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(a) Electrode potentials are measured using either a primary standard or a secondary
one. Name the primary standard and explain why a secondary standard is normally used.
By writing all relevant equations and stating essential experimental conditions, outline
how the standard electrode potential, E , for the formation of metallic iron from aqueous
iron(II) ions could be measured in a cell using the primary standard. Justify the need to
exclude air while this measurement is being made.
(12)
(b)
Use the standard electrode potential data given below to predict the direction of
spontaneous reaction in
(i)
an equimolar solution of iron(II) and iron(III) ions in the presence of metallic iron
(ii)
an equimolar solution of gold(I) and gold(III) ions in the presence of metallic gold.
E /V
3+ (
Fe aq) + 3e
2+
Fe (aq) + 2e
3+
Au (aq) + 3e
+
Au (aq) + e
Fe(s)
Fe(s)
Au(s)
Au(s)
0.04
0.44
+1.40
+1.69
(Total 20 marks)
2.
The table below shows some values for standard electrode potentials.
Electrode
Electrode reaction
2+
Mn (aq) + 2e
Fe (aq) + 2e
Ni (aq) + 2e
Sn (aq) + 2e
2H (g)+ 2e
E /V
Mn(s)
1.18
2+
Fe(s)
0.44
2+
Ni(s)
0.25
2+
Sn(s)
0.14
H2(g)
(a)
(i)
Give the name of electrode E and indicate its role in the determination
of standard electrode potentials.
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
(b)
The electrochemical cell set up between electrodes C and D can be represented by the cell
diagram:
N i(s ) N i2+ (a q ) S n 2+ (a q ) S n (s )
(i)
(ii)
(iii)
(c)
Use the standard electrode potential data given in the table above:
(i)
to explain whether or not you would expect a reaction to occur if a piece of tin
were to be added to a test tube containing aqueous iron(II) sulphate;
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
to predict and explain two observations you would expect to make if a small piece
of manganese were to be added to a test tube containing hydrochloric acid of
3
concentration 1 mol dm .
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
(Total 12 marks)
3.
Ag (aq) + e
AgF(s) + e
AgCl(s) + e
Ag(s) + Cl (aq)
D (aq) + e
+0.08
Ag(s)+
+0.78
Ag(s) + F (aq)
AgBr(s) + e
H (aq) + e
E /V
AgI(s) + e
+0.22
Ag(s) + Br (aq)
+0.07
H2(g)
0.00
D2(g)
0.004
0.15
Ag(s) + I (aq)
2
1
H.
(a)
By considering electron transfer, state what is meant by the term oxidising agent.
.....................................................................................................................................
(1)
(b)
State which of the two ions, H (aq) or D (aq), is the more powerful oxidising agent.
Write an equation for the spontaneous reaction which occurs when a mixture of aqueous
+
+
H ions and D ions are in contact with a mixture of hydrogen and deuterium gas. Deduce
the e.m.f. of the cell in which this reaction would occur spontaneously.
Stronger oxidising agent..........................................................................................
Equation...................................................................................................................
..................................................................................................................................
..................................................................................................................................
e.m.f..........................................................................................................................
..................................................................................................................................
(3)
(c)
Write an equation for the spontaneous reaction which occurs when aqueous F ions and
Cl ions are in contact with a mixture of solid AgF and solid AgCl. Deduce the e.m.f. of
the cell in which this reaction would occur spontaneously.
Equation....................................................................................................................
..................................................................................................................................
e.m.f..........................................................................................................................
..................................................................................................................................
(2)
(d)
Silver does not usually react with dilute solutions of strong acids to liberate hydrogen.
(i)
(ii)
Suggest a hydrogen halide which might react with silver to liberate hydrogen in
aqueous solution. Write an equation for the reaction and deduce the e.m.f. of the
cell in which this reaction would occur spontaneously.
Hydrogen halide...........................................................................................
Equation..........................................................................................................
........................................................................................................................
........................................................................................................................
e.m.f................................................................................................................
........................................................................................................................
(4)
(Total 10 marks)
4.
(a)
(i)
Cu
2
1s 2s 2p 3s 3p ...............................................................................
(1)
(ii)
2+
Cu
1s 2s 2p 3s 3p ..............................................................................
(1)
(b)
Name the type of bonding between the copper ion and the water molecules in the
2+
complex ion, [Cu(H2O)6] .
...........................................................................................................................
(1)
(ii)
[Cu(H2O)6]
..................................................................................................
[CuCl4] .........................................................................................................
(2)
(iii)
Describe the colour change which would be observed as the reaction takes place.
