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Chemistry Question on Electrochemistry

Consider the cell, PtH2(g,1atm)H+(aq,1M)Fe3+(aq)P t \mid H_{2}(g, 1\, atm) H^{+}(a q, 1\, M) \| F e^{3+}(a q) Fe2+(aq)Pt(s)F e^{2+}(a q) \mid P t(s) Given that EoFe3+/Fe2+=0.771VE^{o}{ }_{F e^{3+} / F e^{2+}}=0.771\, V, the ratio of concentration of Fe(aq)2+F e_{(a q)}^{2+} to Fe(aq)3+F e_{(a q)}^{3+} is, when the cell potential is 0.830V0.830\, V.

A

0.101

B

0.924

C

0.12

D

None of these

Answer

0.101

Explanation

Solution

The half-cell reactions of the given cell are as
At anode 12H2H++e;E1o=0.00V\frac{1}{2} H_{2} \rightarrow H^{+}+e^{-} ; E_{1}^{o}=-0.00\, V
At cathode Fe3++eFe2+;E?o=0.771VF e^{3+}+e^{-} \rightarrow F e^{2+} ; E_{?}^{o}=0.771\, V Net reaction
Fe3++12H2Fe2++H+;Ecell o=0.771V0.00V=0.771VFe ^{3+}+\frac{1}{2} H _{2} \rightarrow Fe ^{2+}+ H ^{+} ; E_{\text {cell }}^{o}=0.771\, V -0.00\, V =0.771\, V From Nernst
Ecell =Ecell o=0.0591nlog[Fe2+][H+][Fe3+]+pH21/2E_{\text {cell }}=E_{\text {cell }}^{o}=-\frac{0.0591}{n} \log \frac{\left[ Fe ^{2+}\right]\left[ H ^{+}\right]}{\left[ Fe ^{3+}\right]+ pH _{2}^{1 / 2}}
0.830=0.7710.05911log[Fe2+Fe3+]0.0590.0591=log[Fe2+][Fe3+]0.830=0.771-\frac{0.0591}{1} \log \left[\frac{F e^{2+}}{F e^{3+}}\right]-\frac{0.059}{0.0591}=\log \frac{\left[F e^{2+}\right]}{\left[F e^{3+}\right]}
[Fe2+][Fe3+]=\therefore \frac{\left[ Fe ^{2+}\right]}{\left[ Fe ^{3+}\right]}= antilog
(0.998)=0.101(-0.998)=0.101