CHEM1612 2014-N-12 November 2014

• In the electrolytic production of Al, what mass of Al can be deposited in 2.00 hours 2
by a current of 1.8 A?

The number of moles of electrons passed in 2.00 hours by a current of 1.8 A is:

number of moles of electrons = It / F

= (1.8 A)(2.00 × 60.0 × 60.0 s) / 96485 C mol-1
= 0.13 mol

Aluminium is produced from Al2O3 which contains Al3+. 3 electrons are needed
to produce each Al so 3 mol of electrons are needed to produce 1 mol of Al. This
quantity of electrons will therefore deposit:

number of moles of Al = 0.13 / 3 mol = 0.045 mol

As Al has a molar mass of 26.98 g mol-1, this quantity corresponds to:

mass of Al = number of moles × molar mass

= 0.045 mol × 26.98 g mol-1 = 1.2 g

Answer: 1.2 g

• What products would you expect at the anode and the cathode on electrolysis of a 2
1 M aqueous solution of NiI2? Explain your answers.

At the cathode, there are two possible reduction reactions:

Ni2+(aq) + 2e- à Ni(s) Eo = -0.24 V

2H2O(l) + 4H+(aq) + 4e- à H2(g) + OH-(aq) Eo = -0.41 V

Reduction of Ni2+(aq) is easier, even without considering an overpotential for

water.

At the anode, there are two possible oxidation reactions:

2I-(aq) à I2(g) + 2e- Eo = -0.62 V

2H2O(l) à O2(g) + 4H+(aq) + 4e- Eo = -0.82 V

Both reactions will have an overpotential but oxidation of iodine is easier and
this will probably occur.

Overall, Ni(s) will be produced at the cathode and I2(g) will be produced at the
anode.
CHEM1612 2014-N-13 November 2014
Marks
• An electrochemical cell is consists of 1.0 L half-cells of Fe/Fe2+ and Cd/Cd2+ with the 8
following initial concentrations: [Fe2+] = 0.800 M, [Cd2+] = 0.200 M.
What is the initial Ecell at 25 °C?

From the reduction potential table,

Ecello (Fe2+(aq) + e– → Fe(s)) = -0.44 V

Ecello (Cd2+(aq) + e– → Cd2+(aq)) = -0.40 V

The Fe2+/Fe half cell has the more negative reduction potential so it is the half
cell that is turned around to act as the oxidation half cell: Ecello (Fe(s) → Fe2+(aq)
+ e– ) = +0.44 V

In combination with the Cd2+/Cd reduction half cell, this gives an overall
reaction and cell potential of:

Fe(s) + Cd2+(aq) → Fe2+(aq) + Cd(s) Eo = ((+0.44) + (-0.40)) V = +0.04 V

For this reaction with [Fe2+(aq)] = 0.800 M and [Cd2+(aq)] = 0.200 M:

[𝐅𝐞𝟐! 𝐚𝐪 ] 𝟎.𝟖𝟎𝟎
Q= =
[𝐂𝐝𝟐! 𝐚𝐪 ] 𝟎.𝟐𝟎𝟎

For the 2e- reaction, the Nernst equation gives the cell potential as:

𝑹𝑻
Ecell = E° - lnQ
𝒏𝑭
(𝟖.𝟑𝟏𝟒  𝐉  𝐊 !𝟏  𝐦𝐨𝐥!𝟏 )(𝟐𝟗𝟖  𝐊) 𝟎.𝟖𝟎𝟎
= (0.04 V) – 𝐥𝐧 𝟎.𝟐𝟎𝟎 = +0.02 V
(𝟐  ×  𝟗𝟔𝟒𝟖𝟓  𝐂  𝐦𝐨𝐥!𝟏 )

Answer: +0.02 V

What is Ecell when [Cd2+] reaches 0.15 M?

[Cd2+(aq)] has decreased from 0.200 M to 0.15 M: a change of 0.05 M. [Fe2+(aq)]

will increase by the same amount: [Fe2+(aq)] = (0.800 + 0.05) M = 0.85 M. Using
the Nernst equation again gives:

𝑹𝑻
Ecell = E° - lnQ
𝒏𝑭
(𝟖.𝟑𝟏𝟒  𝐉  𝐊 !𝟏  𝐦𝐨𝐥!𝟏 )(𝟐𝟗𝟖  𝐊) 𝟎.𝟖𝟓
= (0.04 V) – 𝐥𝐧 𝟎.𝟏𝟓 = +0.02 V
(𝟐  ×  𝟗𝟔𝟒𝟖𝟓  𝐂  𝐦𝐨𝐥!𝟏 )

Answer: +0.02 V
ANSWER CONTINUES ON THE NEXT PAGE
CHEM1612 2014-N-13 November 2014

What is [Cd2+] when Ecell reaches 0.015 V?

