Related Formula
For precipitation: [M²⁺][S²⁻] ≥ Kₛₚ$$\text{For precipitation: } [M^{2+}][S^{2-}] \ge K_{sp}$$
[S²⁻] = Kₐ₁ · Kₐ₂ · [H₂S][H^+]²$$[S^{2-}] = \frac{K_{a1} \cdot K_{a2} \cdot [H_2S]}{[H^+]^2}$$
Core Logic
For precipitation of YS(s)$YS(s)$:
[Y²⁺][S²⁻] ≥ Kₛₚ(YS)$[Y^{2+}][S^{2-}] \ge K_{sp}(YS)$
[S²⁻] ≥ 4 × 10⁻¹⁶0.01 = 4 × 10⁻¹⁴ M$[S^{2-}] \ge \frac{4 \times 10^{-16}}{0.01} = 4 \times 10^{-14} \text{ M}$
Since H₂S$H_2S$ dissociates in water:
H₂S leftharpoons 2H^+ + S²⁻$H_2S \rightleftharpoons 2H^+ + S^{2-}$
[S²⁻][H^+]²[H₂S] = Kₐ₁ × Kₐ₂ = 1.0 × 10⁻²¹$\frac{[S^{2-}][H^+]^2}{[H_2S]} = K_{a1} \times K_{a2} = 1.0 \times 10^{-21}$
Substitute the [S²⁻]$[S^{2-}]$ threshold:
[S²⁻] = 1.0 × 10⁻²¹ × [H₂S][H^+]² ≥ 4 × 10⁻¹⁴$[S^{2-}] = \frac{1.0 \times 10^{-21} \times [H_2S]}{[H^+]^2} \ge 4 \times 10^{-14}$
Step 1: Calculate pH
Using [H₂S] = 0.1 M$[H_2S] = 0.1 \text{ M}$:
10⁻²¹ × 0.1[H^+]² = 4 × 10⁻¹⁴$\frac{10^{-21} \times 0.1}{[H^+]^2} = 4 \times 10^{-14}$
10⁻²²[H^+]² = 4 × 10⁻¹⁴$\frac{10^{-22}}{[H^+]^2} = 4 \times 10^{-14}$
[H^+]² = 10⁻²²4 × 10⁻¹⁴ = (1)/(4) × 10⁻⁸ = 0.25 × 10⁻⁸ = 25 × 10⁻¹⁰$[H^+]^2 = \frac{10^{-22}}{4 \times 10^{-14}} = \frac{1}{4} \times 10^{-8} = 0.25 \times 10^{-8} = 25 \times 10^{-10}$
[H^+] = 5 × 10⁻⁵ M$[H^+] = 5 \times 10^{-5} \text{ M}$
pH = - (5 × 10⁻⁵) = 5 - 5 = 5 - 0.70 = 4.3$pH = -\log(5 \times 10^{-5}) = 5 - \log 5 = 5 - 0.70 = 4.3$
Rounding to the nearest integer, pH ≈ 4$\approx 4$.
Pattern Recognition
Equating the S²⁻$S^{2-}$ concentration required for Kₛₚ$K_{sp}$ with the S²⁻$S^{2-}$ provided by the H₂S$H_2S$ equilibrium directly links solubility product to pH.
Chapter Mix
Class 11 Chemistry: Equilibrium
Class 12 Chemistry: Qualitative Analysis