH3COO)2 Ba + 2H2O
c i NH3, Lewis base i 2CH3COOH + Mg → (CH3COO)2Mg + H2
ii AlCl3, Lewis acid j 2HNO3 + CuCO3 → Cu(NO3)2 + H2O + CO2
iii Cu2+, Lewis acid k H2SO4 + ZnO → ZnSO4 + H2O
iv Cl–, Lewis base 3 a Sulfuric acid and either copper(II) carbonate,
v CO, Lewis base copper(II) oxide or copper(II) hydroxide.
The dot-and-cross diagrams for these species b Nitric acid and either zinc, zinc oxide, zinc
can be used to explain these answers. carbonate or zinc hydroxide.
c Ethanoic acid and sodium hydroxide or sodium
i ii iii e.g. in complex ions carbonate.
H N H Cl
(see Topic 13) (Sodium metal is too reactive; this would be dangerous
H Al Cl
although chemically possible. Sodium oxide reacts
Cl Cl 2–
with water to form sodium hydroxide anyway.)
d Hydrochloric acid and ammonia solution
Cl (ammonium hydroxide) or ammonium carbonate
Cl or ammonium hydrogencarbonate.
Cl Cl
Exercise 8.4
iv – v
C O 1 a pH is a measure of the concentration of hydrogen
Cl ions in solution.
pH = –log10[H+]
Figure A8.1 Lewis diagrams. b Its pH will increase by 2 units.
2 a i pH = –log10[H+] = –log10(0.25) = 0.60
Exercise 8.3 ii [H+] = 0.025 × 2 = 0.050
1 a i acid + metal → salt + hydrogen as there are 2H+ ions per H2SO4.
ii acid + metal carbonate → pH = –log10[H+] = –log10 (0.050) = 1.35
salt + water + carbon dioxide b i [H+] = 10–3.0 = 1.0 × 10–3 mol dm–3
iii acid + metal hydrogencarbonate → ii [H+] = 10–4.5 = 3.2 × 10–5 mol dm–3
salt + water + carbon dioxide iii [H+] = 10–7.0 = 1.0 × 10–7 mol dm–3
iv acid + metal oxide → salt + water iv [H+] = 10–10.2 = 6.3 × 10–11 mol dm–3
v acid + metal hydroxide → salt + water 3 a Kw = [H+] [OH–] = 1.0 × 10–14 mol2 dm–6
vi acid + alkali → salt + water at 298 K (this value is given in the data book)
vii acid + base → salt + water If the [OH–] is known, then the [H+] and hence
b An alkali is a soluble base and so all alkalis must be pH can be calculated.
bases. A base is a substance that reacts with an acid. b i [OH–] = 0.10
Some acid–base reactions are not in aqueous Kw 1.0 × 10 −14 = 1.0 ×10
[H+] = = × −13
environments and so the term alkali is not [OH ] − 0 . 10
applicable. pH = –log10[H+] = –log10 (1 × 10–13) = 13.00
2 a Zn + 2HCl → ZnCl2 + H2 ii [OH–] = 0.075 × 2 = 0.15 mol dm–3
b Mg(OH)2 + 2HNO3 → Mg(NO3)2 + 2H2O as Ba(OH)2 contains 2OH– ions
c CuCO3 + H2SO4 → CuSO4 + H2O Kw 1.0 × 10 −14 = 6.67 × 10 −14
d 3NaHCO3 + H3PO4 → Na3PO4 + 3H2O + 3CO2 [H+] = =
OH −  0.15
e CaO + 2CH3COOH → (CH3COO)2Ca + H2O
pH = –log10[H+] = –log10 (6.6.7 × 10–14) = 13.18

ANSWERS 45

Answers.indd 45 2/20/2017 6:01:21 PM

 c i [H+] = 10–pH = 10–2.50 = 3.16 × 10–3 mol dm–3 c The conductivity of the strong acid will be higher
than that of the weak acid.
[OH–] = K w = 1.0 × 10 −3
−14