(𝟖.𝟑𝟏𝟒  𝐉  𝐊 !𝟏  𝐦𝐨𝐥!𝟏 )(𝟐𝟗𝟖  𝐊) [𝐅𝐞𝟐+ 𝐚𝐪 ]

Ecell = (0.04 V) – 𝐥𝐧 𝟐+ = +0.015 V
(𝟐  ×  𝟗𝟔𝟒𝟖𝟓  𝐂  𝐦𝐨𝐥!𝟏 ) [𝐂𝐝 𝐚𝐪 ]

so:

[𝐅𝐞𝟐! 𝐚𝐪 ]
= 7.0
[𝐂𝐝𝟐! 𝐚𝐪 ]

If the change from the initial concentrations is x, [Cd2+(aq)] = (0.200 – x) M and

[Fe2+(aq)] = (0.800 + x) M:

𝟎.𝟖𝟎𝟎  –  𝒙
= 7.0 x = -0.075 M
𝟎.𝟐𝟎𝟎!𝒙

So that [Cd2+(aq)] = (0.200 - 0.075) M = 0.125 M.

Answer: 0.125 M

What are the equilibrium concentrations of both ions?

𝑹𝑻
Using E° = lnK = 0.04 V gives K = 22.5
𝒏𝑭

so:

[𝐅𝐞𝟐! 𝐚𝐪 ]
= 22.5
[𝐂𝐝𝟐! 𝐚𝐪 ]

If the change from the initial concentrations is x, [Cd2+(aq)] = (0.200 – x) M and

[Fe2+(aq)] = (0.800 + x) M:

𝟎.𝟖𝟎𝟎  –  𝒙
= 22.5 x = 0.158 M
𝟎.𝟐𝟎𝟎!𝒙

So that [Cd2+(aq)] = (0.200 – 0.158) M = 0.042 M and [Fe2+(aq)] = (0.800 + 0.158)

M = 0.958 M

[Cd2+] = 0.042 M [Fe2+] = 0.958 M

CHEM1612 2013-N-11 November 2013
Marks
• What is the electrochemical potential of the following cell at 25 oC? 3
Fe│FeSO4 (0.010 M)║(FeSO4 (0.100 M)│Fe

As this is a concentration cell, Eo = 0 V. The cell notation corresponds to the

0.100 M solution being the cathode, where reduction occurs, and the 0.010 M
solution being the anode, where oxidation occurs. The two half cells are:

Anode: Fe(s) à Fe2+(aq, 0.010 M) + 2e-

Cathode: Fe2+(aq, 0.100 M) + 2e- à Fe(s)
Overall: Fe2+(aq, 0.100 M) à Fe2+(aq, 0.010 M)

The potential is given by the Nernst equation for this two electron reaction:

𝑹𝑻
E = E° - lnQ
𝒏𝑭

(𝟖.𝟑𝟏𝟒  𝐉  𝐊 !𝟏  𝐦𝐨𝐥!𝟏 )(𝟐𝟗𝟖  𝐊) (𝟎.𝟎𝟏𝟎)

= (0 V) – ln = +0.0296 V
𝟐  ×  𝟗𝟔𝟒𝟖𝟓  𝐦𝐨𝐥!𝟏 (𝟎.𝟏𝟎𝟎)

Answer: +0.0296 V

• Calculate the mass of aluminium which can be produced with the same quantity of
2
electricity that is used to produce 1.00 kg of copper metal.

As the molar mass of Cu is 63.55 g mol-1, 1.00 kg corresponds to:

number of moles = mass / molar mass

= 1.00 × 103 g / 63.55 g mol-1 = 15.7 mol.

Reduction of Cu2+ requires 2 mol of electrons. Hence, the number of electrons

requires to produce 15.7 mol is:

number of moles of electrons = 2 × 15.7 mol = 31.5 mol

Reduction of a mole of Al3+ requires 3 mol of electrons. Hence, the number of

moles of aluminium produced by 31.5 mol of electrons is:

number of moles of aluminium = 31.5 / 3 mol = 10.5 mol

As the molar mass of aluminium is 26.98 g mol-1, this corresponds to:

mass = number of moles × molar mass = 10.5 mol × 26.98 g mol-1 = 283 g.

Answer: 283 g
ANSWER CONTINUES ON THE NEXT PAGE
CHEM1612 2013-N-11 November 2013

• Explain why Na(s) cannot be obtained by the electrolysis of aqueous NaCl solutions.
2

From the table of standard reduction potentials:

2H2O + 2e– → H2(g) + 2OH–(aq) E° = –0.83 V
Na+(aq) + e– → Na(s) E° = –2.71 V
Water has a much greater reduction potential than Na+ and hence is
preferentially reduced, even when the overpotential of water is considered.
CHEM1612 2012-N-11 November 2012
Marks
• A galvanic cell consists of a Cr3+/Cr half-cell with unknown [Cr3+] and a Ni2+/Ni half- 6
cell with [Ni2+] = 1.20 M. The electromotive force of the cell at 25 °C was measured
to be 0.55 V. What is the concentration of Cr3+ in the Cr3+/Cr half-cell?

