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Ch.17 - Applications of Aqueous Equilibria
Chapter 17, Problem 119

Silver ion reacts with excess CN- to form a colorless complex ion, [Ag(CN)2]-, which has a formation constant Kf = 3.0 x 10^20. Calculate the concentration of Ag+ in a solution prepared by mixing equal volumes of 2.0 x 10^-3 M AgNO3 and 0.20 M NaCN.

Verified step by step guidance
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Step 1: Write the balanced chemical equation for the formation of the complex ion: \[ \text{Ag}^+ + 2\text{CN}^- \rightleftharpoons [\text{Ag(CN)}_2]^- \]
Step 2: Use the initial concentrations of AgNO3 and NaCN to determine the initial concentrations of \( \text{Ag}^+ \) and \( \text{CN}^- \) in the mixed solution. Since equal volumes are mixed, the concentrations are halved: \( [\text{Ag}^+]_0 = 1.0 \times 10^{-3} \text{ M} \) and \( [\text{CN}^-]_0 = 0.10 \text{ M} \).
Step 3: Set up the expression for the formation constant \( K_f \) for the complex ion: \[ K_f = \frac{[\text{Ag(CN)}_2]^-}{[\text{Ag}^+][\text{CN}^-]^2} \]
Step 4: Assume that \( x \) is the change in concentration of \( \text{Ag}^+ \) that forms the complex ion. Then, express the equilibrium concentrations in terms of \( x \): \( [\text{Ag}^+] = 1.0 \times 10^{-3} - x \), \( [\text{CN}^-] = 0.10 - 2x \), and \( [\text{Ag(CN)}_2]^- = x \).
Step 5: Substitute the equilibrium concentrations into the \( K_f \) expression and solve for \( x \), which represents the concentration of \( [\text{Ag(CN)}_2]^- \). Use this to find the concentration of \( \text{Ag}^+ \) at equilibrium.

Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Complex Ion Formation

Complex ion formation occurs when a metal ion, such as Ag+, binds with ligands, like CN-, to create a more stable species. In this case, the silver ion forms the complex ion [Ag(CN)2]-, which is colorless. The stability of this complex is quantified by the formation constant (Kf), indicating the extent to which the complex forms in solution.
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Equilibrium and Kf

The formation constant (Kf) is a measure of the equilibrium position for the formation of a complex ion from its constituent ions. A high Kf value, such as 3.0 x 10^20 for [Ag(CN)2]-, suggests that the complex is favored in solution, meaning that the concentration of free Ag+ ions will be very low when the complex is formed. Understanding Kf is crucial for calculating the concentration of uncomplexed ions.
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Dilution and Concentration Calculations

When mixing solutions, the concentration of each component changes due to dilution. In this problem, equal volumes of 2.0 x 10^-3 M AgNO3 and 0.20 M NaCN are mixed, which requires calculating the new concentrations after dilution. This involves using the dilution formula (C1V1 = C2V2) to find the initial concentrations before considering the formation of the complex.
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