UNIT 16 ELECTROCHEMISTRY REVISION (KCU)

OXIDATION NUMBERS, OXIDATION AND REDUCTION

1. Assign oxidation numbers to each element in the following:

a. MnO2 b. NO2 c. Cl2

Mn + 2O = 0 N + 2O = 0 2Cl = 0
Mn + 2(-2) = 0 N + 2(-2) = 0 Cl = 0
Mn + -4 = 0 N+-4 =0
Mn = + 4 and O = - 2 N = +4 and O = - 2

d. ClO4- e. SO42- f. Fe2O3

Cl + 4O = - 1 S + 4O = - 2 Reverse cross-over
Cl + 4(-2) = - 1 S + 4(-2) = - 2 Fe = +3 and O = - 2
Cl + - 8 = - 1 S+-8 =-2 or
Cl = + 7 and O = - 2 S = + 6 and O = - 2 2Fe + 3O = 0
2Fe + 3(-2) = 0
2Fe + - 6 = 0
2Fe = + 6
Fe = + 3 and O = - 2

g. H3PO4 h. HPO42- i. CH4

3H + P + 4O = 0 H + P + 4O = - 2 C + 4H = 0
3(+1) + P + 4(-2) = 0 +1 + P + 4(-2) = - 2 C + 4(+1) = 0
+3 + P +-8 =0 P-7 =-2 C+ 4 =0
P = + 5, H = +1 P = + 5, H = +1 C = - 4 and O = - 2
and O = -2 and O = - 2

j. CO2 k. H2O2 l. Cu2+

C + 2O = 0 2H + 2O = 0 Cu = + 2
C + 2(-2) = 0 2(+1) + 2O = 0
C+-4 =0 +2 + 2O = 0
C = + 4 and O = - 2 2O = - 2
O = - 1 and H = +1
(An exception to O = - 2)

m. Ag n. Cr2O72- o. IO3-
Ag = 0 2Cr + 8O = -2 I + 3O = - 1
2Cr + 8(-2) = - 2 I + 3(-2) = - 1
2Cr + - 16 = - 2 I +-6 =-1
2Cr = +14 I = + 5 and O = - 2
Cr = +7 and O = - 2

p. Mn2+ q. NO3- r. SO32-

Mn = + 2 N + 3O = - 1 S + 3O = - 2
N + 3(-2) = - 1 S + 3(-2) = - 2
N +-6 =-1 S +-6 =-2
N = + 5 and O = - 2 S = + 4 and O = - 2

s. SO2 t. NO2 u. NO
S + 2O = 0 N + 2O = 0 N+O =0
S + 2(-2) = 0 N + 2(-2) = 0 N + -2 = 0
S+-4 =0 N +-4 =0 N = + 2 and O = - 2
S = + 4 and O = - 2 N = + 4 and O = -2

v. I- w. Al3+ x. H2S
I=-1 Al = + 3 2H + S = 0
2(+1) + S = 0
+2 + S = 0
S = -2 and H = +1
2. Complete the following table

DEFINITION OXIDATION REDUCTION

Gain/Loss of Oxygen Gain of oxygen Loss of oxygen

Gain/Loss of electrons Loss of electrons Gain of electrons

Increase/Decrease in Increase in O.N. Decrease in O.N.

oxidation number

3. Identify which of the following are redox reactions. Justify your answer.

0 ---------ox.---------> +3
a. 2Fe(s) + 3Cu2+(aq) 2Fe3+(aq) + 3Cu(s) Redox reaction oxidation and reduction occurs.
+2 -----------red.----------> 0

0 -------ox.------> +3
b. 4Fe(s) + 3O2(g) 2Fe2O3(s) Redox reaction oxidation and reduction occurs.
0-----red.---> -2

b. HCN(aq) + NaOH(aq) H2O(l) + NaCN(aq)

H = + 1, CN = - 1, Na = + 1 and O = - 2 for reactants and products not a redox reaction.

+2 -------red.--------> 0
c. PbS(s) + O2(g) Pb(s) + SO2(g) Redox reaction oxidation and reduction occurs.
-2 -----------ox.--------------> +4

e. AgNO3(aq) + NaCl(s) AgCl(s) + NaNO3(aq)

Ag = + 1, NO3 = -1, Na = +1 and Cl = - 1 for reactants and products not a redox reaction.

f. Ag+(aq) + Cl-(aq) AgCl(s)

Ag = + 1 and Cl = - 1 for reactants and products not a redox reaction.