From the standard reduction potentials,

Cr3+(aq) + 3e- à Cr(s) Eo = -0.74 V

Ni2+(aq) + 2e- à Ni(s) Eo = -0.24 V

The most negative is reversed to give an overall reaction and cell potential of

3Ni2+(aq) + 2Cr(s) à 3Ni(s) + 2Cr3+(aq) Eo = (+0.74 – 0.24) V = 0.50 V

From the Nernst equation for this 6 electron reaction,

𝑹𝑻 𝑹𝑻 [𝐂𝐫 𝟑! 𝐚𝐪 ]𝟐
E = E° - lnQ = E° - ln
𝒏𝑭 𝒏𝑭 [𝐍𝐢𝟐! 𝐚𝐪 ]𝟑

(𝟖.𝟑𝟏𝟒  𝐉  𝐊 !𝟏  𝐦𝐨𝐥!𝟏 )(𝟐𝟗𝟖  𝐊) [𝐂𝐫 𝟑! 𝐚𝐪 ]𝟐

= (0.50 V) – ln
𝟔  ×  𝟗𝟔𝟒𝟖𝟓  𝐦𝐨𝐥!𝟏 (𝟏.𝟐𝟎)𝟑

Solving this gives,

[Cr3+(aq)] = 3.8 × 10–3 M

Answer: 3.8 × 10–3 M

Calculate the equilibrium constant of the reaction at 25 °C.

The equilibrium constant is related to the standard cell potential through:

𝑹𝑻
Eo = lnK
𝒏𝑭

Using Eo = +0.50 V,

(𝟖.𝟑𝟏𝟒  𝐉  𝐊 !𝟏  𝐦𝐨𝐥!𝟏 )(𝟐𝟗𝟖  𝐊)

0.50 V = lnK
𝟔  ×  𝟗𝟔𝟒𝟖𝟓  𝐦𝐨𝐥!𝟏

Solving this gives:

K = 5.5 × 1050
Answer: 5.5 × 1050
ANSWER CONTINUES ON THE NEXT PAGE
CHEM1612 2012-N-11 November 2012

Calculate the standard Gibbs free energy of the reaction at 25 °C.

The Gibbs free energy change is related to the standard cell potential through:

ΔGo = -nFEo
= - 6 × (96485 mol-1) × (0.50 V) = -290 kJ mol-1

Answer: -290 kJ mol-1

Express the overall reaction in the shorthand voltaic cell notation.

Cr(s) | Cr3+(aq) || Ni2+(aq) | Ni(s)

CHEM1612 2012-N-12 November 2012
Marks
• A strip of copper and a strip of zinc are embedded in a lemon, and are connected by 3
wires to a voltmeter; a voltage is generated and can be read at the voltmeter. What
chemical reactions are occurring that lead to the generation of current?

Zn(s) → Zn2+(aq) + 2e– at the anode

2H+(aq) + 2e– → H2(g) at the cathode

Assuming there are no losses in the circuit and the conditions are similar to standard,
what voltage can be read at the voltmeter?

The Zn2+ / Zn reduction potential is the more negative so is reversed to give Eoox
= +0.76 V. The H+ / H2 reduction potential is Eored = 0.00 V. Overall

Eo = Eoox + Eored = (+0.76 + 0.00) V = +0.76 V

CHEM1612 2012-N-13 November 2012
Marks
• A 20.0 mL sample of 0.121 M Fe2+ in an acid solution was used to titrate 23.5 mL of 4
a KMnO4 solution of unknown concentration. Write the balanced redox reaction that
occurs in solution upon titration, and calculate the molarity of the KMnO4 solution.

From the standard reduction potentials, the two relevant half cells are:

MnO4-(aq) + 8H+(aq) + 5e- à Mn2+(aq) + 4H2O(l)

Fe2+(aq) à Fe3+(aq)

Giving the overall reaction:

5Fe2+(aq) + MnO4-(aq) + 8H+(aq) à 5Fe3+(aq) + Mn2+(aq) + 4H2O(l)

The number of moles of Fe2+ used in the titration is:

number of moles of Fe2+ = concentration × volume

= 0.121 mol L-1) × (0.0200 L) = 2.42 × 10-3 mol

From the balanced equation, the number of moles of MnO4-(aq) is therefore:

number of moles of MnO4- = 1/5 × 2.42 × 10-3 mol = 4.84 × 10-4 mol

This amount is present in 23.5 mL so its concentration must be:

concentration = number of moles / volume

= 4.82 × 10-4 mol / 0.0235 L = 0.0206 M

Answer: 0.0206 M
CHEM1612 2010-N-10 November 2010

• How many minutes would be required to obtain 10.0 g of liquid mercury by passing a
2
constant current of 0.17 A through a solution containing Hg2(NO3)2(aq)?