H  3.16 × 10
+
Exercise 8.6
= 3.16 × 10–12 mol dm–3
1 a Rain is naturally acidic because of dissolved carbon
ii [H+] = 10–pH = 10–0.50 = 0.316 mol dm–3
dioxide.
Kw 1.0 × 10 −14 H2O(l) + CO2(g) ⇋ H2CO3(aq)
[OH–] = =
H +  0.316 H2CO3 is a weak acid;
= 3.16 × 10–14 mol dm–3 it partially dissociates to form hydrogen ions.
4 a [H+] = 10–pH = 10–3.70 = 2.0 × 10–4 mol dm–3 H2CO3 ⇋ H+(aq) + HCO3 –(aq)
Therefore [HNO3] = 2.0 × 10–3 mol dm–3 b Acid deposition can be caused by oxides of sulfur
b [H+] = 10–pH = 10–2.00 = 0.010 mol dm–3 and oxides of nitrogen.
Therefore [H2SO4] = 0.0050 mol dm–3 Any two of the following equations:
c [H+] = 10–pH = 10–11.2 = 6.31 × 10–12 mol dm–3 S(s) + O2(g) → SO2(g)
Kw 2SO2(g) + O2(g) → 2SO3(g)
[OH–] = = 1.0 × 10 −14
N2(g) + O2(g) → 2NO(g)
H +  6.31 × 10 −12
2NO2(g) + O2(g) → 2NO2(g)
= 1.58 × 10–3 mol dm–3 c Sulfur oxides are formed by the burning of sulfur-
Therefore [KOH] = 1.58 × 10–3 mol dm–3 containing fuels.
d [H+] = 10–pH = 10–9.6 = 2.51 × 10–10 mol dm–3 Nitrogen oxides are formed by the reaction of
K 1.0 × 10 −14 = 3.98 × 10 −5 nitrogen and oxygen in the air at high
[OH–] = w+ = moldm–3
H  2.51 × 10 −10 temperatures inside internal combustion engines of
vehicles or the jet engines of aircraft.
Therefore [Ba(OH)2] = ½ × 3.98 × 10–5
d Any three from:
= 1.99 × 10–5 mol dm–3
Damage to buildings or statues: particularly those
made from limestone or marble.
Exercise 8.5
Harmful effect on vegetation: a decrease in the pH
1 a The strength of an acid is a measure of the degree of of soil can reduce the uptake of beneficial nutrients
dissociation into its ions. Strong acids are fully in soils or increase the concentration of substances
dissociated whereas weak acids are partially dissociated. harmful to plants such as aluminium ions.
b HNO3(aq) → H+(aq) + NO3–(aq) Harmful effect in rivers and lakes: many aquatic
c CH3COOH(aq) ⇋ CH3COO–(aq) + H+(aq) species cannot thrive in water with a low pH or at
d NH3 + H2O ⇋ NH4+ + OH– very low pH, it may be killed.
In the equation the (lone pair of electrons on the Harmful to health: acids irritate the respiratory
nitrogen atom of) ammonia has accepted a track and can cause respiratory problems such as
hydrogen ion. asthma and bronchitis.
e The stronger the base, the weaker its conjugate acid. 2 a Pre-combustion; treating the fuel with hydrogen in
2 a In both cases there will be fizzing as hydrogen gas the presence of a catalyst to convert the sulfur into
is evolved, but this will be more vigorous with hydrogen sulfide (hydrodesulfurisation).
the strong acid than with the weak acid. Post-combustion; treating the flue gases with basic
The piece of magnesium will disappear to form a or alkaline substances.
colourless solution, but more quickly with the b i improved vehicle design to decrease fuel
strong acid than with the weak acid. consumption / reducing car use by increasing
The mixture will get hot as the reactions are the use of public transport / reducing the mass
exothermic but the stronger acid will get hotter of packaging so less fuel is used for
than with the weak acid. transportation / improved catalytic convertors
b The pH of the strong acid will be lower than the to reduce vehicle emissions
pH of the weak acid.

