Worked solutions

Chapter 9
Exercises

 1 The numbers are assigned following the strategy (e) Fe2O3:

on page 408. In most of these it is best to assign 0 = 2 × (oxidation state of Fe) + 3 × (–2)
the values for O [–2] and H [+1] first, and then (0 – –6)
assign values to the remaining elements so that Oxidation state of Fe = = +3
2
the sum of the oxidation states of each element Oxidation states of elements: Fe = +3,
in the species is equal to the charge on the O = –2
species (or zero in the case of neutral species),
(f) NO3–:
e.g.
–1 = oxidation state of N + 3 × (–2)
for NH4+:
Oxidation state of N = –1 – (–6) = +5
charge on species = oxidation state of N + 4 ×
Oxidation states of elements: N = +5, O = –2
oxidation state of H
+1 = oxidation state of N + 4 × (+1) (g) MnO2:
Oxidation state of N = +1 – (+4) = –3 0 = oxidation state of Mn + 2 × (–2)
Oxidation states of elements: N = –3, H = +1 Oxidation state of Mn = 0 – (–4) = +4
Remember that the elements P, S and N, as Oxidation states of elements: Mn = +4,
well as the transition metals, can take different O = –2
oxidation states, depending on the compound.
(h) PO43−:
(a) NH4+ = N −3, H +1 –3 = oxidation state of P + 4 × (–2)
(b) CuCl2: As no other information is available Oxidation state of P = –3 – (–8) = +5
we can assume that Cl will be present in the Oxidation states of elements: P = +5, O = –2
–1 oxidation state, which is the preferred
(i) K2Cr2O7: We need to assume that O will be
oxidation state for Group 17 elements that
present with an oxidation state of –2 and,
typically form 1– ions.
as it is a Group 1 element that can only
0 = oxidation state of Cu + 2 × (–1) lose one electron, K will be present with an
Oxidation state of Cu = 0 – (–2) = +2 oxidation state of +1.
Oxidation states of elements: Cu = +2, 0 = 2 × (+1) + 2 × (oxidation state of Cr) +
Cl = –1 7 × (–2)
(c) H2O: See if the oxidations states balance by 2 × (oxidation state of Cr) = 0 – (–14) = +14
assuming both H and O are present in their Oxidation state of Cr = +7
preferred oxidation states. Oxidation states of elements: K = +1,
0 = 2 × (+1) + –2 Cr = +7, O = –2
Oxidation states of elements: H = +1, O = –2 (j) MnO4–:
(d) SO2– –1 = oxidation state of Mn + 4 × (–2)
0 = oxidation state of S + 2 × (–2) Oxidation state of Mn = –1 – (–8) = +7
Oxidation state of S = 0 – (–4) = +4 Oxidation states of elements: Mn = +7,
Oxidation states of elements: S = +4, O = –2 O = –2

1
 2 The best strategy here is to pick out one element 2Fe2+(aq) + Cl2(aq) → 2Fe3+(aq) + 2Cl−(aq)
(b)
at a time and work out its oxidation state on    +2       0        +3       −1
both sides of the equation. If it has increased, oxidation: 2Fe2+(aq) → 2Fe3+(aq) +2e−
it has been oxidized; if it has decreased it has reduction: Cl2(g) + 2e− → 2Cl−(aq)
been reduced. If there is no change in oxidation Sn2+(aq) + 2Fe3+(aq) → Sn4+(aq) + 2Fe2+(aq)
(c)
state that atom has neither been oxidized nor   +2         +3        +4        +2
reduced. Check that you have one element oxidation: Sn2+(aq) → Sn4+(aq) + 2e−
being oxidized and one being reduced on each reduction: 2Fe3+(aq) + 2e− → 2Fe2+(aq)
side of the equation.
Cl2(aq) + 2Br−(aq) → 2Cl−(aq) + Br2(aq)
(d)
(a) reduction   0       −1        −1       0
oxidation: 2Br−(aq) → Br2(aq) + 2e−
Sn21(aq) 1 2Fe31(aq) → Sn41(aq) 1 2Fe21(aq)
12 13 14 12
reduction: Cl2(aq) + 2e− → 2Cl−(aq)
oxidation  4 The steps for writing the redox equations are
(b) reduction given on page 414. The interim steps for each of
Cl2(aq) 1 2NaBr(aq) → Br2(aq) 1 2NaCl(aq) these examples are given below.
0 1121 0 1121
(a) 1 Assign oxidation states and determine
oxidation what is being oxidized and reduced:
(c) reduction
Zn(s) + SO42–(aq) → Zn2+(aq) + SO2(g)
2FeCl2(aq) 1 Cl2(aq) → 2FeCl3(aq) 0 +6 –2 +2 + 4 –2
1221 0 1321
Zn is being oxidized and S is being
oxidation
reduced.
(d) reduction
2 (i) Identify species being oxidized and
2H2O(l) 1 2F2(g) → 4HF(aq) 1 O2(g) reduced in the half-equations:
1122 0 1121 0
oxidation: Zn → Zn2+
oxidation reduction: SO42– → SO2
(e) (ii) Balance the reduction equation for O
reduction
by adding H2O:
I2(aq) 1 SO322(aq) 1 H2O(l) → 2I2(aq) 1 SO422(aq) 1 2H1(aq)
0 1422 1122 21 1622 11 reduction: SO42– → SO2 + 2H2O
oxidation (iii) Balance the reduction equation for H
by adding H+:
 3 Follow the same steps as in Q2, assigning
reduction: SO42– + 4H+ → SO2 + 2H2O
oxidation states to the atoms on both sides of
(iv) Balance each equation for charge by
the equation and using these to deduce what
adding electrons:
is being oxidized and what is reduced. Then
oxidation: Zn → Zn2+ + 2e–
separate these into half-equations as described
reduction: SO42– + 4H+ + 2e–
on pages 412–414. Remember to balance the
→ SO2 + 2H2O
charge of each half-equation by adding electrons
– to the reactants side in reduction half-reactions 3 Electrons are equal (2) in the two half-
and to the products side in oxidation half- equations.
reactions. 4 Add half-equations together:
Zn(s) + SO42–(aq) + 4H+(aq) → Zn2+(aq) +
Ca(s) + 2H+(aq) → Ca2+(aq) + H2(g)
(a)
SO2(g) + 2H2O(l)
    0      +1       +2        0
oxidation: Ca(s) → Ca2+(aq) + 2e−
reduction: 2H+(aq) + 2e− → H2(g)
2
 (b) 1 Assign oxidation states: (iv) Balance each equation for charge by
I–(aq) + HSO4–(aq) → I2(aq) + SO2(g) adding electrons:
–1 +1 +6 –2 0 +4 –2 reduction: NO3– + 10H+ + 8e– →
I– is being oxidized and S is being NH4+ + 3H2O
reduced. oxidation: Zn → Zn2+ + 2e–

