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Question

A silver electrode is immersed in saturated Ag2SO4(aq). The potential difference between silver and the standard hydrogen electrode is found to be 0.711 V.
Determine the Ksp of Ag2SO4 at 25oC.
Given:
E0Ag+/Ag=0.799 V 101.50.031

A
Ksp=4.3×104
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B
Ksp=2.77×104
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C
Ksp=9.4×106
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D
Ksp=1.54×105
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Solution

The correct option is D Ksp=1.54×105
The cell can be represented as :
Pt(s)|H2(g, 1atm)|H+(aq, 1 M)||Ag+(salt)|Ag(s)

E0cell=EAg+/AgE0H+/H2

E0=0.800=0.80 V
Given,
Emf of the cell =0.711 V
The cell reaction is
H2+2Ag+2Ag+2H+
Q=[Ag]2[H+]2[H2][Ag+]2=12×121×[Ag+]2=1[Ag+]2
Applying Nernst equation,

E=E00.05912log1[Ag+]2

0.711=0.800.05912log1[Ag+]2

0.089=0.05912log1[Ag+]2

3.01=log1[Ag+]2

3.01=2log [Ag+]

1.50=log [Ag+]

[Ag+]0.031 mol L1

Ag2SO4(aq)2Ag+(aq)+SO24(aq)

[SO24]=[Ag+]2

[SO24]0.016 mol L

Ksp=[Ag+]2[SO24]=(0.031)2×(0.016)=1.54×105

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