Related Formula
Ecell = Ecell° - (0.059)/(n) Q$$E_{cell} = E_{cell}^{\circ} - \frac{0.059}{n} \log Q$$
pH = pKₐ + [Salt][Acid]$$pH = pK_a + \log \frac{[\text{Salt}]}{[\text{Acid}]}$$
Core Logic
Note: In the question paper, EHSnO₂^-/[Sn(OH)₆]²⁻° = -0.9 V$E_{HSnO_2^-/[Sn(OH)_6]^{2-}}^{\circ} = -0.9\text{ V}$ is given, but standard NTA solution requires assuming E[Sn(OH)₆]²⁻/HSnO₂^-° = -0.9 V$E_{[Sn(OH)_6]^{2-}/HSnO_2^-}^{\circ} = -0.9\text{ V}$ for standard operation. (Our Ans. is Bonus due to this discrepancy, NTA Answer is 78). We will solve using the assumed valid logic.
Ecell° = Ecathode° - Eanode° = -0.44 - (-0.90) = 0.46 V$E_{cell}^{\circ} = E_{cathode}^{\circ} - E_{anode}^{\circ} = -0.44 - (-0.90) = 0.46\text{ V}$
Oxidation Half: HSnO₂^- + H₂O + 3OH^- arrow [Sn(OH)₆]²⁻ + 2e^-$HSnO_2^- + H_2O + 3OH^- \rightarrow [Sn(OH)_6]^{2-} + 2e^-$
Reduction Half: Bi₂O₃ + 3H₂O + 6e^- arrow 2Bi + 6OH^-$Bi_2O_3 + 3H_2O + 6e^- \rightarrow 2Bi + 6OH^-$
Overall: 3HSnO₂^- + Bi₂O₃ + 6H₂O + 3OH^- arrow 3[Sn(OH)₆]²⁻ + 2Bi$3HSnO_2^- + Bi_2O_3 + 6H_2O + 3OH^- \rightarrow 3[Sn(OH)_6]^{2-} + 2Bi$
Here n = 6$n = 6$.
Nernst Eq:
Ecell = Ecell° - (0.059)/(6) ([Sn(OH)₆]²⁻)³([HSnO₂^-]³ [OH^-]³)$E_{cell} = E_{cell}^{\circ} - \frac{0.059}{6} \log \frac{([Sn(OH)_6]^{2-})^3}{([HSnO_2^-]^3 [OH^-]^3)}$
0.2353 = 0.46 - (0.059)/(6) ((0.5)³)/((0.05)³ [OH^-]³)$0.2353 = 0.46 - \frac{0.059}{6} \log \frac{(0.5)^3}{(0.05)^3 [OH^-]^3}$
0.2353 = 0.46 - (0.059)/(2) (10)/([OH^-])$0.2353 = 0.46 - \frac{0.059}{2} \log \frac{10}{[OH^-]}$
( (10)/([OH^-]) ) = ((0.46 - 0.2353) × 2)/(0.059) = (0.2247 × 2)/(0.059) = 7.6$\log \left( \frac{10}{[OH^-]} \right) = \frac{(0.46 - 0.2353) \times 2}{0.059} = \frac{0.2247 \times 2}{0.059} = 7.6$
Step 1: Calculate pH
(10) - [OH^-] = 7.6$\log(10) - \log[OH^-] = 7.6$
1 + pOH = 7.6 pOH = 6.6$1 + pOH = 7.6 \implies pOH = 6.6$
pH = 14 - 6.6 = 7.4$pH = 14 - 6.6 = 7.4$
Step 2: Buffer Equation
Using Henderson-Hasselbalch equation for buffer of NaHCO₃$NaHCO_3$ and H₂CO₃$H_2CO_3$:
pH = pKₐ + nsaltnacid$pH = pK_a + \log \frac{n_{\text{salt}}}{n_{\text{acid}}}$
7.4 = 6.11 + (5x)/(10 × 2)$7.4 = 6.11 + \log \frac{5x}{10 \times 2}$
1.29 = (5x)/(20) = (x)/(4)$1.29 = \log \frac{5x}{20} = \log \frac{x}{4}$
Taking antilog:
(x)/(4) = Antilog(1.29) = 19.5$\frac{x}{4} = \text{Antilog}(1.29) = 19.5$
x = 19.5 × 4 = 78 mL$x = 19.5 \times 4 = 78\text{ mL}$
Pattern Recognition
Merge Nernst equation finding unknown concentration with Buffer equations. Determine overall cell reaction to find exact stoichiometry and 'n' electrons for Nernst.
Chapter Mix
Class 12 Chemistry: Electrochemistry
Class 11 Chemistry: Equilibrium