 BALANCING REDOX EQUATIONS

4. Balance the following reactions using the half-equation method

i) SO2 + H2O + I2 I- + SO42- + H+

OX: SO2(g) + 2H2O(l) SO42-(aq) + 4H+ + 2e-

RED: I2(s) + 2e- 2I-(aq)

O/A: SO2(g) + 2H2O(l) + I2(s) SO42-(aq) + 4H+ + 2I-(aq)

ii) H+ + I- + NO2- I2 + NO + H2O

OX: 2I- I2 + 2e-

RED: NO2- + 2H+ + e- NO + H2O ] x 2

O/A: 2I- + 2NO2- + 4H+ 2NO + 2H2O + I2

iii) Cr2O72- + Sn2+ + H+ Sn4+ + Cr3+ + H2O

OX: Sn2+ Sn4+ + 2e- ]x3

RED: Cr2O72- + 14H+ + 6e- 2Cr3+ + 7H2O

O/A: 3Sn2+ + Cr2O72- + 14H+ 3Sn4+ + 2Cr3+ + 7H2O

iv) MnO4- + O2- + H+ Mn2+ + O2 + H2O

OX: 2O2- O2 + 4e- ]x5

RED: MnO4- + 8H+ + 5e- Mn2+ + 4H2O ]x4

O/A: 10O2- + 4MnO4- + 32H+ 5O2 + 4Mn2+ + 16H2O

5. Using the half-equation method, write balanced equations for the reactions between:

i) Cu2+(aq) and Fe(s). The products are Cu(s) and Fe3+(aq).

OX: Fe(s) Fe3+(aq) + 3e- ]x2

RED: Cu2+(aq) + 2e- Cu(s) ]x3

O/A: 2Fe(s) + 3Cu2+(aq) 2Fe3+(aq) + 3Cu(s)

ii) NO3-(aq) and Cu(s) in an acidic environment. The main products are NO2(g) and Cu2+(aq).

OX: Cu(s) Cu2+(aq) + 2e-

RED: NO3-(aq) + 2H+(aq) + e- NO2(g) + H2O(l) ]x2

O/A: Cu(s) + 2NO3-(aq) + 4H+(aq) Cu2+(aq) + 2NO2(g) + 2H2O(l)

iii) ClO3-(aq) and Br-(aq) in an acidic environment. The main products are Cl-(aq) and Br2(aq).

OX: 2Br-(aq) Br2(aq) + 2e- ]x3

RED: ClO3-(aq) + 6H+ + 6e- Cl-(aq) + 3H2O(l)

O/A: 6Br-(aq) + ClO3-(aq) + 6H+ 3Br2(aq) + Cl-(aq) + 3H2O(l)

iv) MnO4-(aq) and SO2(aq), in acid . The main products are Mn2+(aq) and SO42-(aq).

OX: SO2(g) + 2H2O(l) SO42-(aq) + 4H+(aq) + 2e- ] x 5

RED: MnO4-(aq) + 8H+ + 5e- Mn2+(aq) + 4H2O(l) ]x2

O/A: 2MnO4-(aq) + 16H+ + 10e- + 5SO2(g) + 10H2O(l) 2Mn2+(aq) + 8H2O(l) + 5SO42-(aq) + 20H+(aq) + 10e-

2MnO4-(aq) 5SO2(g) + 2H2O(l) 2Mn2+(aq) + 5SO42-(aq) + 4H+(aq)

6. Balance the following reactions using the oxidation number method

-2 ------------ ox. ---------> 0

i) 3H2S (g) + 2HNO3 (conc) 3S (s) + 4H2O (l) + 2NO (g)
+5 ------------------ red. -----------> +2

S -2 0 +2 ] x 3 multiply all S species by 3

N +5 +2 -3 ] x 2 multiply all N species by 2

Balance all other atoms.

+4 -------------ox.----------> +6
ii) SO2 (g) + 2HNO3 (conc) H2SO4 (aq) + 2NO2 (g)
+5 --------------red.-----------> +4

S +4 +6 +2
N +5 +4 -1 ] x 2 multiplt N species by 2

Balance all other atoms.

