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ChemistryIonic Equilibrium
The equilibrium: BiO(OH)(s) ⇌ BiO⁺(aq) + OH⁻(aq) has K = 4 × 10⁻¹⁰. What will be the pH of the saturated solution?
Options
1
pH = 5
2
pH = 9
3
pH = 7
4
pH = 4
Correct Answer
Option 2 : pH = 9
Step-by-Step Solution
1

Write Ksp expression:

BiO(OH)(s) ⇌ BiO⁺(aq) + OH⁻(aq)

Solid is not included in equilibrium expression:

K = [BiO⁺][OH⁻] = 4 × 10⁻¹⁰
2

Let solubility = s mol/L:

From stoichiometry: [BiO⁺] = s and [OH⁻] = s

s × s = 4 × 10⁻¹⁰

s² = 4 × 10⁻¹⁰

s = 2 × 10⁻⁵ mol/L

3

Find pH:

[OH⁻] = s = 2 × 10⁻⁵ mol/L

pOH = −log[OH⁻] = −log(2 × 10⁻⁵) = 5 − log 2 = 5 − 0.3 = 4.7

pH = 14 − pOH = 14 − 4.7 = 9.3 ≈ 9

Theory: Ionic Equilibrium & Solubility
1. Solubility Product (Ksp)

When a sparingly soluble ionic compound dissolves in water, it establishes an equilibrium between the undissolved solid and the dissolved ions. The solubility product Ksp is the equilibrium constant for this dissolution. Pure solids and liquids have activity = 1 and are not included in the expression.

For AxBy(s) ⇌ xA^(y+)(aq) + yB^(x−)(aq)

Ksp = [A^(y+)]^x × [B^(x−)]^y

Ksp is temperature dependent — it increases with temperature for most salts (endothermic dissolution). A smaller Ksp means a less soluble compound. Ksp is used to predict whether a precipitate will form: if the ionic product Q > Ksp, precipitation occurs; if Q < Ksp, no precipitate.

2. Relation Between Solubility and Ksp

📌 AB type (1:1): Ksp = s² → s = √Ksp

📌 AB₂ or A₂B type: Ksp = 4s³ → s = (Ksp/4)^(1/3)

📌 AB₃ or A₃B type: Ksp = 27s⁴ → s = (Ksp/27)^(1/4)

📌 A₂B₃ type: Ksp = 108s⁵ → s = (Ksp/108)^(1/5)

📌 Here BiO(OH): 1:1 type → Ksp = s² → s = √(4×10⁻¹⁰) = 2×10⁻⁵

3. pH and pOH Relationship

pH = −log[H⁺]

pOH = −log[OH⁻]

pH + pOH = 14 (at 25°C)

Kw = [H⁺][OH⁻] = 10⁻¹⁴ at 25°C

Since [OH⁻] = 2×10⁻⁵: pOH = −log(2×10⁻⁵) = 5 − log2 = 5 − 0.301 ≈ 4.7. Therefore pH = 14 − 4.7 = 9.3. The solution is basic (pH > 7) because OH⁻ ions are released — this makes sense since BiO(OH) is a base-like compound releasing OH⁻.

4. Common Ion Effect

Adding a common ion to a solution of a sparingly soluble salt decreases its solubility (Le Chatelier's Principle). For example, adding NaOH to BiO(OH) solution increases [OH⁻], shifting the equilibrium left, reducing solubility of BiO(OH). This principle is used in qualitative analysis to selectively precipitate ions.

5. Buffer Solutions

A buffer solution resists changes in pH when small amounts of acid or base are added. It contains a weak acid and its conjugate base (acidic buffer) or a weak base and its conjugate acid (basic buffer). Buffer pH = pKa + log([A⁻]/[HA]) — Henderson-Hasselbalch equation. Maximum buffer capacity is at pH = pKa (equal concentrations of acid and conjugate base).

6. Indicators and Acid-Base Titrations

A pH indicator changes colour at its pKIn. For a titration, choose an indicator whose transition range overlaps with the steep portion of the titration curve. Strong acid + strong base: use phenolphthalein (pH 8.3–10) or methyl orange (pH 3.1–4.4). Weak acid + strong base: only phenolphthalein (endpoint at pH 8–9). Strong acid + weak base: only methyl orange. Weak acid + weak base: no suitable indicator (no sharp endpoint).