...........................................................................................................................
(2)
(c)
(i)
Describe the changes which are observed when aqueous ammonia is
added dropwise, until in excess, to aqueous copper(II) sulphate.
...........................................................................................................................
...........................................................................................................................
(2)
(ii)
Give the formula of the copper-containing complex ion which is present at the end
of the changes described in (c)(i).
...........................................................................................................................
(1)
(Total 10 marks)
5.
(a) Explain in terms of electrons what is meant by reducing agent and ligand.
2+
Illustrate your answer using the [Fe(H2O)6] ion.
(5)
(b)
(i)
Transition metals have the characteristic property of variable
oxidation state. State three other characteristics of transition metal chemistry,
giving a specific example to illustrate each characteristic you mention. To what
feature of these metals can such characteristic behaviour be attributed?
(ii)
Describe and account for all the changes that occur when a solution of a copper(II)
compound in concentrated hydrochloric acid is poured into an excess of water.
(14)
(c)
(ii)
determine the oxidation states before and after reaction of any species that are
oxidised;
(iii)
write half-equations, including state symbols, for all redox reactions that occur.
2+
6.
(a) Name the standard reference electrode against which electrode potentials are
measured and, for this electrode, state the conditions to which the term standard refers.
Name ..........................................................................................................................
Conditions ..................................................................................................................
....................................................................................................................................
....................................................................................................................................
(4)
(b)
The standard electrode potentials for two electrode reactions are given below.
2
Ag (aq)
(i)
+ e Ag(s)
= + 2.01 V
= + 0.80 V
value ...........................................................................................................
Equation ............................................................................................................
............................................................................................................................
(ii)
State how, if at all, the electrode potential of the S2O 8 /SO 4 equilibrium would
2
7.
The table below shows some values for standard electrode potentials. These data should be
used, where appropriate, to answer the questions that follow concerning the chemistry of copper
and iron.
Electrode reaction
2+
Fe(s)
0.44
H2(g)
0.00
2+
Cu(s)
+ 0.34
Fe (aq) + 2e
2H (aq) + 2e
Cu (aq) + 2e
O2(g) + 2H2O(l) + 4e
E /V
4OH (aq)
NO(g) + 2H2O(l)
+ 0.40
+ 0.96
(a)
Write an equation to show the reaction that occurs when iron is added to a solution of a
copper(II) salt.
...................................................................................................................................
(1)
(b)
A similar overall reaction to that shown in (a) would occur if an electrochemical cell was
set up between copper and iron electrodes.
(i)
Write down the cell diagram to represent the overall reaction in the cell.
...........................................................................................................................
(2)
(ii)
(1)
10
(c)
(i)
Use the standard electrode potential data given to explain why copper
reacts with dilute nitric acid but has no reaction with dilute hydrochloric acid.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
11
(ii)
Write an equation for the reaction between copper and dilute nitric acid.
...........................................................................................................................
(2)
12
(d)
Although iron is a widely used metal, it has a major disadvantage in that it readily
corrodes in the presence of oxygen and water. The corrosion is an electrochemical
process which occurs on the surface of the iron.
(i)
Use the standard electrode potential data given to write an equation for the overall
reaction that occurs in the electrochemical cell set up between iron, oxygen and
water.
...........................................................................................................................
(1)
13
(ii)
State, with a reason, whether the iron acts as the anode or cathode of the cell.
...........................................................................................................................
...........................................................................................................................
(2)
14
(iii)
Predict and explain whether or not you would expect a similar corrosion reaction to
occur with copper in the presence of oxygen and water.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(Total 14 marks)
15
8.
(a)
Identify the reducing agent in this reaction and write a half-equation for its action.
Reducing agent ...........................................................................................................
Half-equation ..............................................................................................................
(2)
16
(b)
Co (aq) + 2e Co(s)
is measured by reference to a standard hydrogen electrode.
(i)
is measured,
Temperature .....................................................................................................
Concentration ..................................................................................................
17
(ii)
18
(c)
Cobalt in oxidation states +2 and +3 forms complex ions with water, ammonia and
cyanide ligands. Use, where appropriate, the data given below to answer the questions
which follow.
3+
[Co(H2O)6] (aq) + e
V
1
2
O2(g) + 2H (aq) + 2e
V
3+
[Co(NH3)6] (aq) + e
V
+
2H (aq) + 2e
[Co(CN)6] (aq) + e
V
2+
[Co(H2O)6] (aq)
= +1.81
H2O(l)
= +1.23
= +0.10
= 0.80
2+
[Co(NH3)6] (aq)
H2(g) E
[Co(CN)6] (aq)
= 0.00 V
4
19
(i)
Which of the six cobalt species shown above is the most powerful oxidising agent?
