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Question

At 25C,ΔHf(H2O,I)=56700J/mol and energy of ionization of H2O(I)=19050J/molIf the reversible EMF at 25C of the cell is 414×10x, then the value of x is ?
Pt|H2(g)(1atm)|H+||OH|O2(g)(1atm)|Pt, if at 26C the emf increase by 0.001158 V.
Ans in V

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Solution

H2+12O2H2O ΔH1=56700J/mole ...(i)
2H2O2H++2OH ΔH2=2×19050 ....(ii)
call reaction :
at anode : H22H++2e
at cathode : 2e+H2O+12O22OH
net reaction : H2+H2O+12O22H++2OH ...(iii)
equation (i)+(ii)=(iii)
ΔG1+ΔG2=ΔG3
ΔH1TΔS1+ΔH2TΔS2=nFE
(ΔH1+ΔH2)T(ΔS1+ΔS2)=2FE
(ΔH1+ΔH2)T(ΔSnet)=2FE
ΔS=nFdEdT so E=(ΔH1+ΔH2)2F+TDEdT
E=(56700+2×19050)2×96500+298(0.001158)
E=0.09637+0.345
=0.4414V

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