46

Answers.indd 46 2/20/2017 6:01:21 PM

 ii improved efficiency of power stations /  BH +  OH − 
increased use of non-renewable power b Using Kb = and that
generation such as hydro-electric power, wind,
[ B]
solar, tidal power / increased use of renewable  BH +  = OH − 
fuels such as bio-fuels like wood or bio-gas /
[OH − ]2 0.01272
increased use of nuclear power then Kb = = = 5.38 × 10 −4
c Liming is the process of adding bases such as [ B] 0.300
calcium oxide, calcium hydroxide or calcium It is assumed that the concentration of
carbonate which are all obtained from limestone, dimethylamine is 0.300 mol dm–3 as only a very
to lakes. These compounds react with any acid small number of the molecules are dissociated.
present and neutralise it. It is also assumed that the any contribution to the
[OH–] from the dissociation of water can be
Exercise 8.7 ignored.
1 a CH3COOH(aq)  CH3COO–(aq) + H+(aq) H +   A − 
4 a i Using Ka = and knowing this acid
CH3COOO−  H +  [HA ]
Ka =
[CH3COOH] is monoprotic, then [H+] = [A–]
therefore [H+]2 = Ka × [HA]
b NH3(aq) + H2O(l)  NH4+(aq) + OH–(aq)
= 1.48 × 10–5 × 0.100 = 1.48 × 10–6
NH4+  OH −  so [H+] = (1.48 × 110 −6 ) = 1.2165 × 10 –3 mol dm–3
Kb =
[NH3 ] so pH = –log10 (1.2165 × 10–3) = 2.92
ii Using the same method,
2 a i dichloroethanoic acid pH = –log10 (2.95 × 10–3) = 2.53
ii benzoic acid
H +   A − 
iii pKa (3-nitrophenol) = –log10 (4.37 × 10–9)
b Using Ka =
= 8.36 [HA ] and knowing this acid is
therefore 3-nitrophenol is a stronger acid than monoprotic, then [H+] = [A–]
phenol [H+] = 10–pH = 10–5.5
b i methylamine [ H + ]2 (10−5.5 )2
ii sodium carbonate therefore Ka = = = 1 × 10–10
so pKa = 10 [ HA] 0.100
iii pKb(ethlyamine) = –log10 (4.47 × 10–4)
= 3.35 It is assumed that the concentration of phenol is
therefore ethylamine is a stronger base than 0.100 mol dm–3 as only a very small number of the
phenylamine molecules are dissociated.
It is also assumed that the any contribution to the
H +   A − 
3 a Using Ka = and knowing this acid is [H+] from the dissociation of water can be ignored.
[HA ]  BH +  OH − 
monoprotic, then [H+] = [A–] 5 a i Using Kb =  and that
[ B]
[H + ]2 (9.64 × 10 −5 )2  BH +  = OH − 
therefore Ka = = = 3.72 × 10 −8
[HA ] 0.250
then [OH–]2 = Kb × [B] = 1.78 × 10–5 × 0.250
It is assumed that the concentration of HClO is
= 4.45 × 10–6
0.250 mol dm–3 as only a very small number of the
so [OH–] = 4.45 10−6 = 2.11 ×10–3
45 ×10
molecules are dissociated.
pOH = –log10[OH ] = –log10(2.11 × 10–3) = 2.68
–
It is also assumed that the any contribution to the
[H+] from the dissociation of water can be ignored.

ANSWERS 47

Answers.indd 47 2/20/2017 6:01:23 PM

 ii Using the same method, iii Conjugate base is CH3CH2NH2
pOH = –log10 (0.0106) = 1.99 −14
Kb = 1 × 110 −11 = 4.46 × 10 –4
It is assumed that the concentration of the base 2.2244 × 110
is 0.250 mol dm–3 as only a very small number b i Conjugate acid is NH4+
of the molecules are dissociated. as pKw = pKa + pKb
It is also assumed that the any contribution to then pKa = 14 – 4.75 = 9.25
the [OH–] from the dissociation of water can be ii Conjugate acid is C6H5NH3+
ignored. pKa = 14 – 9.13 = 4.87
b Using the expression Kw = [H+][OH–] and iii Conjugate acid is H2CO3
Kw = 1 × 10–14 (assuming 298 K) −14

then pKw = pH + pOH Ka = 1 × 110 −8 = 3.98 × 10–7

2.5511 × 110
so pH = 14 – pOH
i pH = 14 – 2.68 = 11.32 Exercise 8.8
ii pH = 14 – 1.99 = 12.01
1 a i 14
6 a pKa, pKb and pKw all decrease as the temperature
increases.
b Neutral means that [H+] = [OH–]. This is true of
water at all temperatures as water dissociates