....................................................................................................................
20
(ii)
21
(iii)
Hydrogen is evolved when a salt containing the cobalt species [Co(CN)6] (aq) is
reacted with a dilute acid. Use the electrode potentials given above to explain the
formation of the hydrogen gas.
....................................................................................................................
....................................................................................................................
....................................................................................................................
(4)
(Total 10 marks)
22
9.
Use the data given below, where appropriate, to answer the questions which follow.
Standard electrode potentials in acid solution
2+
Mg
Zn
2+
(aq) + 2e Mg(s)
(aq) + 2e Zn(s)
4+
2+
Sn (aq) + 2e Sn (aq)
2+
VO (aq) + 2H (aq) + e
E /V
2.37
0.76
+0.15
3+
V (aq) + H2O(l)
+0.34
3+
Ce (aq) + e Ce (aq)
+1.02
+1.70
23
(a)
Give the components of the standard reference electrode used in determining the standard
electrode potentials above. State the conditions under which this standard reference
electrode has a potential of 0.00 V.
Components.................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
Conditions...................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(6)
24
(b)
M a g n e s iu m
S a lt b rid g e
1 .0 M Z n
2+
(aq )
1 .0 M M g
2+
(aq )
25
(i)
(ii)
26
(c)
S o lu tio n 1 .0 M w ith
re s p e c t to V O 2+ (a q ),
V 3+(a q ) a n d H + (a q )
V
S a lt b r id g e
I n e r t e le c tr o d e
S o lu tio n 1 .0 M w ith
re s p e c t to C e 4+ (a q ),
C e 3+ (a q ) a n d H +(aq )
27
(i)
(ii)
Deduce the direction of electron flow in the external circuit when the inert
electrodes are connected together.
...........................................................................................................................
(2)
28
(d)
Using data from the table on page 6, derive an equation for the overall redox process
4+
which occurs when a solution containing Ce ,(aq) is added to a solution containing
3+
V (aq).
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
29
(e)
2+
3+
(aq), VO
2+
(aq) and
.....................................................................................................................................
(2)
(Total 15 marks)
30
10.
(a)
..................................................................................................................................
(1)
31
(b)
Give an example of a vanadium compound which acts as a catalyst, and give an equation
for the process which it catalysed.
Catalyst .......................................................................................................................
Equation for process catalyses....................................................................................
(2)
32
(c)
Describe briefly how you would show that manganese(II) ions catalyse the reaction
2
between manganate(VII) ions and ethanedioate ions, C 2 O 4 , in dilute sulphuric acid.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(3)
33
(d)
Give the reagents required to carry out each of the following conversions.
(i)
3+
[Cr(H2O)6] CrO 4
...........................................................................................................................
(ii)
2+
3+
[Fe(H2O)6] [Fe(H2O)6]
...........................................................................................................................
(iii)
VO 3 [V(H2O)6]
2+
...........................................................................................................................
(6)
(Total 12 marks)
34
11.
Use the table of standard electrode potentials given below to answer the following questions.
E /V
+ 1.36
+1.07
3+
2+
Fe (aq) + e Fe (aq)
I2(aq) + 2e 2I (aq)
2+
+0.77
+0.54
3+
2+
V (aq) + e V (aq)
2+
Fe (aq) + 2e Fe(s)
+0.94
+0.34
0.26
0.44
35
(a)
(b) (i)
Give the conditions under which the electrode potential for
Cl2(g)/2Cl (aq) is
+1.36 V.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
36
(ii)
Give a change in one of these conditions which would result in the electrode
potential becoming more positive. Explain your answer.
Change in conditions .......................................................................................
Explanation ......................................................................................................
..........................................................................................................................
(5)
37
(c)
(i)
..........................................................................................................................
(ii)
Identify all the species in the table which could convert I aq) into I2(aq) but which
Identify the metal ions which would be left in solution if an excess of powdered
2+
iron metal was added to an acidified solution containing VO (aq) ions.
..........................................................................................................................
(5)
(Total 11 marks)
38
12.
Large blocks of magnesium are bolted onto the hulls of iron ships in an attempt to prevent the
iron being converted into iron(II), one of the steps in the rusting process.
Use the data below, where appropriate, to answer the questions which follow.
