ELECTROCHEMISTRY TUTORIAL # 5

Question 1
(a) When a strip of copper metal is placed in a colourless solution of silver nitrate,
the solution gradually becomes blue. Explain what is happening at the ionic
level and say what else one is likely to observe.
(5 marks)
(b) The standard electrode potential of the silver electrode is said to be +0.80V.
(i)
(ii)

Explain what you understand this to mean, including in your explanation,

a sketch of the cell you would construct to demonstrate practically, that the
electrode potential is indeed +0.80V.
(8 marks)
Explain why you would use a salt bridge in the construction of such a cell,
and also why you would use a voltmeter with a high resistance to make
potential measurements for such a cell.
(5 marks)

(c) Given that the standard electrode potential of the copper electrode is +0.34V,
indicate which electrode is positive in copper-silver standard cell, which is the
cathode and write the overall cell equation in the direction in which it is
spontaneous.
How much work (in Joules) can be done in principle by such a cell?
(7 marks)
Question 2
(a)
Sketch and label the cell you would construct, and say what measurement you
would make, in order to obtain an accurate value of the standard electrode
potential of the Au+ / Au(s) electrode. Identify the important features of any devices
you employ.
(9 marks)
(b)

Given that the standard reduction potential of the Au +/ Au(s) electrode is +1.69V,
represent the cell in standard cell notation and use two half cell reductions to
determine the overall cell reaction in the direction in which it is spontaneous, and
the cell potential. Identify cathode, anode and the positive and negative electrodes
in this cell.
(6 marks)

(c)

Determine (i) the standard Gibbs energy, G, and the equilibrium constant K, for
the reaction. (ii) Write the expression for the reaction quotient, Q, for the cell
reaction and deduce its value for the cell reaction when the cell is in its standard
state.
(6 + 4 marks)

Question 3
(a)

A strip of magnesium metal is immersed in an aqueous 1.0 M solution of Mg 2+

and a strip of silver is immersed in an aqueous 1.0 M solution of Ag + and the two
half-cells are joined together to make a cell. The standard reduction potential of
the Mg2+/ Mg couple is -2.36V and that of the Ag+/Ag is + 0.80. Write the overall

(b)

(c)

cell reaction in the direction in which it is spontaneous and determine the EMF of
the cell.
(6 marks)
Sketch the main features of the cell you would construct from these two half cells,
showing in particular how you would connect the half-cells so that liquid junction
potential is reduced. Label the cathode, anode, positive electrode, negative
electrode, and 2+ shows the direction of the electron current.
(8 marks)
Write the Nernst equation for the cell in terms of the activities of the substances
involved in the cell reaction and show that the measured EMF will initially be the
standard cell potential. Determine also the equilibrium constant for the cell
reaction, explaining carefully any assumptions made.
(11 marks)

Question 4
(a) A galvanic cell consisting of Cu versus a hydrogen electrode was used to determine
the pH of an unknown solution. The unknown was placed in the hydrogen
electrode compartment and the pressure of the hydrogen gas was controlled at 1
atm. The concentration of Cu2+ was 1 mol dm-1 and the e.m.f of the cell at 25 0C
was determined to be +0.48V. (E0 Cu2+/ Cu = 0.34V)
(i)
Write the equation for the cell reaction.
(4 marks)
(ii)
Calculate the pH of the unknown solution.
(10 marks)
(b) Cytochrome (represented as CyFe2+) reacts with the oxygen in air we breathe to
supply energy required to synthesize adenosine triphosphate, (ATP). The body
uses ATP as its source of energy to drive other reactions. At pH 7, the following
equations are involved in the oxidation of cytochromes.
O2 (g) + 4 H+ (aq) + 4 e 2 H2O (l)
E = 0.82 V
CyFe3+(aq) + e(i)
(ii)

CyFe2+(aq)

E = 0.22 V

What is the G for the oxidation of CyFe2+ by air?

[3]
If the synthesis of 1 mol of ATP requires a G of 37.7 kJ, how many
moles of ATP are synthesized per mole of O2?
[4]

Question 5
a)

Sketch a standard Daniell cell which uses a porous pot to separate the two
electrode compartments.

Given that the standard reduction potentials of the

Cu2+/Cu and the Zn2+/Zn electrodes are +0.34 and -0.76 V respectively, show
the anode cathode, and electron current on the sketch.
b)

Write the overall cell reaction in the direction in which it is spontaneous, and
represent the cell in standard notation and determine its standard potential.

c)

When the potential of the cell was measured with a high resistance digital
voltmeter, it was found to be less than that expected, even though all solutions
were in their standard concentrations, and both electrodes were clean and pure

copper and zinc respectively. Explain why this is likely to be so, and explain how
the cell could be arranged to reduce the effect which causes lower than expected
potential to be observed.
d)

Starting with the Nernst equation for the cell, deduce an expression which relates
the measured EMF of the cell to the concentrations of the electrolyte solutions.