pH
7
according to the equation H2O ⇋ H+ + OH–
so equal amounts of H+ and OH– are formed.
c Potassium hydroxide is a strong base so [OH –] =
0.010 mol dm–3. 0
Kw −14.53
Kw = [H+][OH –] so [H+] = = 10 0 5 10 15 20 25 30 35 40 45 50
= 2.95 × 10–13 [OH − ] 0.010 Volume of 0.100 mol dm –3
NaOH added/cm3
so pH = –log10(2.95 × 10–13) = 12.53
Figure A8.2 pH curve 1.
H +   A −  [HA ] OH −  Notice the following
7 a Ka = , Kb = and
[HA ]  A −  - base is added to acid so the pH increases
Kw = [H+][OH–] - the curve starts at around pH = 1 as this is the
rearranging the first equation (for Ka) gives pH of 0.100 mol dm –3 HCl
- the vertical section is long and the inflexion is at
[HA ] = [H + ] pH = 7 (strong acid/strong base)
[A− ] Ka - the equivalence point is at a volume of 25 cm3
substituting this into the second expression gives The volume of NaOH required can be determined
H +  O
OHH −  from a mole calculation; the acid and base are
Kb =    reacting 1 : 1 so (vol × conc)acid = (vol × conc)base
Ka
or Ka × Kb = [H+][OH –] 25 × 0.100 = volume × 0.100
base
1000
therefore, Kw = Ka × Kb
b pKw = pKa + pKb volumebase = 25 cm3
8 a i Conjugate base is CH2FCOO– - the parts of the graph either side of the inflexion
as pKw = pKa + pKb are fairly horizontal
then pKb = 14 – 2.59 = 11.41 - the graph tends towards pH 13 as this is the pH
ii Conjugate base is CH3O– of 0.100 mol dm–3 and so pH cannot be greater
pKb = 14 – 15.5 = –1.5 than this.

48

Answers.indd 48 2/20/2017 6:01:24 PM

 ii 14 This will occur when half of the HA present has
been neutralised and formed A–;
this is the half-neutralisation point.
Ka can be found by using construction lines to read
pH

7 off the pH when half the volume required to reach

equivalence has been added from a weak acid/
strong base titration curve (Figure A8.6).
Kb can be found by using construction lines to read
0
0 10 20 30 40 50 60 70 80 90100 off the pH when half the volume required to reach
Volume of 0.250 mol dm –3 equivalence has been added from a weak base/
NH3 added/cm3 strong acid titration curve (Figure A8.7).
Figure A8.3 pH curve.
iii 14

pH = pKa

pH
pH

x
2
x
0 Volume of base added
0 10 20 30 40 50
x = volume at equivalence
Volume of 0.100 mol dm –3 x 1
CH3COOH added/cm3 2 = 2 neutralisation point
pKa = pH (y-axis value) at x2
Figure A8.4 pH curve.
iv 14 Figure A8.6 Finding Ka for a weak acid.

pKb
pH

7
pH

0
0 10 20 30 40 50 60 70
Volume of 0.100 mol dm –3 x
2
x
CH3COOH added/cm3 Volume of acid added
Figure A8.5 pH curve 1. x = volume at equivalence
x 1
2 a Equivalence describes an equivalent number of 2 = 2 neutralisation point
pKb = pH (y-axis value) at x2
moles of acid and alkali in the mixture. The
mixture is not necessarily neutral as if a weak acid Figure A8.7 Finding Kb for a weak base.
or weak base was used then the salt formed is likely 3 a HIn(aq) ⇋ H+(aq) + In–(aq)
to undergo salt hydrolysis and the pH of the salt HIn is red; In– is yellow
solution will not be neutral. b BOH(aq) ⇋ B+(aq) + OH–(aq)
BOH is purple; B+ is green
H +   A − 
b Using the expression Ka = c pKa = 8.8 (approx. mid-point of its range)
[HA ] It would not be suitable for a titration between
then Ka = [H+] when [A–] = [HA] HCl and NH3 as this is a strong acid/weak base

ANSWERS 49

Answers.indd 49 2/20/2017 6:01:25 PM

 titration. The equivalence point of this would be at Exercise 8.10
a pH < 7 so the indicator would not change a An acidic buffer is a mixture of a weak acid
colour in the vertical section of the pH titration and its conjugate base. There must be
curve; the equivalence point does not fall into the relatively high concentrations of both of these
range of the indicator. species present.
b A basic buffer is a mixture of a weak base and its
Exercise 8.9
conjugate acid. There must be relatively high
1 a CH3COONa(aq) → CH3COO–(aq) + Na+(aq) concentrations of both of these species present.
NH4Cl(aq) → NH4+(aq) + Cl–(aq) c Either a salt of ethanoic acid such as sodium
b CH3COO–(aq) + H2O(l) ⇋ ethanoate, approximately 0.100 mol, should be
CH3COOH(aq) + OH –(aq) added or a strong alkali such as sodium hydroxide
NH4+(aq) + H2O(l) ⇋ NH3(aq) + H3O+(aq) to react with some of the ethanoic acid and
c In the answer to part b, CH3COO– is acting as a produce its salt; approximately 0.05 mol of NaOH
base and so the equation should be added as approximately half of the
[CH3COOH] OH −  ethanoic acid should be neutralised.
Kb = should be used
CH3COO−  d