2+
Mg (aq) + 2e
2+
Fe (aq) + 2e
O2(g) + 2H2O(l) + 4e
Mg(s)
Fe(s)
4OH (aq)
E /V
2.37
0.44
+0.40
39
(a)
2+
2+
Calculate the e.m.f. of the cell represented by Mg(s)|Mg (aq)||Fe (aq)|Fe(s) under
standard conditions. Write a half-equation for the reaction occurring at the negative
electrode of this cell when a current is drawn.
Cell e.m.f. ...............................................................................................................
Half-equation .........................................................................................................
................................................................................................................................
(2)
40
(b)
2+
2+
Deduce how the e.m.f. of the cell Mg(s)|Mg (aq)||Fe (aq)|Fe(s) changes when the
2+
concentration of Mg is decreased. Explain your answer.
Change in e.m.f. ......................................................................................................
Explanation .............................................................................................................
.................................................................................................................................
(3)
41
(c)
2+
Pt(s)|OH (aq)|O2(g)||Fe (aq)|Fe(s) and use it to explain why iron corrodes when in
contact with water which contains dissolved oxygen.
Cell e.m.f. ...............................................................................................................
Explanation ............................................................................................................
................................................................................................................................
(2)
(Total 7 marks)
42
13.
Use the standard electrode potential data in the table below to answer the questions which
follow.
E /V
_____________________________________________________________
4+
Ce (aq)
2+
Mn (aq) + 4H2O(l)
3+
Ce (aq) + e
Fe (aq) + e
+
(aq) + 4H (aq) + 2e
SO4
3+
+1.70
+1.51
2Cl (aq)
+1.36
2+
+1.00
VO (aq) + H2O(l)
2+
Fe (aq)
H2SO3(aq) + H2O(l)
+0.77
+0.17
43
(a)
Name the standard reference electrode against which all other electrode potentials are
measured.
...............................................................................................................................
(1)
44
(b)
3+
2+
When the standard electrode potential for Fe (aq) / Fe (aq) is measured, a platinum
electrode is required.
(i)
45
(ii)
3+
2+
What are the standard conditions which apply to Fe (aq)/Fe (aq) when measuring
this potential?
......................................................................................................................
......................................................................................................................
......................................................................................................................
(3)
46
(c)
2+
47
(d)
(i)
agent?
Which one of the species given in the table is the strongest oxidising
.....................................................................................................................
48
(ii)
2+
3+
Which of the species in the table could convert Fe (aq) into Fe (aq) but could
2+
49
(e)
Use data from the table of standard electrode potentials to deduce the cell which would
have a standard e.m.f. of 0.93 V. Represent this cell using the convention shown in part
(c).
..............................................................................................................................
(2)
(Total 12 marks)
50
14.
Use the data below, where appropriate, to answer the questions which follow.
Standard electrode potentials
+
E /V
2H (aq) + 2e H2(g)
0.00
+1.09
+1.52
51
(a)
State the hydrogen ion concentration and the hydrogen gas pressure when, at 298 K, the
potential of the hydrogen electrode is 0.00 V.
Hydrogen ion concentration ......................................................................................
Hydrogen gas pressure ..............................................................................................
(2)
52
(b)
The electrode potential of a hydrogen electrode changes when the hydrogen ion
concentration is reduced. Explain, using Le Chateliers principle, why this change occurs
and state how the electrode potential of the hydrogen electrode changes.
Explanation of change ...............................................................................................
.....................................................................................................................................
Change in electrode potential ....................................................................................
(3)
53
(c)
V
S a lt B r id g e
S o lu tio n c o n ta in in g
B r 2 (a q ) a n d B r (a q )
S o l u t i o n c o n t a i n i n g B r O 3 ( a q ) ,
H +(a q ) a n d B r 2 (a q )
54
(i)
Use the data above to calculate the e.m.f. of the above cell under standard
conditions.
...........................................................................................................................
(ii)
55
15.
Use the data below, where appropriate, to answer the following questions.
2SO 24 (aq)
(aq) + 8H (aq) + 5e
Mn (aq) + 4H2O(l)
Cl2(aq) + 2e
3+
S2O
MnO 4
Cr2 O 72
2
8
(aq) + 2e
NO 3
(aq) + 3H (aq) + 2e
Fe (aq) +
/ V
+2.01
2+
+1.51
2Cl (aq)
+1.36
3+
+1.33
HNO2(aq) + H2O(l)
+0.94
2+
Fe (aq)
+0.77
56
(a)
(ii)
Cr (aq) ....
(iii)
MnO 4 (aq) ..
3+
(3)
57
(b)
From the table above, select the species which is the most powerful reducing agent.
......................
(1)
58
(c)
2
chromium in Cr2 O 7 ..