2 (i) Identify species being oxidized and 3 Multiply oxidation half-equation by 4

reduced in the half-equations: to equalize electrons in the two half-
oxidation: 2I– → I2 equations:
reduction: HSO4– → SO2 oxidation: 4Zn → 4Zn2+ + 8e–

(ii) Balance the reduction equation for O 4 Add half-equations together:

by adding H2O: 4Zn(s) + NO3–(aq) + 10H+(aq) → 4Zn2+(aq)
reduction: HSO4– → SO2 + 2H2O + NH4+(aq) + 3H2O(l)
(iii) Balance the reduction equation for H (d) 1 Assign oxidation states:
by adding H+: I2(aq) + OCl–(aq) → IO3–(aq) + Cl–(aq)
reduction: HSO4– + 3H+ → SO2 + 0 –2 +1 +5 –2 –1
2H2O (Note: OCl– is unusual in that it contains
(iv) Balance each equation for charge by Cl with an oxidation state of +1. This is
adding electrons: because it is in the presence of the more
oxidation: 2I– → I2 + 2e– electronegative oxygen.)
reduction: HSO4– + 3H+ + 2e– → SO2 I2 is being oxidized and Cl– is being
+ 2H2O reduced.
3 Electrons are equal (2) in the two half- 2 (i) Identify species being oxidized and
equations. reduced in the half-equations:
4 Add half-equations together: oxidation: I2 → 2IO3–
2I–(aq) + HSO4–(aq) + 3H+(aq) → I2(aq) + reduction: OCl– → Cl–
SO2(g) + 2H2O(l) (ii) Balance both equations for O by
(c) 1 Assign oxidation states: adding H2O:
NO3–(aq) + Zn(s) → NH4+(aq) + Zn2+(aq) oxidation: I2 + 6H2O → 2IO3–
+5 –2 0 –3 +1 +2 reduction: OCl– → Cl– + H2O

N is being reduced and Zn is being (iii) Balance reduction equation for H by

oxidized. adding H+:
oxidation: I2 + 6H2O → 2IO3– + 12H+
2 (i) Identify species being oxidized and
reduction: OCl– + 2H+ → Cl– + H2O
reduced in the half-equations:
reduction: NO3– → NH4+ (iv) Balance each equation for charge by
oxidation: Zn → Zn2+ adding electrons:
oxidation: I2 + 6H2O → 2IO3– + 12H+
(ii) Balance the reduction equation for O
+ 10e–
by adding H2O:
reduction: OCl– + 2H+ + 2e– → Cl– +
reduction: NO3– → NH4+ + 3H2O
H2O
(iii) Balance the reduction equation for H
3 Multiply reduction half-equation by 5 to
by adding H+:
equalize electrons:
reduction: NO3– + 10H+ → NH4+ +
reduction: 50CI– + 10H+ + 10e– → 5Cl– +
3H2O
5H2O

3
 4 Add half-equations together, noting that  5 B This is the only equation where any elements
much of the H+ and H2O cancel here: in the reactants change oxidation state
I2(aq) + H2O(l) + 50Cl–(aq) → 2IO3–(aq) + during the course of the reaction. In all the
2H+(aq) + 5Cl–(aq) other reactions the oxidation states of the
(e) 1 Assign oxidation states: elements are the same on both the reactants
MnO4–(aq) + H2SO3(aq) → side and products side as no electrons are
+7 –2 +1 +4 –2 being exchanged and therefore no redox
occurs.
Mn2+(aq) + SO42–(aq)
+2 +6 –2 A: Na = +1, O = –2, H = +1, N = +5 for
both sides
Mn is being reduced and S is being
oxidized. B: Reactants Zn = 0, H = +1, Cl = –1;
products Zn = +2, Cl = –1, H = 0
2 (i) Identify species being oxidized and
reduced in the half-equations: C: Cu = +2, O = –2, H = +1, Cl = –1 for
oxidation: H2SO3 → SO42– both sides
reduction: MnO4– → Mn2+ D: Mg = +2, C = +4, O = –2, H = +1, N =
(ii) Balance both equations for O by +5 for both sides
adding H2O:  6 D We can assume that O is present in
oxidation: H2SO3 + H2O → SO42– oxidation state –2 and Cl is present in
reduction: MnO4– → Mn2+ + 4H2O oxidation state –1, the preferred oxidation
(iii) Balance the reduction equation for H state for Group 17 elements. We can also
by adding H+: take a shortcut for Cr2(CO3)3 by assigning an
oxidation: H2SO3 + H2O → SO42– + oxidation state of –2 to the CO32– ion rather
4H+ than to the component elements.
reduction: MnO4– + 8H+ → Mn2+ +
A CrCl3 B Cr2O3
4H2O
+3 –1 +3 –2
(iv) Balance each equation for charge by
C Cr2(CO3)3 D CrO3
adding electrons:
+3 (–2) +6 –2
oxidation: H2SO3 + H2O → SO42– +
4H+ + 2e– Oxidation state of chromium in CrO3 = +6,
reduction: MnO4– + 8H+ + 5e– → Mn2+ but in CrCl3, Cr2O3 and Cr2(CO3)3 it is +3.
+ 4H2O
 7 In each case, calculate the oxidation state of the
3 Multiply oxidation half-equation by 5 and metal (or nitrogen) and use this to help name
reduction half-equation by 2 to equalize the compound. Remember that the sum of the
electrons: oxidation states has to equal zero. The oxidation
oxidation: 5H2SO3 + 5H2O → 5SO42– + states of the other elements under consideration
20H+ + 10e– are O = –2, H = +1 and Cl = –1.
reduction: 2MnO4– + 16H+ + 10e– →
2Mn2+ + 8H2O (a) Cr2O3
4 Add half-equations together, noting that 0 = 2 × (oxidation state of Cr) + 3 × (–2)
much of the H+ and H2O cancel here: 0 – (–6)
Oxidation state of Cr = = +3
5H2SO3(aq) + 2MnO4–(aq) → 5SO42–(aq) + 2
The name of the compound is chromium(III)
4H+(aq) + 2Mn2+(aq) + 3H2O(l)
oxide.

