Part of JPC-02 — Equilibrium: Chemical & Ionic (pH, Buffer, Ksp)

Weak Acid Equilibrium — Derivation and Approximation

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For weak acid HA at concentration C: HA <=> H+ + A-. If degree of dissociation = alpha, then [H+] = Calpha, [A-] = Calpha, [HA] = C(1-alpha). Ka = Calpha^21alpha\frac{2}{1-alpha}. When alpha << 1 (less than 5%), the approximation gives Ka = Calpha2alpha^2, so alpha = sqrtKaC\frac{Ka}{C} and [H+] = sqrt(KaC). The pH formula becomes pH = 12\frac{1}{2}(pKa + pC) where pC = -log(C). Always verify the approximation: if alpha > 5%, use the quadratic formula. Ostwald's dilution law states that alpha increases upon dilution (alpha = sqrtKaC\frac{Ka}{C} — as C decreases, alpha increases). However, the actual [H+] = sqrt(KaC) decreases upon dilution (pH increases). These two trends seem contradictory but are both true.

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