The number of moles of Hg in 10.0 g is:

amount of mercury = mass / molar mass = (10.0 g) / (200.59 g mol-1)

= 0.0499 mol
The redox reaction is the 2 electron process below:
Hg22+(aq) + 2e- Æ 2Hg
Hence, for each mole of Hg, 1 mol of electrons is required so 0.0499 mol of
electrons are required.
The number of moles of electrons passed by a current I in a time t is given by:
number of moles of electrons = It / F
The time required to pass 0.0499 mol of electrons using I = 0.17 A is therefore:
t = (0.0499 mol) × (96485 C mol-1) / (0.17 A) = 28000 s = 470 mins

Answer: 470 mins

CHEM1612 2010-N-11 November 2010
Marks
• Calculate ΔG° for the following reaction: 3
3+ +
3Cu(s) + Cr (aq) 3Cu (aq) + Cr(s)

The two electrode potentials are:

Cu(s) à Cu+(aq) + e- Eox° = -0.53 V

Cr3+(aq) +3e- à Cr(s) Ered° = -0.74 V

The overall cell potential is therefore:

E° = Eox° + Ered° = (-0.53 V) + (-0.74 V) = -1.27 V

Using ΔG° = -nFE° for this 3 electron transfer reaction:

ΔG° = -(3 × 96485 C mol-1) × (-1.27 V) = +368 kJ mol-1

Answer: +368 kJ mol-1

Is the reaction spontaneous under standard conditions? Give a reason for your
answer.

No. ΔG° > 0 and it must be negative for a spontaneous reaction.

Equivalently, E° < 1 and it must be positive for a spontaneous reaction.
CHEM1612 2009-N-15 November 2009
Marks
• The standard reduction potential of phosphorous acid to hypophosphorous acid is 3
−0.499 V, with the following half-reaction:
H3PO3(aq) + 2H+(aq) + 2e− → H3PO2(aq) + H2O(l)
What would the reduction potential be for this half reaction at a temperature of 25 °C
in an aqueous solution with pH of 2.3 and concentrations of [H3PO3(aq)] = 0.37 M
and [H3PO2(aq)] = 0.00025 M?

As pH = -log10[H+(aq)], [H+(aq)] = 10-2.3 M. With [H3PO3(aq)] = 0.37 M and

[H3PO2(aq)] = 0.00025 M, the reaction quotient, Q, is given by:
𝐇𝟑 𝐏𝐎𝟐 𝐚𝐪 (𝟎.𝟎𝟎𝟎𝟐𝟓)
Q= = = 27
𝐇𝟑 𝐏𝐎𝟐 𝐚𝐪 [𝐇 ! 𝐚𝐪 ]𝟐 𝟎.𝟑𝟕 (𝟏𝟎!𝟐.𝟑 )𝟐
The reduction potential for this 2 electron reduction is given by the Nernst
equation:
𝑹𝑻 (𝟖.𝟑𝟏𝟒  ×(𝟐𝟓!𝟐𝟕𝟑)
E = E° - lnQ = (-0.499 – × ln(27)) V = -0.541 V
𝒏𝑭 𝟐  ×𝟗𝟔𝟒𝟖𝟓

Answer: -0.541 V

• A number of bacteria can reduce the nitrate ion in the presence of sulfur. A 2
simplified unbalanced redox reaction can be written as:
S(s) + NO3–(aq) → SO2(g) + NO(g)
Balance this redox equation for acidic conditions.

3S(s) + 4H+(aq) + 4NO3–(aq) → 3SO2(g) + 4NO(g) + 2H2O(l)

CHEM1612 2009-N-16 November 2009
Marks
• What is the value of the equilibrium constant for the following reaction at 298 K? 3
2Fe3+(aq) + 3Sn(s) → 2Fe(s) + 3Sn2+(aq)
Relevant electrode potentials can be found on the data page.

The relevant reduction potentials are:

Fe3+(aq) + 3e- à Fe(s)   E° = -0.04 V
2+ -
Sn (aq) + 2e à Sn(s)   E° = -0.14 V
2+
As the Sn / Sn couple is the more negative, it is reversed giving:
E° = (-0.04 + 0.14) V = 0.10 V
The equilibrium constant, K, is related to the standard reduction potential using:
E° = (RT/nF) × lnK
lnK = nFE° / RT = (6 × 96485 × 0.10) / (8.314 × 298) = 23.37
K = e23.37 = 1.4 × 1010

Answer: 1.4 × 1010

CHEM1612 2008-N-9 November 2008
Marks
 A galvanic cell is made of a Zn2+/Zn half cell with [Zn2+] = 2.0 M and an Ag+/Ag half 5
cell with [Ag+] = 0.050 M. Calculate the electromotive force of the cell at 25 °C.