4
 (b) CuCl  9 Note the following:
0 = oxidation state of Cu + –1 ●● the more reactive metal always gets oxidized
Oxidation state of Cu = 0 – (–1) = +1 (acts as reducing agent)
The name of the compound is copper(I) ●● the more reactive non-metal always gets
chloride. reduced (acts as oxidizing agent).
(c) HNO3 (a) CuCl2(aq) + Ag(s)
0 = +1 + oxidation state of N + 3 × (–2) No reaction, Cu is a more reactive metal
Oxidation state of N = 0 – (+1) – (–6) = +5 than Ag.
The name of the compound is nitric(V) acid.
(b) Fe(NO3)2(aq) + Al(s)
(From Chapter 8 we can recognize that this
Al is a more reactive metal than Fe, so is
is an acidic compound.)
able to reduce Fe3+ to Fe(s). (Al(s) will be
(d) HNO2 oxidized to Al3+ ions.)
0 = +1 + oxidation state of N + 2 × (–2)
The balanced equation is 3Fe(NO3)2(aq) +
Oxidation state of N = 0 – (+1) – (–4) = +3
2Al(s) → 2Al(NO3)3(aq) + 3Fe(s).
The name of the compound is nitric(III) acid.
(From Chapter 8 we can recognize that this (c) NaI(aq) + Br2(aq)
is an acidic compound.) Br is a more reactive non-metal than I, so is
able to oxidize I– to I2. (Br2 will be reduced to
(e) PbO2
Br– ions.)
0 = oxidation state of Pb + 2 × (–2)
Oxidation state of Pb = 0 – (–4) = +4 The balanced equation is 2NaI(aq) + Br2(aq)
→ 2NaBr(aq) + I2(aq).
The name of the compound is lead(IV) oxide.
(d) KCl(aq) + I2(aq)
 8 Again the first thing to do here is to assign
No reaction, Cl is a more reactive non-metal
oxidation states to each element on both sides
than I.
of the equation. The species that contains the
element that is oxidized acts as the reducing 10 (a) A more reactive metal will displace a less
agent, the one that contains the element that is reactive metal from its salt in solution.
reduced acts as the oxidizing agent. From the reactions given:
(a) H2(g) + Cl2(g) → 2HCl(g) W + X+ → W+ + X
0 0 +1 –1
therefore W is more reactive than X
oxidizing agent: Cl2
X + Z+ → X+ + Z
reducing agent: H2
therefore X is more reactive than Z
(b) 2Al(s) + 3PbCl2(s) → 2AlCl3(s) + 3Pb(s)
0 +2 –1 +1 –1 0 Y+ + Z → no reaction
oxidizing agent: Pb2+ therefore Z is less reactive than Y
reducing agent: Al X + Y+ → X+ + Y
(c) Cl2(aq) + 2KI(aq) → 2KCl(aq) + I2(aq) therefore X is more reactive than Y
0 +1 –1 +1 –1 0 So the overall order of reactivity is W > X > Y
oxidizing agent: Cl2 >Z
reducing agent: I−
(b) (i) No reaction as Y is less reactive than W
(d) CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) (ii) No reaction as Z is less reactive than W
–4 +1 0 +4 –2 +1 –2
oxidizing agent: O2
reducing agent: CH4
5
11 (a) The solution changes from purple to Hence percentage of calcium chloride in
colourless (since MnO4–(aq) is purple and 0.684 g
original mixture = × 100% = 24.7%
Mn2+(aq) ions are very pale pink). 2.765 g
12 (a) Moles of K2Cr2O7 = cV = 0.0550
(b) Oxidation reaction involves oxalate ions
being oxidized to CO2(g): C2O42−(aq) → mol dm–3 × ( )
9.25
1000
dm3 = 5.09 × 10–4 mol
2CO2(g) This reacts with 2.54 × 10–4 moles of
All elements are balanced so only need to C2H5OH (as K2Cr2O7 and C2H5OH react in
balance charge by adding electrons: the ratio 2 : 1).
C2O42−(aq) → 2CO2(g) + 2e– Mass of C2H5OH = nM(C2H5OH) =
(2.54 × 10–4 mol) × 46.08 g mol–1 = 0.0117 g
(c) Reduction reaction involves permanganate
0.0117 g
ions being reduced to manganese (II) ions: Therefore percentage by mass =
10.000 g
MnO4−(aq) → Mn2+(aq) × 100% = 0.117%
Balance O by adding water:
(b) K2Cr2O7(aq) is orange, Cr3+(aq) is dark green
MnO4 (aq) → Mn (aq) + 4H2O(l)
− 2+
so the solution changes from orange to
Balance H by adding H+: green.
MnO4−(aq) + 8H+(aq) → Mn2+(aq) + 4H2O(l) 13 (a) Zn is a more reactive metal than Fe, so is
Balance charge by adding electrons: oxidized.
MnO4−(aq) + 8H+(aq) + 5e– → Mn2+(aq) + Zn/Zn2+ is the anode, where oxidation
4H2O(l) occurs

(d) Multiply equation (b) by 5 and equation (c) by Fe/Fe2+ is the cathode, where reduction
2 so that both reactions involve 10 electrons occurs
and when they are added together the Zn(s) → Zn2+(aq) + 2e–
electrons cancel out. Fe2+(aq) + 2e– → Fe(s)
5 × (b) 5C2O42−(aq) → 10CO2(g) + 10e–
(b) Mg is a more reactive metal than Fe, so is
2 × (c) 2MnO4−(aq) + 16H+(aq) + 10e– → oxidized.
2Mn2+(aq) + 8H2O(l)
Fe/Fe2+ is the cathode, where reduction
Combined: 2MnO4 (aq) + 16H (aq) + 5C2O4
− + 2−
occurs
(aq) → 2Mn2+(aq) + 8H2O(l) + 10CO2(g)
Mg/Mg2+ is the anode, where oxidation
(e) Moles of KMnO4 ions = cV = 0.100 mol occurs

dm–3 × (
24.65
1000 )
dm3 = 2.465 × 10–3 mol Fe2+(aq) + 2e– → Fe(s)
Mg(s) → Mg2+(aq) + 2e–
Hence moles of oxalate ions = 2.465 × 10–3
5
mol × = 6.16 × 10–3 mol (since oxalate (c) Mg is a more reactive metal than Cu, so is
2
oxidized.
reacts with permanganate in the ratio of
5 to 2). Mg/Mg2+ is the anode, where oxidation
occurs
(f) Moles of Ca2+ in original sample =
Cu/Cu2+ is the cathode, where reduction
6.16 × 10−3 (since the ratio of calcium ions to
occurs
carboxylate ions is 1 to 1).
Mg(s) → Mg2+(aq) + 2e–
(g) Mass of calcium chloride = nM(CaCl2) =
Cu2+(aq) + 2e– → Cu(s)
(6.16 × 10−3 mol) × 110.98 g mol–1 = 0.684 g

