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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.

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