The standard reduction reactions and potentials for the two half cells are:

Zn2+(aq) + 2e-  Zn(s) E° = -0.76 V

Ag+(aq) + e-  Ag(s) E° = +0.80 V

The least positive (Zn2+/Zn) couple is reversed giving the overall reaction:

Zn(s) + 2Ag+(aq)  Zn2+(aq) + 2Ag(s) E° = (+0.76 V) + (0.80) = 1.56 V

As non-standard concentrations are used, the cell potential is calculated using

the Nernst equation. The reaction involves the transfer of 2e- so with n = 2 this
becomes:

𝑹𝑻 𝑹𝑻 [𝐙𝐧𝟐+ 𝐚𝐪 ]
E = E° − lnQ = E° − ln
𝒏𝑭 𝒏𝑭 [𝐀𝐠 + 𝐚𝐪 ]𝟐

−𝟏 −𝟏
𝟖.𝟑𝟏𝟒 𝐉 𝐊 𝐦𝐨𝐥 (𝟐𝟗𝟖 𝐊) 𝟐.𝟎
= (+1.56 V) - − −𝟏 ln = +1.47 V
(𝟐 ×𝟗𝟔𝟒𝟖𝟓 𝐂 𝐦𝐨𝐥 ) 𝟎.𝟎𝟓𝟎𝟐

Answer: +1.47 V

Calculate the equilibrium constant of the reaction at 25 °C.

The equilibrium constant is related to the standard cell potential:

𝑹𝑻
E° = lnK
𝒏𝑭

Hence,
𝒏𝑭 (𝟐 ×𝟗𝟔𝟒𝟖𝟓 𝐂 𝐦𝐨𝐥−𝟏 )
lnK = E° × = (1.56 V) × = 121.5
𝑹𝑻 𝟖.𝟑𝟏𝟒 𝐉 𝐊 −𝟏 𝐦𝐨𝐥−𝟏 (𝟐𝟗𝟖 𝐊)

K = 5.9 × 1052

Answer: K = 5.9 × 1052

Calculate the standard Gibbs free energy of the reaction at 25 °C.

Using ΔG° = nFE°:

ΔG° = -(2 × 96485 C mol-1) × (+1.56 V) = –301 kJ mol–1

Answer: –301 kJ mol–1

ANSWER CONTINUES ON THE NEXT PAGE
CHEM1612 2008-N-9 November 2008

Indicate whether the reaction is spontaneous or not. Give a reason for your answer.

As E > 0, ΔG° < 0 and K is very large: the reaction is spontaneous.

Express the overall reaction in the shorthand voltaic cell notation.

Zn(s)  Zn2+(aq) (2.0 M)  Ag+(aq) (0.050 M)  Ag(s)

CHEM1612 2008-N-11 November 2008

• A melt of NaCl is electrolysed for 35 minutes with a current of 3.50 A. Calculate the 4
mass of sodium and volume of chlorine at 40 °C and 1.00 atm that are formed.

The number of moles of electrons delivered by a current, I, of 3.50 A in 35

minutes is:

 .
   
number of moles of electrons = = = 0.076 mol
     

The overall electrolysis reaction, NaCl(l)
Na(s) + ½Cl2(g), corresponds to

reduction of Na+ and oxidation of Cl-:

Na+ + e-
Na and Cl-
½Cl2 + e-

As one mole of electrons would produce one mole of Na and half a mole of Cl2:

number of moles of Na = 0.076 mol

number of moles of Cl2 = ½ × 0.076 mol = 0.038 mol

The mass of Na produced is therefore:

mass of Na = number of moles × atomic mass

= (0.076 mol) × (22.99 g mol-1) = 1.8 g

Using the ideal gas law, PV = nRT, the volume of Cl2 produced is:

 . .  ! "   # "

V=  = 0.98 L
 . !
CHEM1612 2008-N-13 November 2008
Marks
• A concentration cell containing aqueous solutions of Cu(NO3)2 and solid copper 2
metal is constructed so that the Cu2+ ion concentration in the cathode half-cell is 0.66
M. Calculate the concentration of the Cu2+ ion in the anode half-cell if the cell
potential for the concentration cell at 25 °C is 0.03 V.

The cathode and anode reactions are:

Cu2+(aq) + 2e- à Cu(s)   (cathode)

Cu(s) à Cu2+(aq) + 2e- (anode)

The standard electrode potential E° = 0 V and the potential can be calculated

using the Nernst equation for this 2 electron reaction, n = 2:

𝑹𝑻 𝑹𝑻 [𝐂𝐮𝟐! 𝐚𝐪 ]𝐚𝐧𝐨𝐝𝐞
E = E° − 𝒏𝑭 lnQ = − 𝒏𝑭 ln
[𝐂𝐮𝟐! 𝐚𝐪 ]𝐜𝐚𝐭𝐡𝐨𝐝𝐞

−𝟏 −𝟏
𝟖.𝟑𝟏𝟒  𝐉  𝐊  𝐦𝐨𝐥 (𝟐𝟗𝟖  𝐊) [𝐂𝐮𝟐! 𝐚𝐪 ]𝐚𝐧𝐨𝐝𝐞
=− −𝟏 ln = +0.03 V
(𝟐  ×𝟗𝟔𝟒𝟖𝟓  𝐂  𝐦𝐨𝐥 ) 𝟎.𝟔𝟔

This gives [Cu2+(aq)]anode = 0.06 M.