6
14 (a) Mg is a more reactive metal than Zn so will Due to its higher (less negative) E value, BrO3–
be oxidized in the voltaic cell. will be reduced. Now the E ⊖ values can be
oxidation reduction substituted.
Mg(s) → Mg2 (aq)  2e Zn2 (aq)  2e → Zn(s)
V
e flow
The half-equations are:
anions
zinc
Reduction: BrO3–(aq) + 6H+ + 6e– → Br–(aq) +
magnesium
electrode salt bridge electrode 3H2O(l)
cations
solution of
magnesium solution of
As the iodine half-cell is where oxidation occurs,
nitrate zinc nitrate its (reduction) equation will be reversed. It also
Anode Cathode
needs to be multiplied by three as it only has 2e–
(b) Mg(s) | Mg2+(aq) || Zn2+(aq) | Zn(s) compared to the 6e– in the reduction reaction,
before adding it to that of the bromide half-cell.
15 First establish from the reactivity series that Fe is
Oxidation: 6I– → 3I2(s) + 6e–
a more reactive metal than Cu and so will reduce
Overall equation: BrO3–(aq) + 6H+ + 6I– → Br–(aq)
Cu2+ ions in solution (and form Fe2+ ions). The
+ 3H2O(l) + 3I2(s)
observations depend on knowledge that Cu2+
ions are blue in solution and that copper metal is E ⊖cell = E ⊖(BrO3–) – E ⊖(I2) = +1.44 V – (+0.54 V)
red/brown. Overall equation will be: = +0.90 V
Fe(s) + Cu2+(aq) → Fe2+(aq) + Cu(s) 18 E ⊖(Cu2+) = +0.34 V, E ⊖(Mg2+) = –2.37 V,
(blue) (red/brown) E ⊖(Zn2+) = –0.76 V
The iron spatula would slowly dissolve as it is The species with the higher E ⊖ value is the most
oxidized to Fe2+ ions. Copper metal (red/brown) easily reduced. Cu2+ is the most easily reduced,
would precipitate as Cu2+ ions are reduced. The so is the strongest oxidizing agent.
blue colour of the solution would fade, as Cu2+ The species with the lowest E ⊖ value is the
ions are removed. hardest to reduce but its reverse reaction will
16 E ⊖cell = E ⊖half-cell where reduction occurs – E ⊖half-cell where oxidation occurs have the species that is the most easily oxidized.
Mg2+ has the lowest E ⊖ value therefore Mg is the
From the given standard electrode potential
species most easily oxidized, so is the strongest
values, first deduce in which half-cell reduction
reducing agent.
will occur. The species with the higher E ⊖ value
will be reduced. 19 (a) No reaction can occur as both I2 and Cu2+
E ⊖(Cr3+) = –0.75 V, E ⊖(Cd2+) = –0.40 V can only be reduced based on the equations
Due to its higher (less negative) E value, Cd2+ provided: I2 to I– and Cu2+ to Cu. With no
will be reduced. Now the E ⊖ values can be species present that can be oxidized a redox
substituted: equation cannot occur.

E ⊖(Cd2+) – E ⊖(Cr3+) = –0.40V – (–0.75V) = +0.35 V (b) BrO3– can be reduced to Br– while Cd can be
oxidized to Cd2+.
17 This question needs a similar approach to that
Half-equations:
in Q16, using the E values to deduce where
Reduction: BrO3–(aq) + 6H+(aq) → Br–(aq) +
reduction and oxidation occur, respectively.
3H2O(l)
E ⊖cell = E ⊖half-cell where reduction occurs – E ⊖half-cell where oxidation occurs
The Cd2+ reduction reaction needs to
From the given standard electrode potential
be reversed for the oxidation of Cr(s)
values, first deduce in which half-cell reduction
and multiplied by three as it only has
will occur. The species with the higher E ⊖ value
2e– compared to the 6e– in the reduction
will be reduced:
reaction.
E ⊖(BrO3–) = +1.44 V, E ⊖(I2) = +0.54 V
7
 Oxidation: 3Cd(s) → 3Cd2+(aq) Therefore ΔG = –nFE ⊖ = –3 mol × 96 500
Overall equation: BrO3–(aq) + 6H+(aq) + C mol–1 × 0.92 V = –2.7 × 105 J = –270 kJ
3Cd(s) → Br–(aq) + 3H2O(l) + 3Cd2+(aq) 21 The question is best tackled by:
E ⊖cell = E ⊖half-cell where reduction occurs – E ⊖half-cell where oxidation ●● writing out the formula for the ions present in
occurs each compound
E ⊖cell = E ⊖ (BrO3–) – E ⊖ (Cd2+) = +1.44 V – ●● stating that negative ions are oxidized at the
(–0.40 V) = +1.84 V anode
The E ⊖cell is > 0, therefore the reaction is ●● stating that positive ions are reduced at the
spontaneous. cathode
(c) As given in the question, Cr would be ●● writing the equations by adding (reduction)
oxidized to Cr3+ and Mg2+ would be reduced or losing (oxidation) the appropriate number
to Mg(s). of electrons to form the neutral element.
Half-equations: (a) KBr: Ions present are K+ and Br–. K+ will be
reduced at cathode and Br– will be oxidized
Reduction: Mg2+(aq) +2e− → Mg(s)
at anode.
The Cr3+ reduction reaction needs to be
Oxidation occurs at the anode:
reversed.
2Br–(l) → Br2(l) + 2e–
Oxidation: Cr(s) → Cr3+(aq) + 3e–
Reduction occurs at the cathode:
The reduction reaction needs to be 2K+(l) + 2e– → 2K(l)
multiplied by two and the oxidation reaction
(b) MgF2: Ions present are Mg2+ and F–. Mg2+
by three so both have a total of 6e–.
will be reduced at the cathode and F– will be
Reduction: 3Mg2+(aq) + 6e− → 3Mg(s) oxidized at the anode.
Oxidation: 2Cr(s) → 2Cr3+(aq) + 6e– Oxidation occurs at the anode:
Overall: 3Mg (aq) + 2Cr(s) → 3Mg(s) +
2+
2F−(l) → F2(g) + 2e−
2Cr3+(aq) Reduction occurs at the cathode:
E ⊖
cell
=E ⊖
half-cell where reduction occurs
–E ⊖
half-cell where
Mg2+(l) + 2e− → Mg(l)
oxidation occurs (c) ZnS: Ions present are Zn2+ and S2–. Zn2+ will
E cell = E (Mg ) – E (Cr ) = –2.37 V –
⊖ ⊖ 2+ ⊖ 3+ be reduced at the cathode and S2– will be
(–0.75 V) = –1.62 V oxidized at the anode.
The E ⊖cell is <0, therefore the reaction is non- Oxidation occurs at the anode:
spontaneous as written. No reaction occurs. S2–(l) → S(l) + 2e–
Reduction occurs at the cathode:
20 Al(s) + Cr3+(aq) → Al3+(aq) + Cr(s)
Zn2+(l) + 2e– → Zn(l)
Half-equations:
Oxidation: Al(s) → Al3+(aq) + 3e– 22 (a) e−

