Physical Chemistry, Ninth Edition

Peter Atkins and Julio de Paula

6.20(a) Write the cell reaction and electrode half-reactions and

calculate the standard potential of each of the following cells:

(a) Zn | ZnSO4(aq) || AgNO3(aq) | Ag

Answer: cell reaction: Zn + 2 Ag+ Zn2+ + 2 Ag

Eocell = +0.8 -(-0.76)= 1.56V

(b) Cd | CdCl2(aq) || HNO3(aq) | H2(g) | Pt

Answer: cell reaction: Cd + 2H+ Cd2+ + H2

Eocell = +0.0 -(-0.40)= +0.4V

(c) Pt | K3 [Fe(CN)6](aq),K4 [Fe(CN)6](aq) || CrCl3(aq) | Cr

Answer: cell reaction: 3[Fe(CN)6]4-+ Cr3+ 3[Fe(CN)6]3-+ Cr

Eocell = -0.74 -(+0.36)= -0.38V

6.20(b) Write the cell reaction and electrode half-reactions and

calculate the standard potential of each of the following cells:

(a) Pt | Cl2(g) | HCl(aq) || K2 CrO4(aq) | Ag2 CrO4(s) | Ag

(b) Pt | Fe3+(aq),Fe2+(aq) || Sn2+(aq) | Pt

(c) Cu | Cu2+(aq) || Mn2+(aq),H+(aq) | MnO2(s) | Pt

6.21(a) Devise cells in which the following are the reactions and
calculate the standard cell potential in each case:

(a) Zn(s) + CuSO4(aq) ZnSO4(aq) + Cu(s)

(b) 2 AgCl(s) + H2(g) 2 HCl(aq) + 2 Ag(s)

Answer: Pt(s)/H2(g)/HCl(aq)/AgC(s)l/Ag(s)

(c) 2 H2(g) + O2(g) 2 H2O(1)

Answer: Pt(s)/H2(g)/H+(aq)/O2(g)/Pt(s)

6.21(b) Devise cells in which the following are the reactions and
calculate the standard cell potential in each case:

(a) 2 Na(s) + 2 H2O(1) 2 NaOH(aq) + H2(g)

(b) H2(g) + I2(s) 2 HI(aq)

Answer: Pt(s)/H2(g)/HI(aq)/I2(s)/Pt(s)

(c) H3O+(aq) + OH(aq) 2 H2O(1)

6.22(a) Use the DebyeHckel limiting law and the Nernst

equation to estimate the potential of the cell Ag | AgBr(s) | KBr(aq,
0.050 mol kg1) || Cd(NO3)2 (aq, 0.010 mol kg1) | Cd at 25C

Answer:
LHE: 2Ag + 2Br- 2AgBr +2e Eo= +0.0713V
RHE: Cd2+ +2e Cd Eo= -0.4V
- 2+ o
Cell reaction: 2Ag + 2Br + Cd 2AgBr + Cd E cell= -0.4713V
o 2 2+
Nernst equation: E= E + RT/2F ln a Br- aCd
E= -0.4713 =(8.314x298)/(2x96500) ln (0.05)2(0.01)
E= -0.607V

6.22(b) Consider the cell , for which

the cell reaction is 2 AgCl(s) + H2(g) 2 Ag(s) + 2 HCl(aq). At
25C and a molality of HCl of 0.010 mol kg1, Ecell = +0.4658 V. (a)
Write the Nernst equation for the cell reaction. (b) Calculate rG for
the cell reaction. (c) Assuming that the DebyeHckel limiting law
holds at this concentration, calculate .
6.23(a) Calculate the equilibrium constants of the following
reactions at 25C from standard potential data:

(a)

Answer:
LHE: Sn Sn2+ +2e Eo=-0.14V
RHE: Sn4++2e Sn2+ Eo=+0.15V
EoCell = +0.15 -(-0.14)= +0.29V
lnK= nF EoCell/RT
= (2x96500x0.29)/(8.314x298)
= 22.59
K= 6.467x109

(b)

6.23(b) Calculate the equilibrium constants of the following

reactions at 25C from standard potential data:

(a)

Answer:
LHE: Sn Sn2+ +2e Eo=-0.14V
RHE: Cu2++2e Cu Eo=+0.34V
EoCell = +0.34 -(-0.14)= +0.48V
lnK= nF EoCell/RT
= (2x96500x0.48)/(8.314x298)
= 37.39
K= 1.731x1016

(b)

6.24(a) The potential of the cell Ag | AgI(s) | AgI(aq) | Ag is

+0.9509 V at 25C. Calculate (a) the solubility product of AgI and
(b) its solubility.