Chemistry 9701 · AS & A Level · Chemistry of transition elements

Chemistry of transition elements — practice question

Cadmium ions can make complexes with primary amines as well as with 1,2-diaminoethane. $ \text{Cd}^{2+}(aq) + 4\text{CH}_3\text{NH}_2(aq) \rightleftharpoons [\text{Cd}(\text{CH}_3\text{NH}_2)_4]^{2+}(aq) \qquad K_{\text{stab}} = 3.6 \times 10^6 \; \text{(equilibrium I)} $ $ \text{Cd}^{2+}(aq) + 2\text{H}_2\text{NCH}_2\text{CH}_2\text{NH}_2(aq) \rightleftharpoons [\text{Cd}(\text{H}_2\text{NCH}_2\text{CH}_2\text{NH}_2)_2]^{2+}(aq) \qquad K_{\text{stab}} = 4.2 \times 10^{10} \; \text{(equilibrium II)} $
(a(i))[2]

Write the stability-constant expression, $K_{\text{stab}}$, for equilibrium I, and state the units.

(a(ii))[2]

In a groundwater sample, the concentration of $\text{Cd}^{2+}(aq)$ is $1.00 \times 10^{-4} \text{ mol dm}^{-3}$. Calculate the concentration of $\text{CH}_3\text{NH}_2(aq)$ needed to lower the concentration of $\text{Cd}^{2+}(aq)$ in this dilute solution by a factor of one thousand.

(b(i))[1]

Suggest a reason why the $\Delta H^{\circ}$ values for the two equilibria are so similar.

(b(ii))[1]

Calculate the value of $\Delta S^{\circ}$ for equilibrium II.

(b(iii))[1]

Suggest a reason for the difference between the $\Delta S^{\circ}$ you calculated for equilibrium II and the value for equilibrium I shown in the table.

(b(iv))[1]

Which of the two complexes is more stable? Give your reason.

Worked solution & mark scheme

This 8-mark question has a full step-by-step worked solution and mark scheme. One marking point: $K_{\text{stab}}=\frac{[\mathrm{Cd(CH_3NH_2)_4^{2+}}]}{[\mathrm{Cd^{2+}}][\mathrm{CH_3NH_2}]^4}$; the units are $\mathrm{mol^{-4}\,dm^{12}}$

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