Reduction: Cr3+(aq) + 3e– → Cr(s)

anode + − cathode
The standard free energy change is calculated oxidation reduction
using ΔG⊖ = –nFE ⊖ inert electrodes

where n = 3 mol (as shown in the half-

Cl− Mg2+ MgCl 2(l)
equations 3 moles of electrons are
transferred) (b) anode: 2Cl–(aq) → Cl2(g) + 2e−
F = 96 500 (C mol–1) cathode: Mg2+(aq) + 2e− → Mg(s)
E ⊖ = 0.92 V overall: Mg2+(aq) + 2Cl−(aq) → Mg(s) + Cl2(g)
8
23 D MgCl2 contains Mg2+ and Cl– ions. In the Based on the –E ⊖ values, the oxidation of
molten state the Mg2+ and Cl– ions can H2O will be preferred as it has the higher –E ⊖
migrate to the electrodes (A is correct). value. This is the case when [Cl–] is low, but
Mg2+ will be reduced at the cathode and at higher [Cl–] the oxidation of Cl– becomes
Cl– (chloride ions) will be oxidized at the more likely given the greater number of Cl–
anode (B is correct). During electrolysis the ions that will be found closer to the surface
electrons being transferred travel through the of the electrode.
external circuit (C is correct). Chlorine (Cl2) is At the cathode possible reduction reactions
not present in the reactants so it cannot be are:
oxidized at the cathode so D is incorrect. D
Cu2+(aq) + 2e– → Cu(s) –E ⊖ = +0.34 V
is also incorrect as reduction takes place at
the cathode, not oxidation. 2H2O(l) + 2e– → H2(g) + 2OH–(aq)
–E ⊖ = –0.83 V
24 Follow the steps on page 444 but recognize that
Cu2+ has the highest E ⊖ so will be
as the electrolysis involves aqueous solutions it is
preferentially reduced; Cu(s) will be
possible that water could also be either oxidized
discharged.
at the anode or reduced at the cathode. Note it
Reactions that occur with low CuCl2
is prudent to show awareness that concentration
concentration
could affect the discharge at the anode, but
without information on this it is correct to predict Reduction at cathode: Cu2+(aq) + 2e– →
the outcome based on E ⊖ values. Cu(s)
1. Identify the ions present: K+(aq), F–(aq). Oxidation at anode: 2H2O(l) → 4H+(aq) +
O2(g) + 4e–
At the anode possible oxidation reactions are:
Observations: Carbon cathode will change
2F–(aq) → F2(g) + 2e––E ⊖ = –2.87 V
to a pinky brown colour as Cu(s) is
2H2O(l) → 4H+(aq) + O2(g) + 4e––E ⊖ = –1.23 V
deposited on it. The colour of the solution
H2O has the highest –E ⊖ so will be preferentially will fade as the blue Cu2+(aq) ions are
reduced; H+(aq) and O2(g) will be discharged at reduced to Cu(s). Bubbles will be observed
the anode. forming at the anode due to the discharge of
At the cathode possible reduction reactions are: O2(g).
K+(aq) + e– → K(s) E ⊖ = –2.93 V Reactions that occur with high CuCl2
2H2O(l) + 2e → H2(g) + 2OH (aq)
– –
E = –0.83 V
⊖ concentration

H2O has the highest E ⊖ so will be preferentially Reduction at cathode: Cu2+(aq) + 2e– →
reduced; OH–(aq) and H2(g) will be discharged. Cu(s)

Products will be O2(g) and H2(g). Oxidation at anode: 2Cl– → Cl2(g) + 2e–
Observations: Carbon cathode will change
25 Different reactions occur for the electrolysis of
to a pinky brown colour as Cu(s) is
CuCl2(aq) depending on the electrodes used.
deposited on it. The colour of the solution
(a) Carbon electrodes will fade as the blue Cu2+(aq) ions are
Ions present: Cu2+(aq), Cl–(aq). reduced to Cu(s). Bubbles will be observed
At the anode possible reactions are: forming at the anode due to the discharge
of Cl2(g) and a green gas will be observed
2Cl–(aq) → Cl2(g) + 2e– –E ⊖ = –1.36 V
leaving the solution.
2H2O(l) → 4H+(aq) + O2(g) + 4e–
(b) Copper electrodes
–E ⊖ = –1.23 V
Ions present: Cu2+(aq), Cl–(aq).

