Advanced Electrochemistry Tutorial 1

1) A rod of the metallic element cobalt is placed in a solution containing dissolved

Co2+ ions. Describe the processes that will take place and explain how at
equilibrium, the metal can acquire a net negative charge with respect to the
solution.
2) What would be the potential of Mg2+/Mg couple with respect to the SCE
(EoMg2+/Mg= -2.375, E0SCE= 0.242)
3) What is the electrode potential for a half-cell consisting of a cadmium electrode
immersed in a solution that is 0.0150 M in Cd2+ (EoCd2+/Cd= - 0.403 V).
4) Calculate the electrode potentials of the following half-cells.
(a) Ag+ (0.0261 M)I Ag ( EoAg+/Ag = 0.7996 V)
(b) Fe3+ (6.72 x10-4 M), Fe2+(O.l00 M) /Pt (EoFe3+/Fe2+= 0.77 V)
(c) AgBr (sat'd),Br- (0.050 M)I Ag (EoAgBr/Ag,Br-= 0.0713 V)
5) Design a cell in which the following reaction occurs:
Cu(S) + 2Ag+(Aq) Cu2+(Aq) + 2Ag(S)
Write the two half-cell reactions and so identify the anode and the cathode reactions
also write down the cell notation. Calculate the standard e.m.f. of the cell at 25C
using the values of the standard electrode potentials ( EoCu2+,Cu= 0.34 V and EoAg+,Ag=
0.78 V) evaluate the Gibbs free energy change (G) for the reaction.
6) Calculate Ecell of the reactions and predict whether it is spontaneous reaction or
not.
A) Sn2+(aq) + Zn(s) ==== Zn2+(aq) + Sn(s), (EoSn2+/Sn= -0.136, EoZn2+/Zn= -0.763)
B) 2Fe2+(aq) + Sn4+(aq) ==== 2Fe3+(aq) + Sn2+(aq) (EoSn4+/Sn2+ = +0.154 , EoFe3+/Fe2+
= +0.771)
7) Ecell of the following reaction was measured as 0.35 V, find the EoSc3+/Sc,
3Mg (s) + 2Sc3+(aq) ==== 3Mg2+(aq) + 2Sc(s) (EoMg2+/Mg= -2.375)
8) Determine whether or not Cd in the following electrochemical cell will undergo
corrosion and evaluate the free energy change (G) of the reaction,
Cd | Cd2+(aq), Cl (aq) | | H+ (aq), O2 (g) | Pt,
The pH of the solution is 3.5, the oxygen pressure is 2.1 104 Pa and the metal ion
concentration is 1 106 mol dm3. EoCd2+/Cd = -0.403 V, EoO2/H2O = 1.229 V.
9) Nickel is placed in a solution of 1.0 103 M HNO3 at 298 K. Given that the
solution is exposed to air containing O2 at 2.1 104 Pa and the cathodic reaction is:
O2 + 4H+ + 4e 2H2O

E = 1.23 V,

Evaluate ECell and thus show that nickel will indeed corrode under these conditions.

{E(Ni/Ni2+) = 0.23 V; [Ni2+] = 1.0 106 M; standard pressure = 1.013 x 105 Pa }

(15 marks).
10) What is a Pourbaix diagram and explain four types of lines that are present in it
taking Cu metal as example.