0 -------------ox. ---------> +10

iii) I2 (g) + 10HNO3 (conc) 2HIO3 (aq) + 10NO2 (g) + 13H2O (l)
+5 ------------red.---------->+4

I 0 +5 +5
N +5 +4 -1 ] x 10 multiply all N species by 10

Balance all other atoms

+5 ------red.------->+2
iv) 8HNO3 (dil) + 6KI 2NO (g) + 3I2 (g) + 6KNO3(aq) + 4H2O (l)
-1 ------ox-------->0

Balance N and I (Place a 2 out the front of KI)

N +5 +2 -3 ] x 2 multiply all N species by 2
I -2 0 +2 ] x 3 multiply all I species by 3

Balance all other atoms

v) HNO3 + 3HCl (conc) NOCl + Cl2 (g) + 2H2O

 ELECTROCHEMICAL SERIES/STANDARD REDUCTION POTENTIALS

7. Using the following reactions, place the metals in order of increasing reactivity. Explain your
reasoning.

i) Mn(s) + Hg2+(aq) Mn2+(aq)+ Hg(l)

ii) Ni2+(aq) + Mn(s) Ni(s) + Mn2+(aq)
2+
iii) Hg (aq) + Ni(s) Hg(l) + Ni2+(aq)

From (i) Mn is a stronger reducing agent (more reactive) than Hg as it reduces Hg 2+ to Hg while
being oxidised itself. Mn > Hg
From (ii) Mn is a stronger reducing agent (more reactive) than Ni as it reduces Ni2+ to Ni while
being oxidised itself. Mn > Ni
From (iii) Ni is a stronger reducing agent (more reactive) than Hg as it reduces Hg 2+ to Hg while
being oxidised itself. Ni > Hg
From the above conclusions Hg < Ni < Mn

8. The following information is given about reactions involving the metals X, Y and Z and
solutions of their sulfates.

(i) X(s) / YSO4(aq) no reaction

(ii) Z(s) + YSO4(aq) Y(s) + ZSO4(aq)

When the metals are listed in decreasing order of reactivity (most reactive first), what is the
correct order? Explain your reasoning.

From (i) Y is more reactive than X as it remains in its oxidised form while X remains in its
reduced form. Y2+ is not able to oxidise X and X is not able to reduce Y2+ suggesting X is a
weaker reducing agent than Y. Y > X
From (ii) Z is a stronger reducing agent (more reactive) than Y as it reduces Y2+ to Y and is
oxidised itself. Z > Y
From the above conclusions Z > Y > X

9. Predict whether reactions could occur in the following. Assume standard conditions. Justify your
responses.
a) Chlorine gas is bubbled through a solution of potassium bromide
b) Fluorine gas is bubbled through a solution of sodium chloride
c) Iodine is added to a solution of potassium fluoride

a) Cl2 (aq) + 2Br-(aq) 2Cl-(aq) + Br2(aq) + 0.29V (spontaneour)

Cl2 is a strong oxidising agent while Br- is a reducing agent. This reaction will occur.
b) F2(aq) + 2Cl-(aq) 2F-(aq) + Cl2(aq) +1.52V (spontaneous)
F2 is a strong oxidising agent while Cl- is a reducing agent. This reaction will occur.
c) I2(aq) + F-(aq) no reaction -2.34V (non-spontaneous)
F2 is a stronger oxidising agent than I2. This reaction will not occur.
10. Three beakers, labelled A, B and C, were set up containing solutions as shown below. A rod of
nickel is placed in each beaker. Aqueous solution of lead (II) nitrate and magnesium nitrate are
colourless. Nickel nitrate solution is green.

a) In which, if any, of the three beakers will a reaction occur?

b) Write half-equations for any reactions that occur, identifying the beaker in which the
reactions occur
c) Identify the reductant in any reactions that occur
d) Describe any colour changes that you would expect to see in any of the beakers and explain
why this occurs

a) A reaction will only occur in beaker A. (Justify)

b) Beaker A
OX: Ni(s) Ni2+(aq) + 2e-
RED: Pb2+(aq) + 2e- Pb(s)
O/A: Ni(s) + Pb2+(aq) Ni2+(aq) + Pb(s)

c) Ni is the reductant (reducing agent)

d) The solution will become Ni(NO3)2 which is green. The solution will turn from colourless to
green.
11. Three beakers, labelled 1, 2 and 3, were set up containing aqueous solutions of B2+, C2+ and C2+
respectively as shown below

Rods of metal A were placed in beakers 1 and 3, and a rod of metal B was placed in beaker 2.
Reactions occurred in beakers 2 and 3, but not in beaker 1.

a) Write half-equations for the reactions that occur in beakers 2 and 3.

