ANSWERS TO PROBLEM SET No.

2 - ELECTROCHEMISTRY

1. 17.25 (a) Ag(s) | Ag+(aq) || Fe2+(aq) | Fe(s)

(b) Pt(s) | H2O2(aq) | O2(g) || NO(g) | NO31-(aq) | Pt(s)
(c) Pt(s) | H3O+(aq) | H2(g) || Cl2(g) | Cl1-(aq) | Pt(s)

2. 17.26 (a) 3Cu + 14H+ + Cr2O72- → 2Cr3+ + 7H2O + 3Cu2+

(b) 16H+ + 2MnO41- + 10Cl1- → 5Cl2 + 2Mn2+ + 8H2O
(c) 2Ag+ + C2O42- → 2CO2 + 2Ag

3. 17.32 ε⁰ = 0.410 V, anode is Fe of the Fe/Fe2+ half cell

4. 17.33 To reduce Be2+ to Be, need metals with oxidation potentials greater than 1.97 V (or
reduction potentials more negative than -1.97 V). Ba, Ca, Cs, Li, Mg, K and Na all fit this
requirement, they are all either group IA or IIA metals, the most reactive metals on the
periodic table (remember your 1110 elemental properties.

5. (a) cell = +0.81 V

(b) cell = +0.78 V
(c) [Mn2+] = 0.110 M and [Cd2+] = 4.8 x 10-28 M

6. (i) YES, reaction will occur because cell > zero.

(ii) NO, reaction will not occur because
cell < zero. (iii) YES, reaction will occur
because cell > zero.

7. Copper cannot be oxidized by HCl because

for the reaction, Cu + 2H+ H2 + Cu2+ the
cell < zero.
However for the reactions: Cu + HNO3 Cu2+ + NO2 or NO the cell > zero.

8. Zinc would be better than nickel because it has a more positive value for its oxidation
potential than does iron, and thus would be oxidized more readily than iron. However
if it were coated with nickel, the iron would be oxidized before the nickel and thus
would not protect the iron.

9. For [Au3+] = 1.0 x 10-6 M the half-cell = +1.380 V

For [Fe3+] = 0.50 M the half-cell = -0.0419 V
For [Ni2+] = 1.0 x 10-3 M the half-cell = -0.3387 V
Since the half-cell for the Au3+/Au is the most positive it will be the first metal to plate
out of the solution.

10. Hg2Cl2(s) + H2(g) → 2Hg(l) + 2HCl(aq) εcell = +0.517 V

11. 17.42 4099 hours

12. 17.59 (a) connect the negative wire to the Cd electrode
(b) 4.54 hours required for complete charging

13. 17.80 495 g Ca

14. 17.91 [Fe3+] = 5.6 x 10-8 M

15. a) Ag+(aq) + 2S2O32-(aq) Ag(S2O3)23-(aq) = + 0.799 - 0.017 = +0.782 V

at equilibrium = 0 and therefore the Nernst equation becomes
0 = +0.782 - (0.05916/1)log Keq and Keq = 1.65 x 1013

b) Ag(s) S2O32-(aq),cations(aq),Ag(S2O3)23-(aq) Ag+(aq),anions(aq) Ag(s )