9
 With carbon electrodes, which are inert, At the anode possible reactions are:
the species that could be oxidized at the 2Cl–(aq) → Cl2(g) + 2e– –E ⊖ = –1.36 V
anode were Cl–(aq) and H2O(l). With copper
2H2O(l) → 4H+(aq) + O2(g) + 4e––E ⊖ = –1.23 V
electrodes it is also possible that the
Based on the –E ⊖ values, the oxidation of H2O
oxidation can involve the copper metal of the
will be preferred as it has the higher –E ⊖ value.
electrode.
At the cathode possible reduction reactions are:
At the anode possible reactions are:
Na+(aq) + e– → Na(s) –E ⊖ = –2.71 V
2Cl–(aq) → Cl2(g) + 2e––E ⊖ = –1.36 V
2H2O(l) + 2e– → H2(g) + 2OH–(aq)
2H2O(l) → 4H+(aq) + O2(g) + 4e–
–E ⊖ = –0.83 V
–E ⊖ = –1.23 V
Based on the E ⊖ values, the reduction of H2O
Cu(s) → Cu2+(aq) + 2e––E ⊖ = –0.34 V
will be preferred as it has the higher E ⊖ value and
Based on the –E ⊖ values, the oxidation of
H2(g) will be discharged at the cathode.
Cu will be preferred as it has the higher –E ⊖
At any concentration of NaCl(aq) the reaction
value.
at the cathode for aqueous NaCl is different to
At the cathode the possible reactions are:
the reaction that occurs at the cathode with
Cu2+(aq) + 2e– → Cu(s)  –E ⊖ = +0.34 V molten NaCl. H2O is preferentially reduced in the
2H2O(l) + 2e– → H2(g) + 2OH–(aq)  aqueous solution to form H2(g): 2H2O(l) + 2e– →
–E ⊖ = –0.83 V H2(g) + 2OH–(aq).
Cu2+ has the highest E ⊖ so will be (At low NaCl(aq) concentrations the reaction
preferentially reduced; Cu(s) will be at the anode is also different for aqueous NaCl
discharged. than with molten NaCl. H2O is preferentially
Reactions that occur with low copper oxidized in the aqueous solution to form O2(g):
electrodes 2H2O(l) → 4H+(aq) + O2(g) + 4e–. At high NaCl(aq)
concentrations the same reaction occurs at the
Reduction at cathode: Cu2+(aq) + 2e– →
anode as with molten NaCl: 2Cl–(aq) → Cl2(g) +
Cu(s)
2e–.)
Oxidation at anode: Cu(s) → Cu2+(aq) + 2e–
27 Molten AlCl3 consists of dissociated Al3+ and Cl–
Observations: If it is tarnished and old the
ions: AlCl3 → Al3+(l) + 3Cl–(l).
copper cathode will change to a pinky
brown colour as fresh Cu(s) is deposited Ions present Al3+ and Cl–
on it. The colour of the solution will remain Reduction at cathode: Al3+(aq) + 3e– → Al(s)
constant – each blue Cu2+(aq) ion reduced Oxidation at anode: 2Cl– → Cl2(g) + 2e–
to Cu(s) at the cathode is replaced by a
If 0.2 mol of Cl2(g) is formed at the cathode then
Cu2+(aq) ion formed at the anode. The
this can be used to determine the total amount
copper anode will start disintegrating as the
of electrons released in the oxidation of Cl– at the
Cu(s) it is made of is oxidized to Cu2+(aq)
anode:
ions.
n(e–) = 2 × n(Cl2) = 2 × 0.2 mol = 0.4 mol
26 Molten NaCl, i.e. NaCl (l)
The number of electrons released in the
Ions present: Na+ and Cl– oxidation at the anode must equal the number
Reduction at cathode: Na+(aq) + e– → Na(s) of electrons accepted in the reduction at the
Oxidation at anode: 2Cl– → Cl2(g) + 2e– cathode. We can use this to determine the
number of moles of Al(s) discharged at the
Aqueous NaCl, i.e NaCl(aq)
cathode.
Ions present Na+ and Cl–
10
 n(e–) 0.4 mol The mass of the silver anode will decrease as Ag
n(Al) = = = 0.13 mol*
3 3 is oxidized to Ag+ ions that are released into the
mass (Al) = nM(Al) = 0.13 mol × 26.98 g mol–1 solution.
= 3.5 g* The mass of the spoon (which is the cathode)
(*Because the question only gave a value of 0.2 will increase as a layer of Ag is deposited on
moles of Cl2, which has one significant figure, its surface. The metal surface of the spoon
then all answers calculated from this value will become shiny/grey as the layer of Ag(s) is
should actually be expressed to one significant deposited.
figure as well, i.e. moles(Al) = 0.1 mol and mass Impurities may be visible collecting as a sludge
(Al) = 3 g. An extra figure has been given in at the bottom of the electrolyte solution as they
these answers to avoid the large rounding errors fall from the decomposing impure silver anode.
associated with working with only one significant
figure.)

28 C As this is a multiple-choice question it is Practice questions

necessary to be able to deduce the answer
without determining the exact amount  1 Cu2+(aq) + 2e– → Cu(s) is a two-electron
of Cu(s) that would be formed in each reduction.
electrolysis. The answer can be determined
Ag+(aq) + e– → Ag(s) is a one-electron reduction.
by calculating the total charge (C) involved in
each process and then how many electrons The total charge available for each cell = current
are involved in each reduction. × time.

Cu+ requires 1 mole of electrons per mole of Has 500 C available for a two-electron
A
Cu reduction.

Cu2+ requires 2 moles of electrons per mole Has 500 C available for a one-electron
B
of Cu reduction.

charge = current × time Has 750 C available for a two-electron

C
reduction.
A Charge= 5.00 A × (10 × 60) s = 3000 C
for a one-electron reduction (Cu+ → Cu) Has 375 C available for a one-electron
D
reduction.
B Charge = 5.00 A × (10 × 60) s = 3000 C
for a two-electron reduction (Cu2+ → Cu) Cell B will have the most metal ions being
converted to the solid metal and the greatest
C Charge = 2.00 A × ( 30 × 60) s = 3600 C
mass of metal formed.
for a one-electron reduction (Cu+ → Cu)
Correct answer is B.
D Charge = 2.00 A × (30 × 60) s = 3600 C
for a two-electron reduction (Cu2+ → Cu)  2 As the oxidation state of oxygen is –2 we can
Option C has the greatest charge (related determine that the oxidation state of nitrogen in
to the number of electrons) available for a NO2 is +4. The species being reduced to form
reduction that only involves one electron NO2 must contain nitrogen in an oxidation state
per reduction therefore this will produce the greater than +4.
most Cu(s) product. A N2O B NO3– C HNO2 D NO
+1 +5 +3 +2
29 In electroplating the metal is deposited at the
cathode as the anode decomposes. Correct answer is B.
Reduction at cathode: Ag+(aq) + e– → Ag(s)  3 A spontaneous reaction occurs when E ⊖cell is
Oxidation at anode: Ag(s) → Ag (aq) + e
+ –
positive. Oxidation occurs at the electrode with
11
 the most negative electrode potential. Reversing BrO3–(aq), therefore Br has been oxidized and
the reaction inverses the potential, multiplying Br –(aq) is the reducing agent.
the reaction has no effect on the potential as it is Correct answer is A.
an intensive property:
 8 In a voltaic cell reduction occurs at the positive
2Al(s) → 2Al3+(aq) + 6e– –E ⊖ = +1.66 V
electrode.
3Ni2+(aq) + 6e– → 3Ni(s) E ⊖ = –0.23 V
I. Change in oxidation state for Zn is +2 → 0,
2Al(s) + 3Ni2+(aq) → reduction occurs.
2Al3+(aq) + 3Ni(s) E ⊖cell = +1.43 V II. Change in oxidation state for Cl is 0 → –1,
Correct answer is D. reduction occurs.
 4 This reaction is discussed on page 450. The III. Change in oxidation state for Mg is 0 → +2,
oxidation and reduction half-reactions for the oxidation occurs.
electrolysis of CuSO4(aq) are: Correct answer is A.
reduction: Cu2+(aq) + 2e– → Cu(s)  9 Reduction occurs at the cathode and oxidation
oxidation: 2H2O(l) → 4H+(aq) + O2(g) + 4e– occurs at the anode.
overall: 2Cu2+(aq) + 2H2O(l) → 2Cu(s) + For molten MgBr2, Mg2+ will be reduced at the
4H+(aq) + O2(g) cathode and Br– will be oxidized at the anode.
From the overall reaction we see that Cu(S) and For aqueous MgBr2, Mg2+ or H2O can be
O2(g) are produced in a mole ratio of 2:1. reduced at the cathode. The species that is
Correct answer is C. preferentially reduced is the one with the highest
E ⊖ potential, in this case H2O will be reduced
 5 MnO4–(aq) + 8H+(aq) + 5Fe2+(aq) → Mn2+(aq) + (E ⊖(Mg) = –2.37 V, E ⊖(H2O) = –1.23 V). Br– will
+7 +2
still be the species oxidized at the anode.
5Fe3+(aq) + 4H2O(l)
Correct answer is B.
The oxidation state of Mn changes from +7 in
MnO4–(aq) to +2 in Mn2+(aq). This means that 10 In a voltaic cell the negative electrode is the
Mn has been reduced, therefore it has gained anode and oxidation occurs. In an electrolytic
electrons and MnO4– is the oxidizing agent. cell the negative electrode is the cathode and
reduction occurs.
Correct answer is C.
Correct answer is A.
 6 Electroplating with silver is discussed on
page 454. The silver bar must be the positive 11 A spontaneous reaction occurs when E ⊖cell is
electrode and the spoon must be the negative positive. Oxidation occurs at the electrode with
electrode. There is no need to acidify the the most negative electrode potential. Reversing
electrolyte solution for the electrolysis of metal the reaction inverses the potential, multiplying
ions. the reaction has no effect on the potential as it is
an intensive property.
Correct answer is C.
3Fe(s) → 3Fe2+(aq) + 6e––E ⊖ = +0.44 V
 7 2MnO4 (aq) + Br (aq) + H2O(l) →
– –