(Note that metal A forms A2+ ions.)

b) From the substances in the three beakers name:

i) The strongest reductant
ii) The strongest oxidant

c) Write an electrochemical series for the three elements in beakers 1, 2 and 3.

a) Beaker 2 Beaker 3
OX: B(s) B2+(aq) + 2e- OX: A(s) A2+(aq) + 2e-
RED: C2+(aq) + 2e- C(s) RED: C2+(aq) + 2e- C(s)
O/A: B(s) + C2+(aq) B2+(aq) + C(s) O/A: A(s) + C2+(aq) A2+(aq) + C(s)

b) B is the stronger reductant A is the stronger reductant

C2+ is the stronger oxidant C2+ is the stronger oxidant

c) Oxidising strength C2+ > A2+ > B2+ (Using beaker 1 A2+ > B2+)
Reducing strength B > A > C (Using beaker 1 B > A)
12. For the electrochemical cell shown below state:
a) the direction of electron flow in the external circuit
b) the half-equations that occur at each electrode
c) the overall reaction
d) which electrode is the anode
e) which electrode is positive
f) which way negative ions flow in the salt bridge

a) Electrons flow from the anode (Fe) to the cathode (Pb)

b) OX: Fe(s) Fe2+(aq) + 2e- RED: Pb2+(aq) + 2e- Pb(s)
c) Fe(s) + Pb2+(aq) Fe2+(aq) + Pb(s) +0.31V
d) Fe is the anode (-)
e) Pb is the cathode (+)
f) The negative ions flow from the reduction half-cell to the oxidation half-cell via the salt
bridge.
13. An electrochemical cell was setup by joining two half-cells. One half-cell consisted of a piece of
nickel standing in an aqueous solution of nickel chloride. The other half-cell consisted of a
piece of copper standing in a solution of copper (II) sulfate.

a) Draw a labelled diagram of the cell and show

i) The direction of electron flow in the external circuit
ii) Which electrode is the anode
iii) Which electrode is positive
iv) Which way negative ions flow in the salt bridge
--------- e- -------->

Ni ANODE (-) Cu CATHODE (+)

<--anions

Cu(SO4)2
NiCl2

b) Write a half-equation for the reaction at each electrode

ANODE OXIDATION: Ni(s) Ni2+(aq) + 2e-

CATHODE REDUCTION: Cu2+(aq) + 2e- Cu(s)

c) Write a full equation for the overall reaction in the electrochemical cell

Ni)s) + Cu2+(aq) Ni2+(aq) + Cu(s)

14. Calculate the cell voltage predicted for a cell made from tin in a Sn2+ solution and aluminium in
an Al3+ solution.

RED: Sn2+(aq) + 2e- Sn(s) -0.14V

OX: Al(s) Al3+(aq) + 3e- +1.66V

O/A: 3Sn2+(aq) + 2Al(S) 3Sn(s) + 2Al3+(aq) +1.52V

15. Draw and fully label the electrochemical cell in Question 14. Specify all solutions used and the
direction of electron and ion flow.
--------- e- -------->

Al ANODE (-) Sn CATHODE (+)

<--anions

Al3+(aq) Sn2+(aq)

16. Predict whether the following reactions (unbalanced) could proceed under standard
conditions. Justify your responses.

a. Sn4+(aq) + H2O2(aq) Sn2+(aq) + H+(aq) + O2(g)

Sn4+(aq) + 2e- Sn2+(aq) +0.13V

+
H2O2 2H (aq) + O2(g) +2e- -0.68V
-0.55V non-spontaneous

b. Cr2O72-(aq) + F-(aq) + H+(aq) Cr3+(aq) + F2(g) + H2O(l)

