Chemical Equilibrium: MDCAT Notes and MCQs
Equilibrium
- In a reversible reaction, equilibrium is reached when rate of forward = rate of reverse reaction. It is dynamic; concentrations stay constant (not necessarily equal); macroscopic properties (colour, pressure, density) become constant.
- Can be approached from either side; needs a closed system.
- For aA + bB ⇌ cC + dD: Kc = [C]c[D]d / [A]a[B]b. Kp = Kc(RT)Δn; Kp = Kc when Δn = 0.
- Large K → products favoured. K changes only with temperature.
Le Chatelier's principle
If a stress is applied to a system at equilibrium, the system shifts to partially undo the stress.
- Concentration: adding reactant → shifts forward.
- Pressure: increase → shifts to side with fewer gas moles; no effect if Δn = 0 (e.g. H2 + I2 ⇌ 2HI).
- Temperature: increase favours endothermic direction (and changes K).
- Catalyst: no shift — equilibrium reached faster only.
Haber process
N2 + 3H2 ⇌ 2NH3; ΔH = −92.4 kJ/mol (exothermic, Δn = −2). Conditions: ≈ 200–300 atm, ≈ 400–450 °C, iron catalyst (promoters K2O/Al2O3). High pressure favours NH3; low temperature favours yield but is too slow → compromise (optimum) temperature. NH3 removed by liquefaction.
Solubility product (Ksp)
For a sparingly soluble salt AgCl ⇌ Ag+ + Cl−: Ksp = [Ag+][Cl−]. For PbCl2: Ksp = [Pb2+][Cl−]2 = 4s3. Precipitation occurs when ionic product > Ksp.
Common ion effect
Suppression of ionization/solubility of a weak electrolyte or sparingly soluble salt by adding a strong electrolyte with a common ion. E.g. passing HCl gas into saturated NaCl solution precipitates pure NaCl; adding CH3COONa to CH3COOH suppresses its ionization; NH4Cl suppresses NH4OH ionization (used in group III analysis).
Buffers
- Solutions that resist change in pH on adding small amounts of acid or base.
- Acidic buffer: weak acid + its salt with strong base — CH3COOH + CH3COONa (pH < 7). Basic buffer: weak base + its salt with strong acid — NH4OH + NH4Cl (pH > 7).
- Henderson equation: pH = pKa + log([salt]/[acid]); pOH = pKb + log([salt]/[base]). Maximum buffer capacity when [salt] = [acid] → pH = pKa.
- Blood pH 7.35–7.45 maintained by H2CO3/HCO3− buffer.
PMDC learning outcomes for this unit
- Chemical Equilibrium: 6.1 Define chemical equilibrium in terms of reversible reaction.
- Chemical Equilibrium: 6.2 Write both forward and reverse reactions; describe the macroscopic characteristics of each
- Le Chatelier's principle: 6.3 State Le Chatelier's principle and be able to apply it to systems in equilibrium with changes in concentration, pressure, temperature or addition of catalyst.
- Solubility Products: 6.4 Define and explain solubility products.
- Common Ion Effect: 6.5 Define and explain the common ion effect by giving suitable examples.
- Buffer Solution: 6.6 Define buffer solution and explain types of buffers.
- Haber's Process: 6.7 Explain synthesis of ammonia by Haber's process.