Answer: 0.06 M

• In acid solution, dichromate ion oxidises iron(II) to iron(III) as illustrated in the 3

partial equation:
Fe2+ + Cr2O72– → Fe3+ + Cr3+
Write a balanced equation for this reaction.

The half reactions are:

Fe2+ à Fe3+ + e-
Cr2O72- + 14H+ + 6e- à 2Cr3+ + 7H2O

where H+ has been added to the Cr2O72- / Cr3+ couple to give H2O.

To balance the electrons, the first reaction needs to be multiplied by 6. Hence:

6Fe2+ + Cr2O72- + 14H+ à 6Fe3+ + 2Cr3+ + 7H2O

What would happen to the cell potential if the concentration of Cr3+ were increased?

It would decrease. If [Cr3+] is increased, Le Châtelier’s principle predicts that

the reaction will shift towards reactants, reducing the cell potential.
CHEM1612 2007-N-10 November 2007
Marks
• How many minutes would be required to electroplate 25.0 g of manganese by passing 2
a constant current of 4.8 A through a solution containing MnO4–?

25.0 g of manganese corresponds to

mass 25.0 g
number of moles = = = 0.455 mol
atomicmass 54.94 g mol −1

The reduction of MnO4- is a 7e- process:

MnO4-(aq) + 8H+(aq) + 7e-
Mn(s) + 4H2O(l)

Production of 0.455 mol of Mn(s) requires (7 × 0.455) = 3.19 mol of electrons.

The number of moles of electrons passed by a current I in a time t is given by

I×t
number of moles of electrons =
F
(4.8 A) × t
3.19 mol = so t = 64000 s = 1100 minutes
96485C mol −1

Answer: 1100 minutes

CHEM1612 2007-N-11 November 2007
Marks
 The solubility product constant of AgCl is Ksp = 1.8 × 10–10 M2. Using the relevant 6
electrode potentials found on the data page, calculate the reduction potential at 298 K
of a half-cell formed by:
(a) an Ag electrode immersed in a saturated solution of AgCl.

The standard electrode potential for Ag+(aq) + e-  Ag(s) is E° = +0.80 V. This

refers to the potential with [Ag+(aq)] = 1 M.

For the dissolution of AgCl(s) Ag+(aq) + Cl-(aq), Ksp = [Ag+(aq)][Cl-(aq)].

As [Ag+(aq)] = [Cl-(aq)],

[Ag  (aq)]  K sp = 1.8  1010 = 1.3 × 10-5 M

Using the Nernst equation, the cell potential at 298 K (25 °C) is,

0.0592
E = E° - log Q
n

The Ag+(aq) + e-  Ag(s) half cell involves one electron and so n = 1. The
1
reaction quotient is . Hence,

[Ag (aq)]

0.0592  1 
E = (+0.80) - log   = +0.52 V
1 5
 1.3  10 

Answer: E = +0.52 V

(b) an Ag electrode immersed in a 0.5 M solution of KCl containing some AgCl

precipitate.

[Cl-(aq)] = 0.5 M and as Ksp = [Ag+(aq)][Cl-(aq)],

K sp 1.8  1010 M 2
[Ag+(aq)] = = = 3.6 × 10-10 M
 0.5 M
[Cl (aq)]

The electrode potential is now,

0.0592  1 
E = (+0.80) - log   = +0.24 V
1  3.6  1010 

Answer: E° = +0.24 V
ANSWER CONTINUES ON THE NEXT PAGE
CHEM1612 2007-N-11 November 2007

Each of these half-cells is connected to a standard Cu2+(1 M)/Cu(s) half-cell. In

which half-cell, (a) or (b), will clear evidence of a reaction be seen? Describe the
change(s) observed.

For the Cu2+ (1 M)/Cu(s) half cell, the reduction potential is E° = +0.34 V.

If the half cell is combined with half cell (a), the former has the least positive cell
potential and is reversed:

Cu(s)  Cu2+(aq) + 2e- E = -0.34 V

Ag+(s) + e-  Ag(s) ([Ag+(aq)] =1.3×10-5 M) E = +0.52 V
Cu(s) + 2Ag+(aq)  Cu2+(aq) + 2Ag(s) E = (-0.34)+(+0.52) = +0.18 V

If the half cell is combined with half cell (b), the latter has the least positive cell
potential and is reversed:

Cu2+(aq) + 2e-  Cu(s) E = +0.34 V

+ - + -10
Ag(s)  Ag (s) + e ([Ag (aq)] =3.6×10 M) E = -0.24 V
Cu2+(aq) + 2Ag(s)  Cu(s) + 2Ag+(aq) E = (+0.34)+(-0.24) = +0.10 V

Although both reactions have E > 0 V and so are spontaneous, only the second
reaction will give clear evidence of a reaction. The Ag+(aq) ions produced will
react with the excess Cl-(aq) present to give a white precipitate of AgCl around
the electrode
CHEM1612 2006-N-10 November 2006
3
• The physiological properties of chromium depend on its oxidation state. Consider the
half reaction in which Cr(VI) is reduced to Cr(III).
CrO42–(aq) + 4H2O(l) + 3e– → Cr(OH)3(s) + 5OH–(aq) Eo = –0.13 V
Calculate the potential for this half reaction at 25 oC, where pH = 7.40 and
[CrO42–(aq)] = 1.0 × 10–6 M.

