Answer the following :
Derive Ostwald's dilution law for the CH3COOH.
Solution
i.
Consider an equilibrium of weak acid CH3COOH that exists in solution partly as the undissociated species CH3COOH and partly H+ and CH3COO– ions. Then
\[\ce{CH3COOH_{(aq)} ⇌ H^+_{ (aq)} + CH3COO^-_{ (aq)}}\]
ii.
The acid dissociation constant is given as:
`"K"_"a" = (["H"^+]["CH"_3"COO"^-])/[["CH"_3"COOH"]]` ....(1)
iii.
Suppose 1 mol of acid CH3COOH is initially present in volume V dm3 of the solution. At equilibrium, the fraction dissociated would be α, where α is the degree of dissociation of the acid. The fraction of an acid that remains undissociated would be (1 - α).
\[\ce{CH3COOH_{(aq)}⇌ H^+_{ (aq)} + CH3COO^-_{ (aq)}}\] | |||
The amount present at equilibrium (mol) | (1 - α) | α | α |
Concentration at equilibrium (mol dm−3) | `(1 - α)/"V"` | `α/"V"` |
`α/"V"` |
iv.
Thus, at equilibrium [CH3COOH] = `(1 - α)/"V"` mol dm-3,
[H+] = [CH3COO-] = `α/"V"` mol dm-3
v.
Substituting these in equation (1),
Ka = `(α / "V" α / "V") /((1 - α) / "V") = α^2/(1 - α "V")` ...(2)
vi.
If c is the initial concentration of CH3COOH in mol dm–3 and V is the volume in dm3 mol–1 then c = 1/V. Replacing 1/V in equation (2) by c,
we get
Ka = `(α^2"c")/(1 - α)` ...(3)
vii.
For the weak acid CH3COOH, α is very small, or (1 − α) ≅ 1. With this equation (2) and (3) becomes:
Ka = `α^2/"V"` and Ka = α2c ...(4)
α = `sqrt("K"_"a")/"c"` or α = `sqrt("K"_"a". "V")` ...(5)
Equation (5) implies that the degree of dissociation of a weak acid (CH3COOH) is inversely proportional to the square root of its concentration or directly proportional to the square root of the volume of the solution containing 1 mol of the weak acid.