as [CH3COOH ] = OH −  then buffer region

 
[OH − ]2
pH
Kb =
CH3COO− 
[OH–]2 = Kb × [CH3COO–] = 10–9.24 × 0.100
= 10–10.24
[OH –] = √ 10 −10.24 = 7.56 × 10–6 Volume of weak base
Kw = [H+][OH –] so added to a strong acid
Kw −14
[H+] = −
= 1 × 10 −6 = 1.32 × 10–9 Figure A8.8 Buffer region for a strong acid/weak base titration.
[OH ] 7.56 × 10
pH = –log10 (1.32 × 10–9) = 8.88
In the answer to part b, NH4+ is acting as an acid
and so the equation
pH

Ka =
[NH3 ] H3O+  should be used, where buffer region
NH4+ 
[H3O+] = [H+] [H + ]2
[ ]
as NH3 = H  then Kb =
+
  +
NH4  Volume of weak acid
added to a strong base
[H+]2 = Ka × [NH4+] = 10–9.25 × 0.100 = 10–10.25 Figure A8.9 Buffer region of a weak acid/strong base titration.
+ −10.25 –6 In the shaded sections of the curves, the solution
[H ] = √ 10 = 7.50 × 10
pH = –log10 (7.50 × 10–6) = 5.13 contains a mixture of the excess weak base and its
d As the pKb value for CH3COO– and the pKa value salt/excess weak acid and its salt. Buffer solutions
for NH4+ are approximately equal then the pH of are mixtures of weak acids & their salts/weak bases
their salt would be around pH 7. and their salts so these mixtures act as buffers.
2 [Fe(H2O)6]3+ ⇋
[Fe(H2O)5(OH)]2+(aq) + H+(aq)
As hydrogen ions are liberated, the solution will be
acidic.

50

Answers.indd 50 2/20/2017 6:01:26 PM

 2 a An acidic buffer contains a mixture of a weak acid The mixtures will fizz as bubbles of carbon
and its conjugate base. dioxide are produced; the stronger acid will
The weak acid and its conjugate base are in bubble more vigorously. [1]
equilibrium HA ⇋ H+ + A– c HCl(aq) → H+(aq) + Cl –(aq)
The concentrations of the weak acid, HA, and its [1 mark – full arrow essential]
conjugate base, A–, need to be relatively high and HClO(aq) ⇋ H+(aq) + ClO –(aq);
approximately equal so that they act as a reservoir [1 mark– reversible sign essential]
to react with any acid or alkali that is added. Conjugate bases are Cl – and ClO –
On addition of a small amount of acid, the [both answers needed for 1 mark]
reservoir of A– ions reacts with the acid, the d pH is a measure of the concentration of hydrogen
equilibrium shifts to the left to minimise the effect ions in a solution and so although the pH of a
of the increase in [H+] by converting it to HA and strong acid will be lower than that of a weak acid,
approximately maintain the [H+] at its original this is only true if both acids are at the same
level. This is possible because there is a relatively concentration [1] and they are both monoprotic
large number of A– ions available. or both diprotic etc.
On addition of a small amount of base, the H+ ions The strength of an acid depends on how
react with the base according to the equation dissociated it is and is described by its Ka or pKa
H+ + OH– ⇋ H2O. The equilibrium above shifts value. [1]
to the right and HA dissociates to replenish the H+ 12 a Acid deposition describes the process in which
that has reacted with the added alkali and so acidic substances leave the atmosphere and are
minimises the effect of the increase in [OH–], deposited on the Earth’s surface. [1]
approximately maintaining the [H+] at its original b Wet deposition: acid rain/fog/snow [1]
level. This is possible because there is a relatively Dry deposition: acidic gases/particulates [1]
large number of HA molecules available. c Fossil fuels can contain sulfur and when the fuel is
burnt the sulfur is burnt too. [1]
Exam-style questions S(s) + O2(g) → SO2(g) [1]
1 B 2 C This can undergo oxidation in the atmosphere to
3 D 4 B form SO3. [1]
5 A 6 B 2SO2(g) + O2(g) → 2 SO3(g) [1]
7 A 8 A Both of these gases dissolve in water to produce
9 C 10 C acids: [1]
11 a Cl2(g) + H2O(l) → HCl(aq) + HClO(aq) [1] H2O(l) + SO2(g) → H2SO3(aq) [1]
b i Strong acids are fully dissociated into their ions H2O(l) + SO3(g) → H2SO4(aq) [1]
whereas in a weak acid only a small proportion d Oxides of nitrogen are formed from the reaction
of the molecules are dissociated into their ions. between nitrogen and oxygen at the high
ii Any 3 experiments, for example: temperatures found in internal combustion
Add a small piece of magnesium to both acids engines/jet engines. [1]
in separate test tubes. [1] N2(g) + O2(g) → 2NO(g) [1]
Bubbles of hydrogen gas will be produced; the 2NO(g) + O2(g) → 2NO2(g) [1]
stronger acid will react more vigorously. [1] e Any four from
Measure the conductivity of the two acids. [1] - liming of soils/lakes
The conductivity of the stronger acid will be - improving design of vehicle engines/power
higher. [1] stations
Measure the pH of the two solutions. [1] - removing sulfur from fossil fuels/
The stronger acid will have a lower pH. [1] pre-combustion desulfurisation
Add a little sodium carbonate to the - post-combustion desulfurisation/treatment of
two acids. [1] exhaust emissions