Cr2O72-(aq) + 14H+(aq) + 6e- 2Cr3+(aq) + 7H2O(l) +1.33V

2F-(aq) F2 (g) + 2e- -2.87V
-1.54V non-spontaneous

c. Cu(s) + H+(aq) Cu2+(aq) + H2(g)

Cu(s) Cu2+(aq) + 2e- -0.34V

+
2H (aq) + 2e- H2(g) 0.00V
-0.34V non-spontaneous

d. K(s) + H2O(l) KOH(aq) + H2(g)

K(s) K+(aq) + e- +2.93V

2H2O(l) + 2e- 2OH-(aq) + H2(g) -0.83V
+2.10V spontaneous
17. Using the table of standard reduction potentials find:

a) A reducing agent that will convert Pb2+ to Pb but not Cd2+ to Cd

Anything between 0.13 and 0.40 e.g. Sn, Ni or Co.

b) An oxidising agent that will convert Cl- to Cl2 but not F- to F2

Anything between 2.87 and 1.36 e.g. Co2+, PbSO4, Au or Mn2+.

c) A metal that will reduce water to hydrogen and a metal that will not

Anything below on the SRP e.g. Mn, Al, Mg, Na etc will reduce water to hydrogen.
Anything above will not e.g. Zn, Fe, Ni etc.

18. A standard Zn2+/Zn half-cell and a standard Cu2+/Cu half-cell were connected and allowed to
run spontaneously.

a) Write the oxidation and reduction half-equations as well as the overall reaction equation

ANODE OXIDATION: Zn(s) Zn2+(aq) + 2e- +0.76V

2+
CATHODE - REDUCTION: Cu (aq) + 2e- Cu(S) +0.34V
OVERALL: Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s) +1.10V

b) Using the SRP table calculate the voltage produced as the cell first starts to operate

+1.10V

c) Describe the effect on cell voltage of (Refer to Le Chateliers Principle)

i) Increasing the concentration of Zn2+

Decrease voltage

ii) Increasing the concentration of Cu2+

Increase voltage

iii) Doubling the size of the Cu electrode

No significant effect on voltage. Minor increase in voltage.

iv) Letting the cell run for half an hour

Decrease in voltage
 ELECTROLYTIC CELLS/ELECTROLYSIS

19. Compare and contrast electrochemical cells with electrolytic cells

Electrochemical Cell Electrolytic Cell

Spontaneous redox reactions Redox reactions Non-spontaneous redox
E0 positive involve reduction and reactions
oxidation reactions. E0 negative
Cathode (+) Reduction occurs at the Cathode (-)
cathode
Anode (-) Oxidation occurs at the Anode (+)
anode
Produces a voltage Requires a voltage to occur
Salt bridge connects two half- Electrons move Anode and cathode in a
cells Anode cathode common electrolyte

20. In the electrolysis of the following molL-1 solutions, predict

i. The products formed at each electrode

ii. The equations for the anode and cathode reactions
iii. The overall reaction
iv. The minimum voltage that must be applied to produce the overall reaction

a. CuI2

i. Anode: I2 produced Cathode: Cu produced

ii. Anode Cathode

2H2O(l) O2(g) + 4H+(aq) + 4e- -1.23V 2H2O(l) + 2e- H2(g) + 2OH-(aq) -0.83V
or or
2I-(aq) I2(aq) + 2e- -0.53V Cu2+(aq) + 2e- Cu(s) +0.34V

iii. Cu2+(aq) + 2I-(aq) Cu(s) + I2(aq) -0.19V

iv. At least 0.19V must be applied for the overall reaction to occur

b. HBr

i. Anode: Br2 produced Cathode: H2 produced

ii. Anode Cathode

2H2O(l) O2(g) + 4H+(aq) + 4e- -1.23V 2H2O(l) + 2e- H2(g) + 2OH-(aq) -0.83V
Or or
2Br-(aq) Br2(aq) + 2e- -1.07V H+(aq) + e- H2(g) 0.00V

iii. 2Br-(aq) + 2H+(aq) Br2(aq) + H2(g) -1.07V

iv. At least 1.07V must be applied for the overall reaction to occur
 c. AgNO3 with a silver anode