7. Degree of Hydrolysis

Salts of weak acids/bases undergo hydrolysis in water. For a salt of weak acid (Ka) and strong base: pH = 7 + ½(pKa + log C). For salt of strong acid and weak base: pH = 7 − ½(pKb + log C). For salt of weak acid and weak base: pH = 7 + ½(pKa − pKb). The degree of hydrolysis h ≈ √(Kh/C) where Kh = Kw/Ka (or Kw/Kb).

8. Solubility and pH Dependence

Solubility of metal hydroxides increases in acidic solutions — added H⁺ reacts with OH⁻ (common ion removed), shifting equilibrium right. Solubility of CaF₂ increases in acid (F⁻ + H⁺ → HF). Solubility of AgCl is independent of pH (Cl⁻ doesn't react with H⁺ to form a weak acid significantly). This pH dependence of solubility is extensively used in qualitative analysis and separation schemes.

Frequently Asked Questions
1. Why is the solid BiO(OH) not in Ksp expression?
Pure solids have constant activity = 1 (their "concentration" doesn't change as long as some solid remains). Including them would make Ksp dependent on the amount of solid, which makes no physical sense. Only dissolved species (aqueous ions) appear in Ksp.
2. Why is [BiO⁺] = [OH⁻] = s?
From the balanced equation, each formula unit of BiO(OH) that dissolves produces exactly 1 BiO⁺ and 1 OH⁻. Starting from pure water where neither ion is present, if s moles dissolve per litre, both ions are produced in equal amounts: [BiO⁺] = [OH⁻] = s mol/L.
3. How does adding NaCl affect the solubility of AgCl?
AgCl(s) ⇌ Ag⁺ + Cl⁻. Adding NaCl increases [Cl⁻] (common ion). By Le Chatelier's principle, equilibrium shifts left, reducing Ag⁺ and decreasing AgCl solubility. Ksp stays the same (temperature hasn't changed), but now [Ag⁺]×[Cl⁻] must still equal Ksp — since [Cl⁻] increased, [Ag⁺] must decrease.
4. What is the ionic product Q and how does it predict precipitation?
Q = [M^n+][X^m−] calculated using current (actual) concentrations. If Q > Ksp: solution is supersaturated → precipitation occurs until Q = Ksp. If Q = Ksp: solution is just saturated, equilibrium. If Q < Ksp: solution is unsaturated → no precipitation, more solid can dissolve.
5. For Mg(OH)₂ (Ksp=1.8×10⁻¹¹), what is the solubility?
Mg(OH)₂(s) ⇌ Mg²⁺ + 2OH⁻. If solubility = s: [Mg²⁺] = s, [OH⁻] = 2s. Ksp = s×(2s)² = 4s³ = 1.8×10⁻¹¹. s³ = 4.5×10⁻¹², s = (4.5×10⁻¹²)^(1/3) ≈ 1.65×10⁻⁴ mol/L. Note the 4s³ formula for 1:2 type salts.
6. What is the Henderson-Hasselbalch equation?
pH = pKa + log([A⁻]/[HA]). Used for calculating pH of buffer solutions. When [A⁻] = [HA]: pH = pKa (half-equivalence point). When [A⁻]/[HA] = 10: pH = pKa + 1. Effective buffer range: pH = pKa ± 1. The equation is derived from the Ka expression for the weak acid equilibrium.
7. What is the pH at the equivalence point of CH₃COOH + NaOH titration?
At equivalence point, all CH₃COOH has been converted to CH₃COO⁻Na⁺. The solution contains sodium acetate — a salt of weak acid and strong base, which undergoes hydrolysis: CH₃COO⁻ + H₂O ⇌ CH₃COOH + OH⁻. The solution is basic (pH > 7). pH = 7 + ½(pKa + log C). For acetic acid (Ka=1.8×10⁻⁵), pKa=4.74, at 0.1M: pH ≈ 8.87.
8. How does temperature affect Kw?
Kw increases with temperature (water autoionisation is endothermic). At 25°C: Kw = 10⁻¹⁴, neutral pH = 7. At 37°C (body temperature): Kw ≈ 2.4×10⁻¹⁴, neutral pH = 6.8. At 60°C: Kw ≈ 10⁻¹³, neutral pH = 6.5. So "neutral" is not always pH=7 — it's when [H⁺]=[OH⁻], which depends on temperature. The pH + pOH = 14 formula is only valid at 25°C.
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