ANSWERS 51

Answers.indd 51 2/20/2017 6:01:27 PM

 - increased use of catalytic convertors b 14
- incentivise/increase the use of alternative
energies
- incentivise/increase the use of public transport

pH
13 a i It can donate two hydrogen ions. [1] 7
ii H2SO4(aq) → H+(aq) + HSO4–(aq) [1]
HSO4–(aq) ⇋ H+(aq) + SO42–(aq) [1]
[accept reversible sign or full arrow]
0
iii [H+] = 0.200 mol dm–3 [1] 0 10 20 30 40 50
pH = –log10(0.200) = 0.70 [1] 0.150 mol dm –3
Volume of
iv The pH would increase by 1 pH unit/would NaOH added/cm3
increase to 1.7. [1] Figure A8.10 NaOH vs 2-methylpropanoic acid.
The conductivity would decrease. [1] Axis labels: pH and volume alkali added, pH
b i KOH is a strong base so increases. [1]
[OH–] = 0.500 mol dm–3 General shape: sloping before inflexion, more
Kw = [H+][OH –] so horizontal after the inflexion. [1]
Kw −14
[H+] = −
= 1 × 10 = 2.0 × 10–14 [1] Inflexion at pH > 7. [1]
[OH ] 0.500 Curve starts at approx. pH 2.77 (value calculated
pH = –log10 (2.0 × 10–14) = 13.7 [1] in part a) [1]
ii Ba(OH)2 is also a strong base but, as it c phenolphthalein [1]
dissociates to form two OH– ions, the [OH–] The end point of the titration is within the range
value will be higher than for KOH of the of the indicator. [1]
same concentration. [1] d pH is not equal to 7 as a weak acid has been used. [1]
Therefore, the pH of the barium hydroxide The 2-methylpropanoate ions present at the
solution will be higher. [1] equivalence point undergo salt hydrolysis. [1]
iii Ammonia is a weak base; it is not fully CH3CH(CH3)COO –(aq) + H2O(l) ⇋
dissociated into ions and so the [OH–] will be CH3CH(CH3)COOH + OH –(aq) [1]
lower. [1] The formation of OH – ions means that pH > 7. [1]
Its pH will therefore be lower than both KOH 15 a For HX
and Ba(OH)2. [1] H +   X −  H + 
2

H +   A −  Ka =     =   as [H+] = [X–] [1]