+7 –1
CrO72–(aq) + 14H+(aq) + 6e– →
2Cr3+(aq) + 7H2O(l) E ⊖ = +1.33 V
2MnO2(s) + BrO3–(aq) + 2OH–(aq)
+4 +5 3Fe(s) + 3 CrO72–(aq) +
14H+(aq) → 3Fe2+(aq) +
The reducing agent is the species that gets
2Cr3+(aq) + 7H2O(l) E ⊖cell = +1.77 V
oxidized. In the reaction the oxidation state for
Br has changed from −1 in Br –(aq) to +5 in (E ⊖cell = E ⊖red – E ⊖ox =+1.33 V – (–0.44 V) = +1.77 V)
Correct answer is C.
12
12 (a) (i) The standard electrode potential is the (E ⊖cell = E ⊖red – E ⊖ox = –0.45 V – (–1.66 V
voltage obtained for a half-cell when it = +1.21 V)
is connected to the standard hydrogen The salt bridge is required to complete
(v)
electrode. This measurement must be the electrical circuit and to allow the
conducted under standard conditions of movement of ions into the half-cells to
298 K with 1 mol dm−3 solutions and an maintain the balance of charges as ions
H2(g) pressure of 100 kPa. are formed and consumed by the redox
The negative value of the standard reactions occurring.
electrode potential indicates that the (b) (i) As water is a neutral ligand the overall
electrons flow from the half-cell to the charge is due to the oxidation state of
hydrogen electrode. This means that the central cobalt ion. The oxidation
oxidation is occurring in the half-cell and state of cobalt is +2.
that Fe is oxidized more readily than H2.
The charge on the sulfate ion is –2. This
(ii)
(Fe is a better reducing agent than H2.)
gives a total negative charge due to the
The question tells us that cobalt is
(ii) three sulfate ions of –6. To be neutral
produced during the reaction so overall a +6 charge must be shared by
reduction must be occurring in the the two cobalt centres. The oxidation
cobalt half-cell. state of cobalt is +3.
E ⊖cell = 0.17 V, E ⊖ox = E ⊖(Fe2+/Fe) = –0.45 V
The charge on the chloride ion is –1.
(iii)
E ⊖cell = E ⊖red – E ⊖ox This gives a total negative charge due
0.17 V = E ⊖red – (–0.45) V to the four chloride ions of –4. For an
0.17 V = E ⊖red + 0.45 V overall charge of –2 on the complex ion
E ⊖red = –0.28V the charge on the cobalt centre must be
+2. The oxidation state of cobalt is +2.
The standard electrode potential for the
cobalt half-cell is –0.28 V. (c) (i) electron
flow
When the voltaic cell is operating cobalt
(iii)
is being produced: Co2+(aq) + 2e– → + −
Co(s).
As Co2+(aq) is being reduced in this
process it is the oxidizing agent.
The reduction half-reactions and the
(iv)
potentials for the two half-cells are:
Al3+(aq) + 3e– Al(s) E ⊖ = –1.66 V NaCl(aq)

Fe2+(aq) + 2e– Fe(s) E ⊖ = –0.45 V The ions present will be Na+, Cl–, H+ and
(ii)
The reactions occurring are: OH–.