As pH + pOH = 14.00 and pOH = -log10([OH-(aq)]), at pH = 7.40,

pOH = 14.00 – 7.40 = 6.60 = -log10([OH-(aq)])

[OH-(aq)] = 10-6.60

The reaction quotient for the half-cell reaction is,

[OH − (aq)]5 (10−6.60 )5

Q= = = 1.0 × 10-27
2− −6
[CrO4 (aq)] (1.0 × 10 )

Using the Nernst equation for this three electron process,

RT 8.314 × (25+273)
E = Eo − ln Q = (-0.13) − ln(1.0 × 10−27 ) = +0.40 V
nF 3 × 96485

Answer: E = +0.40 V
CHEM1612 2006-N-11 November 2006
Marks
 Consider the following reaction at 298 K. 5
2+ 2+
Ni (aq) + Zn(s) Ni(s) + Zn (aq)
Calculate ΔGo for the cell. (Relevant electrode potentials can be found on the data
page.)

The half-cell reduction reactions and potentials are:

Ni2+(aq) + 2e-  Ni(s) E0 = -0.24 V

Zn2+(aq) + 2e-  Zn(s) E0 = -0.76 V

In the reaction above, the Zn is undergoing oxidation so its potential is reversed

and the overall cell potential is:

0
Ecell = (-0.24) – (-0.76) = +0.52 V

Using G0 = -nFE0 for this two electron reaction:

G0 = -(2) × (96485) × (+0.52) = -100000 J mol1 = -100 kJ mol1

Answer: -100 kJ mol-1

What is the value of the equilibrium constant for the reaction at 298 K?

RT
Using E0 = ln K ,
nF

(8.314)  (298)
+0.52 = ln K so K = 3.89 × 1017
(2)  (96485)

Alternatively, using G0 = -RTlnK,

-100 × 103 = -(8.314) × (298) × lnK so K = 3.89 × 1017

Answer: 3.89 × 1017

Express the overall reaction in voltaic cell notation.

In the reaction, Zn is being oxidized and hence is the anode. Ni2+ is being
reduced and so Ni is the cathode. In the standard cell notation, the anode is
written on the left and the cathode on the right:

Zn(s) | Zn2+(aq) || Ni2+(aq) | Ni(s)

ANSWER CONTINUES ON THE NEXT PAGE

CHEM1612 2006-N-11 November 2006
2
 Using a current of 2.00 A, how long (in minutes) will it take to plate out all of the
silver from 0.250 L of a 1.14 × 10–2 M Ag+(aq) solution?

The number of moles of Ag+(aq) in a 0.250 L of a 1.14 × 10-2 M solution is,

number of moles = volume×concentration = 0.250×1.14×10-2 = 2.85×10-3 mol

The reduction of Ag+(aq) is a one electron process, Ag+(aq) + e-  Ag(s), so this

number of moles of electrons are required.

As the number of moles of electrons delivered by a current I in a time t is,

It 2.00  t
number of moles of electrons = = = 2.85 × 10-3
F 96485

t = 137 s = 2.29 minutes

CHEM1612 2006-N-12 November 2006
2
• Calculate the standard free-energy change for the following reaction at 298 K.
2Au(s) + 3Mg2+(1.0 M) → 2Au3+(1.0 M) + 3Mg(s)

The half-cell reduction reactions and potentials are:

Au3+(aq) + 3e-
Au(s) E0 = +1.50 V

Mg2+(aq) + 2e-
Mg(s) E0 = -2.36 V

In the reaction above, the Au is undergoing oxidation so its potential is reversed

and the overall cell potential is:

0
Ecell = (-2.36) – (+1.50) = -3.86 V

Using ∆G0 = -nFE0 for this six electron reaction:

∆G0 = -(6) × (96485) × (-3.86) = +2.23 × 106 J mol1 = +2.23 × 103 kJ mol1

Answer: +2.23 × 103 kJ mol-1

CHEM1612 2005-N-8 November 2005
Marks
 Calculate the standard free-energy change for the following reaction at 298 K. 2
2+ 3+
2Au(s) + 3Ca (1.0 M)  2Au (1.0 M) + 3Ca(s)

The reduction half cell reactions and E0 values are:

Au3+(aq) + 3e-  Au(s) E0 = + 1.50 V

Ca2+(aq) + 2e-  Ca(s) E0 = -2.87 V

In the reaction, Au is being oxidized and so the overall cell potential is:

E0 = ((-2.87) – (+1.50)) V = -4.37 V

The reaction involves 6 electrons so, using ΔG0 = -nFE0:

