In two vessels each containing 500 mL water, 0.5 m mol of aniline (Kb = 10–9) and 25 m mol of HCl are added separately. Two hydrogen electrodes are constructed using these solutions. Calculate the emf of cells made by connecting them appropriately.
Answer & explanation
Correct answer: option 1
The correct answer is option 1. 0.395 V.
We know from the Nernst equation,
\(E_{cell} = E^0_{cell} − \frac{0.0591}{n}log Q\)
For hydrogen electrode, \(E^0_{cell} = 0\)
At Anode: \(H_2 − 2e^− \rightarrow 2H^+ (aq)\)
At Cathode: \(2H^+(aq) + 2e^− \rightarrow H_2 (g)\)
\(E_{cell} = 0 − \frac{0.0591}{2} log\frac{[H^+]^2_A}{[H^+]^2_C}\)
At Cthode:
\([H^+] = \frac{25 × 10^{−3}}{500 × 10^{−3}} = 5 × 10^{−2}\)
At Anode:
\(PhNH_2 + H_2O\) ⇌ \(PhNH_3^+ + OH^−\)
Also,
\([OH^−] = \sqrt{\frac{K_b}{C}}\)
\(∴ [OH^−]^2 = \frac{10^{−9}}{\frac{0.5}{500}} = 10^{−6}\)
\(∴ [H^+] = 10^{−8}\)
\(∴ E_{cell} = \frac{0.0591}{2}log\frac{(5 × 10^{−2})^2}{(10^{−8})^2}\)
or, \(E_{cell} = \frac{0.0591}{2} log[5 × 10^{−6}]\)
or, \(E_{cell} = 0.0591 × 6.7\)
∴ \(E_{cell} = 0.395 V\)