2Al(s) → 2Al3+(aq) + 6e–  Reduction occurs at the cathode and

(iii)
–E ⊖ = +1.66 V there are two possible reductions that
can occur:
3Fe2+(aq) + 6e– → 3Fe(s)
 E ⊖ = –0.45 V 2H2O(l) + 2e– →
H2(g) + 2OH–(aq) E ⊖ = –0.83 V
overall equation:
Na+(aq) + e– → Na(s) E ⊖ = –2.71 V
2Al(s) + 3Fe2+(aq) → 2Al3+(aq) +
3Fe(s) E cell = +1.21 V
⊖ The reduction with the highest E ⊖ value
happens preferentially so the product
13
 formed at the cathode is H2(g) and the anode reaction (oxidation)
half-equation is 2H2O(l) + 2e– → H2(g) +  2Br−(l) → Br2(g) + 2e–
2OH–(aq).
13 (a) A voltaic cell involves a spontaneous
Oxidation occurs at the anode and there reaction and converts chemical energy to
are two possible oxidations that can electrical energy whereas an electrolytic
occur: cell involves a non-spontaneous reaction
2H2O(l)+(aq) → 4H+(aq) + with electrical energy being converted to
O2(g) + 4e––E ⊖ = –1.23 V chemical energy.
2Cl–(aq) → Cl2(g) + In a voltaic cell the cathode is negative
2e–(s)–E ⊖ = –1.36 V and the anode is positive whereas in an
The oxidation with the highest E ⊖ value electrolytic cell the anode is negative and
happens preferentially so the product the cathode is positive. (In both types of cell
formed at the anode is O2(g) and the oxidation occurs at the anode and reduction
half-equation is 2H2O(l)+(aq) → 4H+(aq) + at the cathode.)
O2(g) + 4e–. A voltaic cell requires two separate
(If the solution had contained a solutions joined by a salt bridge whereas an
concentrated solution of NaCl then the electrolytic cell involves a single solution and
second reaction would be favoured does not require a salt bridge.
despite the higher potential.) For a substance to conduct electricity it
(b)
Reduction:
(iv) must have charged species that are mobile.
 4H2O(l) + 4e– → 2H2(g) + 4OH–(aq) In solid NaCl the ions are unable to move
and it cannot conduct electricity. In molten
Oxidation:
(liquid) NaCl the ions are able to move and it
 2H2O(l)+(aq) → 4H+(aq) + O2(g) + 4e–
is able to conduct electricity.
Overall:
Molten NaCl contains Na+ and Cl– ions.
(c)
 2H2O(l)+(aq) → 2H2(g) + O2(g)
Reduction occurs at the cathode:
(4H2O(l) on reactants cancelled by 4H2O(l) on
 Na+(l) + e– → Na(s)
products as 4H+(aq) + 4OH−(aq) → 4H2O(l))
Oxidation occurs at the anode:
Ratio of H2(g) to O2(g) is 2:1.
 2Cl–(l) → Cl2(g) + 2e–
(d) (i) If concentrated NaCl(aq) was used the
reduction: 2Na+(l) + 2e– → 2Na(s)
products would be H2(g) and Cl2(g).
oxidation: 2Cl–(l) → Cl2(g) + 2e–
The same reaction occurs at the
cathode: overall: 2Na+(l) + 2Cl–(l) → 2Na(s) + Cl2(g)
2H+(aq) + 2e– → H2(g) Aluminium is less dense and more malleable
(d)
than iron as well as being more resistant
However, at the anode the higher
to corrosion, all of which makes aluminium
concentration of Cl–(aq) favours the
preferable to iron in many applications, such
reduction of Cl– rather than H2O:
as aircraft and car construction. Aluminium
2Cl–(aq) → Cl2(g) + 2e–
is also a better heat conductor, which makes
If molten sodium bromide was used
(ii) it more suitable for uses such as saucepans,
the products would be Na(s) and Br2(g). and a better electrical conductor than iron,
Molten sodium bromide contains Na+ which makes it more suitable for electronics.
and Br− ions:
For the electroplating of silver the anode
(e)
cathode reaction (reduction) has to be a silver bar or rod as this is
 Na+(l) + e– → Na(s)
14
 where oxidation occurs and silver ions are the circuit to the nickel cathode. Anions
generated: Ag(s) → Ag+(aq) + e–. flow to the aluminium electrode to balance
The cathode has to be the object that the the formation of Al3+ and cations flow to
silver is being electroplated onto as this is the nickel electrode to replace the Ni2+ ions
where reduction and the formation of solid being reduced.
silver occurs: Ag+(aq) + e– → Ag(s).
The electrolyte needs to be a silver salt
solution, e.g. aqueous silver nitrate, Challenge yourself
AgNO3(aq), to ensure that only Ag+ ions are
present and reduction cannot involve other 1 Oxidation state of elements in H2O2: H = +1,
metal ions. O = −1.
1 2 e2 The oxidation state of the oxygen atom in H2O2
e2 is halfway between 0 (element) and −2 (usual
anode cathode oxidation state of oxygen in compounds), so it
can be oxidized (to 0) or reduced (to −2) and
H2O2 will act as a reducing agent or oxidizing
agent, respectively. As oxygen is a very
cathode electronegative element it will more easily be
anode bar of metal object to be plated
impure silver reduced from −1 to −2 and hydrogen peroxide is
solution of silver salt
e.g. silver cyanide more likely to act as an oxidizing agent.

2 Cl2(aq) + 2NaOH(aq) →
14 (a)   Ni2+(aq) + 2e– Ni(s) E ⊖ = –0.26 V
0
 Al3+(aq) + 3e– Al(s) E ⊖ = –1.66 V
NaCl(aq) + NaClO(aq) + H2O(l)
The reactions occurring will be: –1 +1
 2Al(s) → 2Al (aq) + 6e –E = +1.66 V
3+ – ⊖
Consider the changes that occur in the oxidation
 3Ni (aq) + 6e → 3Ni(s)
2+ –
E = –0.26 V
⊖ state for Cl in the reaction above:
overall equation: ●● In forming NaCl from Cl2 the oxidation state
  2Al(s) + 3Ni2+(aq) → changes from 0 to −1 and reduction occurs.
 2Al3+(aq) + 3Ni(s) E ⊖cell = +1.40 V ●● In forming NaClO from Cl2 the oxidation state
(E cell = E red – E ox = –0.26 V – (–1.66 V) =
⊖ ⊖ ⊖ changes from 0 to +1 and oxidation occurs.
+1.40 V) As the oxidation and reduction of Cl2 occur
From the answer to (a), the cell potential is
(b) simultaneously this is a disproportionation
+1.40 V. reaction.
(c) voltmeter 3 The Lewis structure of I3– is:
e− V e−

cations anions
−
salt bridge
Al anode Ni cathode I I I

As the central atom has five electron domains

with two bonding electron pairs this gives a
Al anode is
negative
nickel cathode is
positive
linear shape. The negative charge is spread out
over the linear ion and due to the large size of
Electrons are generated at the anode by the the iodine atoms there is a low charge density.
oxidation of aluminium and they flow through This low charge density enables I3– to form a
15
 stable complex in the hydrophobic interior of the www.pearsonhotlinks.co.uk/url.
amylose helix. aspx?urlid=68468)

4 As the temperature of water increases the 6 The relevant equations are ΔG⊖ = −RTlnKc and
amount of dissolved oxygen decreases as more ΔG⊖ = −nFEcell = −nFE ⊖cell
gas molecules will have sufficient kinetic energy Combining these equations we get
to escape the water surface. The discharge of RTlnKc = nFE ⊖cell
hot water will cause a decrease in the dissolved RTlnKc
oxygen in the lake (with possible negative E ⊖cell =
nF
consequences for aquatic life) . RT 8.314 J K–1 mol–1 × 298 K
At 298K, =
5 The Faraday constant, F, is the charge carried F 96 500 C mol–1
by 1 mole of electrons. = 0.0257 V
lnKc
Charge of an electron (e) = 1.602176565 × log Kc =
10–19 C 2.303
0.0257 V × 2.303 logKc
Avogadro’s number (NA) = 6.02214129 × E ⊖cell =
1023 mol–1 n
0.0592
F = e × NA = 1.602176565 × 10–19 C × = logKc
n
6.02214129 × 1023 mol–1 = 96485.3365 C mol–1

(For precise values, also see the NIST

Reference on Constant, Units and Uncertainty,

16