G0 = - (6) × (96485 C mol-1) × (-4.37 V) = +2530000 J mol-1

= +2.53 × 103 kJ mol-1

Answer: +2.53 × 103 kJ mol-1

Complete and balance the following equation for the reaction between iron(II) ions 2
and permanganate ions in an acidic solution.
Fe2+ + MnO4– → Fe3+ + Mn2+

In acid, the relevant half cells are:

Fe2+(aq)  Fe3+(aq) + e-
MnO4-(aq) + 8H+(aq) + 5e-  Mn2+(aq) + 4H2O(l)

Giving an overall reaction:

5Fe2+(aq) + MnO4-(aq) + 8H+(aq)  5Fe3+(aq) + Mn2+(aq) + 4H2O(l)

ANSWER CONTINUES ON THE NEXT PAGE

CHEM1612 2005-N-8 November 2005
2
 What is the value of the equilibrium constant for the following reaction at 298 K?
2Fe3+(aq) + Sn(s) Sn2+(aq) + 2Fe2+(aq)

The reduction half cell reactions and E0 values are:

Fe3+(aq) + e-  Fe2+(aq) E0 = +0.77 V

Sn2+(aq) + 2e-  Sn(s) E0 = -0.14 V

In the reaction, Sn is being oxidized and so the overall cell potential is:

E0 = ((+0.77) – (-0.14)) V = +0.91 V

RT
The reaction involves 2 electrons so, using E0 = lnK:
nF

nF  2  96485Cmol 1 
lnK = E0 × = (+0.91 V) ×   = 70.9
RT  8.314 J K 1 mol 1  298 K 
 

K = e70.9 = 6.05 × 1030

Answer: 6.05 × 1030

CHEM1612 2004-N-8 November 2004
Marks
 Consider the following balanced redox reaction. 2
+ 3+ 2+
2In(s) + 3MnO2(s) + 12H (aq)  2In (aq) + 3Mn (aq) + 6H2O
o
If E = 1.568 V, what would be the measured potential of this cell at 298 K at the
following concentrations?
[H+(aq)] = 0.25 M; [In3+(aq)] = 0.20 M; [Mn2+(aq)] = 0.42 M

The reaction quotient Q is given by:

[In 3 (aq)]2 [Mn 2 ]3

Q=
[H  (aq)]12

The cell reaction involves a 6e- process (2In  2In(III) and 3Mn(IV) 
3Mn(II)). The cell potential can be calculated using the Nernst equation,

RT
E = Eo  ln Q
nF
(8.314 J K 1 mol 1 )  (298 K)  (0.20)2 (0.42) 3 
= (1.568 V)  ln    1.52 V
(6)  (96485Cmol -1 )  (0.25)
12


Answer: 1.52 V
2
 What is the value of the equilibrium constant for the following reaction at 298 K?
Cu2+(aq) + Zn(s)  Zn2+(aq) + Cu(s)
Relevant electrode potentials can be found on the data page.

The standard reduction potentials for Cu2+(aq) / Cu(s) and Zn2+(aq) / Zn(s) are
+0.34 V and -0.76 V respectively. The Zn2+(aq) / Zn potential is the less positive
and is reversed. The cell potential is therefore:
o
Ecell = ((0.34) – (-0.76)) V = 1.10 V

The equilibrium constant for this 2e- process can be calculated using Ecell
o

RT
= ln K :
nF

(2)  (96485Cmol 1 )
lnK = × (1.10) = 85.7
(8.314 JK -1 mol -1 )  (298K)

K = e85.7 = 1.62 × 1037

Answer: 1.62 × 1037

CHEM1611 2003-J-8 June 2003
3
• Consider the following half-reactions and their standard reduction potentials.
2ClO3 + 12H+ + 10e– → Cl2 + 6H2O
−
E° = 1.47 V
S2O82 + 2e– → 2SO42
− −
E° = 2.01 V
Give the overall cell reaction.

The half cell with the least positive reduction potential is reversed:

Cl2 + 6H2O + 5S2O82- à 2ClO3- + 12H+ + 10SO42-

Calculate ΔG° and hence the value of Kc for the cell reaction at 298 K.

As the ClO3- / Cl2 half cell is reversed, the standard cell potential is:

Eo = ((2.01) + (-1.47) V = 0.54 V

Using ΔGo = -nFEo, the free energy change for this 10e- process is:

ΔGo = -(10) × (96485 C mol-1) × (0.54 V) = -521000 J mol-1 = -521 kJ mol-1

Using ΔGo = -RTlnKc, the equilibrium constant is given by:

-521000 kJ mol-1 = -(8.314 J K-1 mol-1 × 298 K) × lnKc so Kc = 2.14 × 1090

Alternatively, Kc can be obtained directly from Eo using the Nernst equation:

RT
Eo = ln K c = 0.54 V
nF
(8.314 J K −1 mol −1 × 298K)
0.54 V = ln Kc so Kc = 2.14 × 1090
(10 × 96485Cmol −1 )

The reaction essentially proceeds to completion.

ΔG° = -521 kJ mol-1 Kc = 2.14 × 1090