(ii)
nitrogen in HNO2
(2)
59
(d)
The concentration of iron(II) ions in aqueous solution can be determined by titrating the
solution, after acidification, with a standard solution of potassium manganate(VII).
(i)
Explain, by reference to the data given in the table above, why hydrochloric
acid should not be used to acidify the solution containing iron(II) ions.
............
............
60
(ii)
Explain, by reference to the data given in the table above, why nitric acid should
not be used to acidify the solution containing iron(II) ions.
............
............
(4)
61
(e)
(i)
2
2
2+
Pt | Mn (aq), MnO 4 (aq) || S 2 O 8 (aq), SO 4 (aq) | Pt
............
(ii)
2
Deduce an equation for the reaction which occurs when an excess of S 2 O 8 (aq) is
2+
added to an aqueous solution of Mn (aq) ions.
............
............
............
(3)
(Total 13 marks)
62
16.
Use the standard electrode potential data given in the table below, where appropriate, to answer
the questions which follow.
E
2
4O
2 +
S
V
O
V
2
+
2
2 I O
M
4n
( a +q
( a+ q
( g )+
F 3e +
( a +q
( a q+
( +a
)
)
+
)
)
q
/ V
( a q )
+V 2 +
(e a q )
0 . 2
+ 4 H H 2 ( 3 Sa qO ) 2 (+ a q )2 + e 0+ . 1
+
2 H V 3 + ( a ( aq 2q) ) + +
+ H e 0 . 3O
2 H
H( 2 a 2 q O )
+ ( a q 2) e + 0 . 6
( a q )
+F 2 e +
e( a q )
+ 0 . 7
+
2 H V 2 O ( + a q )( 2a q+ )
+ + e 1 H. 0
+ 1 2 IH 2
( a( aq q )2 ) + + 6 1 +H 0 1e . O1
)
+
8 MH 2 n+ ( a q ( a) 2 q +)
+ + 5 1 e 4 . H5
6
H7
O
4 ( l )
8
7
0 O
( l )
9( l )
2
O
( l )
63
Pt | H2SO3(aq), SO
(i)
2
4
3+
2+
(ii)
64
(b)
(ii)
Give one reason why the e.m.f. of this cell changes when the electrodes are
connected and a current flows.
.......................................................................................................................
65
(iii)
State how, if at all, the e.m.f. of this standard cell will change if the surface area
of each platinum electrode is doubled.
.......................................................................................................................
(iv)
State how, if at all, the e.m.f. of this cell will change if the concentration of IO
ions is increased. Explain your answer.
66
(c)
2+
67
17.
Where appropriate, use the standard electrode potential data in the table below to answer the
questions which follow.
E /V
2+
Zn (aq) + 2e
3+
V (aq) + e
Fe (aq) + e
VO +2 (aq) + 2H+(aq) + e
Cl2(aq) + 2e
(a)
Zn(s)
0.76
V2+(aq)
0.26
SO 32 (aq)
V3+(aq)
+ H2O(l)
+0.17
+ H2O(l)
+0.34
Fe2+(aq)
2+
VO (aq)
+0.77
+ H2O(l)
2Cl(aq)
+1.00
+1.36
From the table above select the species which is the most powerful reducing agent.
.....................................................................................................................................
(1)
(b)
+
2+
a species which, in acidic solution, will reduce VO 2 (aq) to VO (aq) but will not
2+
3+
reduce VO (aq) to V (aq),
...........................................................................................................................
(ii)
+
2+
a species which, in acidic solution, will oxidise VO (aq) to VO2 (aq) .
...........................................................................................................................
(2)
68
(c)
3+
3+
Tl (aq) + 2e Tl (aq)
...........................................................................................................................
...........................................................................................................................
(ii)
(d)
(i)
Use the equation for this reaction to determine the concentration, in g dm , of the
hydrogen peroxide solution.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
69
(ii)
18.
Use the data in the table below, where appropriate, to answer the questions which follow.
2+
Fe (aq) + e F2 (aq)
E /V
+0.77
+1.36
+1.52
O3(g) + 2H (aq) + 2e
F2O(g) + 2H (aq) + 4e
O2(g) + H2O(l)
2F (aq) + H2O(l)
+2.08
+2.15
(a)
(i)
...........................................................................................................................
(ii)
(iii)
Identify all the species in the table which can be oxidised in acidic solution by BrO
(aq).
...........................................................................................................................
(4)
70
(b)
2+
(aq), Fe
3+
(ii)
Write a half-equation for the reaction occurring at the negative electrode when
current is taken from this cell.
...........................................................................................................................
(iii)
3+
71