i. Anode: Ag+(aq) produced Cathode: Ag(s) produced

ii. Anode Cathode
2H2O(l) O2(g) + 4H+(aq) + 4e- -1.23V 2H2O(l) + 2e- H2(g) + 2OH-(aq) -0.83V
Or or
Ag(s) Ag+(aq) + e- -0.80V Ag+(aq) + e- Ag(s) +0.80V

iii. Ag(s) + Ag+(aq) Ag+(aq) + Ag(s) 0.00V

iv. 0.00V is required for the overall reaction to occur

Q = It n(e-) = Q/96500

21. How many coulombs per hour pass through an electroplating bath that uses a current of 5
amperes.

Q = 5 x (60 x 60) = 18,000 C (1.8x104C)

22. Calculate the current required to deposit 5.0g of gold per hour on the cathode from a solution
containing Au3+.

Au3+(aq) + 3e- Au(s)

m(Au) = 5.0g
n(Au) = m/MM = 5.0/197.0 = 0.02538 mol
n(e-) = n(Au) x 3 3:1 ratio
= 0.07614 mol
Q = n(e-) x F
= 0.07614 x 96500
= 7347.7 C
I = Q/t
= 7347.7/(1 x 60 x 60)
= 7347.7/3600
= 2.04A

23. The Hall-Heroult cell is used to electrolytically extract Al from alumina (Al 2O3). In the process
Al2O3 is dissolved in molten cryolite and an electric current 250 000A is passed through the
solution. The Al3+ is reduced to molten Al at the cathode and the carbon anode is oxidised to
carbon dioxide. What would be the daily output of Al from the Hall-Heroult cell?

Q = 250000 x (24 x 60 x 60) = 21600000000 C = 2.16 x 1010 C

n(e-) = Q/96500 = 2.16 x 1010/96500 = 223 834 moles of electrons

3 : 1
Al3+(aq) + 3e- Al(s)

n(Al) = n(e-)/3
= 223 834/3
= 74 611.4 moles of Al

m = n x MM = 74 611.4 x 26.98 = 2 010 777g = 2 010.8kg = 2.011 tonnes

24. What volume of O2 (g) at OC and 101.3 kPa is produced when 5 A of current is passed through
a dilute aqueous solution of KCl for 5 minutes.

Anode
2H2O(l) O2(g) + 4H+(aq) + 4e- -1.23V

Q = It
= 5 x 5 x 60
= 1500 C

n(e-) = Q/96500
= 1500/96500
= 0.0155 moles

n(O2) = n(e-)/4
= 0.0155/4
=0.0039

V = n x MV
= 0.0039 x 22.4
= 0.0874 L
= 87.4 mL

25. By referring to the SRP table design an electrochemical cell that could act as a power source to
electrolyse molten lead(II)iodide, PbI2, to produce lead metal and iodine

Electrolysis

Anode: 2I-(aq) I2(aq) + 2e- -0.53V

Cathode: Pb2+(aq) + 2e- Pb(s) -0.13V

O/A: 2I-(aq) + Pb2+(aq) I2(aq) + Pb(s) -0.66V

The electrochemical cell needs to produce at least 0.66V.

26. Lithium metal is prepared by electrolysis of a molten mixture of lithium chloride and
potassium chloride.

a) Write a half-equation for the reaction occurring at the cathode in this cell

Li+(aq) + e- Li(l)

b) Write a half-equation for the reaction occurring at the anode in this cell

2Cl-(aq) Cl2(g) + 2e-

c) Why is it not possible to produce lithium metal by the electrolysis of an aqueous solution of
lithium chloride?

Anode Cathode
2H2O(l) O2(g) + 4H+(aq) + 4e- -1.23V 2H2O(l) + 2e- H2(g) + 2OH-(aq) -0.83V
or or
2CI-(aq) CI2(aq) + 2e- -1.36V Li+(aq) + e- L(s) -3.05V

If an aqueous solution was present. Water would be reduced and not the Li+. Li would not be
able to be produced.

d) Suggest why a mixture of lithium chloride and potassium chloride is used rather than pure
lithium chloride, in this electrolytic process?

e) Assuming that lithium reacts in a similar way to sodium, describe two precautions that
would need to be taken in this preparation