14 a Using Ka = and as this acid is
[HX ] [HX ]
[HA ] (10 −4.51 )2
monoprotic, then [H+] = [A–] Ka = = 9.54 × 10–9 mol2 dm–6 [1]
0.100
therefore [H+]2 = Ka × [HA] Similarly, for HY
= 10–4.84 × 0.200 = 2.89 × 10–6 [1]
(10 −3.78 )2
+ −6 Ka = = 2.75 × 10–7 mol2 dm–6 [1]
so [H ] = ( 2.89 × 110 ) 0.100
= 1.70 × 10–3 mol dm–3 [1] b HY(aq) ⇋ H+(aq) + Y–(aq)
so pH = –log10 (1.70 × 10–3) = 2.77 [1] [1 mark – must select HY]
Conjugate base is Y –. [1]
c Y– is a weaker base than X– (or the reverse). [1]
d i Y–(aq) + H2O(l) ⇋ HY(aq) + OH–(aq) [1]
Y– is a base because it accepts a hydrogen ion. [1]

52

Answers.indd 52 2/20/2017 6:01:27 PM

 ii pKw = pKa + pKb so pKb = 14 – pKa [1] Al2O3 + 2OH– + 3H2O → 2[Al(OH)4]– shows
pKb = 14 – 3.78 = 10.22 [1] aluminium oxide reacting with a base. [1]
[HY ] OH −  As hydrogen ions are not accepted nor donated
iii Rearranging Kb = gives by the aluminium oxide, it is not amphiprotic. [1]
 Y − 
[OH–]2 = Kb × [Y–] as [HY] = [OH–] Chapter 9: Redox processes
[OH–]2 = 10–10.22 × 0.500 = 3.01 × 10–11 Exercise 9.1
[OH–] = 5.49 × 10–6 mol dm–3 [1]
1 a oxidation
pOH = –log10(5.49 × 10–6) = 5.26 [1]
b reduction
pH = 14 – pOH
c reduction
pH = 8.74 [1]
d oxidation
16 a A buffer solution is a solution that minimises
e reduction
changes in pH [1]
f oxidation
when a small amount of acid or alkali is added. [1]
g oxidation
b The buffer solution needs to contain a relatively
h reduction
high concentration of both C2H5NH2 and
2 a i Copper is reduced (it changes from Cu2+,
C2H5NH3+. [2]
oxidation state +2, to Cu, oxidation state 0).
When a small amount of acid is added, it reacts
ii CH3CHO is oxidised (oxygen is added, the
with OH– ions according to the equation
formula changes from C2H4O to C2H4O2).
H+(aq) + OH–(aq) ⇋ H2O(l) [1]
iii Zinc is oxidised (it loses electrons to become a
This shifts the equilibrium C2H5NH2+ H2O ⇋
2+ charged ion).
C2H5NH3+ + OH– to the right. [1]
iv C2H4 is reduced (hydrogen is added).
When a small amount of alkali is added, the
b i oxidising agent CuO reducing agent CH4
equilibrium C2H5NH2+ H2O ⇋
ii oxidising agent [O] reducing agent CH3CHO
C2H5NH3+ + OH – shifts to the left. [1]
iii oxidising agent Ag+ reducing agent Zn
These shifts in the equilibrium minimise:
iv oxidising agent C2H4 reducing agent H2
the effect of the acid or alkali added and
maintains the pH approximately constant. [2]
Exercise 9.2
17 a H2O(l) ⇋ H+(aq) + OH–(aq) [1]
b Kw = [H+][OH–] [1] 1 a +1
The graph shows that Kw increases as temperature b +3
increases and the dissociation is endothermic. [1] c +3
c Kw at 87 °C = 34.0 × 10–14 d +3
Kw = [H+][OH–], as [H+] = [OH–] then e +6
[H+]2 = Kw f –1
g –1
[H+] = 34.0 × 10 10 −14 = 5.83 × 10 −7 h –2
pH = –log10(5.83 × 10–7) = 6.23 [1] i –3
d Water is neutral when [H+] = [OH–] [1] j +3
This is true at all temperatures and so water is 2 a FeO
neutral at all temperatures. [1] b NaClO
e Amphiprotic means that it can both donate and c KBrO3
accept a proton. [1] d FeSO4
f i Amphoteric means that a substance reacts with e H2SO3
both acids and bases. f KMnO4
ii Al2O3 + 6H+ → 2Al3+ + 3H2O shows g Cr(NO3)3
aluminium oxide reacting with an acid. [1] h N2O

ANSWERS 53

Answers.indd 53 2/20/2017 6:01:28 PM