IChO 2003 · Theory problem 5

Converting silver chromate into silver chloride

The equilibrium constant of the reaction:

Figure 1

is given by the equation:

(a) \(K = K_{sp}(\ce{Ag2CrO4}) / K_{sp}(\ce{AgCl})^{2}\qquad(\quad)\)

(b) \(K = K_{sp}(\ce{Ag2CrO4}) \times K_{sp}(\ce{AgCl})^{2}\qquad(\quad)\)

(c) \(K = K_{sp}(\ce{AgCl}) / K_{sp}(\ce{Ag2CrO4})\qquad(\quad)\)

(d) \(K = K_{sp}(\ce{AgCl})^{2} / K_{sp}(\ce{Ag2CrO4})\qquad(\quad)\)

(e) \(K = K_{sp}(\ce{Ag2CrO4}) / K_{sp}(\ce{AgCl})\qquad(\quad)\)

Official English text of the problem.

Answers

  • (a) Correct. Tick this box: \(\displaystyle K=\frac{K_{sp}(\ce{Ag2CrO4})}{[K_{sp}(\ce{AgCl})]^2}\).
  • (b) Incorrect; leave blank.
  • (c) Incorrect; leave blank.
  • (d) Incorrect; leave blank.
  • (e) Incorrect; leave blank.

Solution

The species involved are silver chromate [Ag+].[Ag+].[O-][Cr](=O)(=O)[O-], silver chloride [Ag+].[Cl-], silver(I) ion [Ag+], chloride ion [Cl-], and chromate ion [O-][Cr](=O)(=O)[O-]. The salt SMILES specify their constituent ions and stoichiometry; the solids form extended ionic lattices. Chromate has tetrahedral coordination around chromium.

The two solubility equilibria are

\[ \ce{Ag2CrO4(s) <=> 2Ag+(aq) + CrO4^2-(aq)} \]

and

\[ \ce{AgCl(s) <=> Ag+(aq) + Cl-(aq)}. \]

Using dimensionless activities and taking each pure solid’s activity as unity,

\[ K_{sp}(\ce{Ag2CrO4}) =a(\ce{Ag+})^2a(\ce{CrO4^2-}), \]

\[ K_{sp}(\ce{AgCl}) =a(\ce{Ag+})a(\ce{Cl-}). \]

Reverse the second equilibrium and double it:

\[ \ce{2Ag+(aq) + 2Cl-(aq) <=> 2AgCl(s)}. \]

Reversing an equilibrium inverts its constant, and doubling its coefficients squares the constant. Thus this precipitation reaction has constant

\[ \frac{1}{[K_{sp}(\ce{AgCl})]^2}. \]

Adding it to silver chromate dissolution cancels the silver ions and gives the required reaction:

\[ \ce{Ag2CrO4(s) + 2Cl-(aq) <=> 2AgCl(s) + CrO4^2-(aq)}. \]

Equilibrium constants multiply when reactions are added, so

\[ \boxed{ K=\frac{K_{sp}(\ce{Ag2CrO4})}{[K_{sp}(\ce{AgCl})]^2} }. \]

Equivalently, division of the solubility-product expressions gives

\[ K=\frac{a(\ce{CrO4^2-})}{a(\ce{Cl-})^2}, \]

which is exactly the equilibrium expression for the stated reaction. Therefore (a) is the correct choice.

The answers were checked against the official answers published by the organisers.