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Exercises 1

This document contains sample problems and answers related to electrochemistry concepts including writing cell reactions and half reactions, calculating standard cell potentials, using the Nernst equation, and calculating equilibrium constants from standard potential data. Several examples are provided for writing cell reactions and calculating standard potentials for different galvanic cells. Thermodynamic calculations related to cell reactions are also demonstrated.

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4K views

Exercises 1

This document contains sample problems and answers related to electrochemistry concepts including writing cell reactions and half reactions, calculating standard cell potentials, using the Nernst equation, and calculating equilibrium constants from standard potential data. Several examples are provided for writing cell reactions and calculating standard potentials for different galvanic cells. Thermodynamic calculations related to cell reactions are also demonstrated.

Uploaded by

monogod
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© Attribution Non-Commercial (BY-NC)
We take content rights seriously. If you suspect this is your content, claim it here.
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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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