IChO 1983 · Theory problem 3

Analysis of a NaCl-KCl mixture with silver nitrate and a copper strip

A sample containing a mixture of sodium chloride and potassium chloride weights 25 g. After its dissolution in water 840 ml of \(\ce{AgNO3}\) solution (\(c = 0.5\ \mathrm{mol\,dm^{-3}}\)) is added. The precipitate is filtered off and a strip of copper weighing 100.00 g is dipped into the filtrate. After a given time interval the strip weights 101.52 g.

Calculate the mass percent composition of the mixture.

Official English text of the problem.

Answers

  • 3. Assuming complete reaction of the excess silver ions with copper, the mixture contains approximately 70% sodium chloride, \(\ce{NaCl}\), [Na+].[Cl-], and 30% potassium chloride, \(\ce{KCl}\), [K+].[Cl-], by mass.

Solution

3. Silver nitrate, \(\ce{AgNO3}\), [Ag+].[O-][N+](=O)[O-], supplies silver(I) ions, \(\ce{Ag+}\), [Ag+]. These precipitate chloride ions, \(\ce{Cl-}\), [Cl-], as silver chloride, \(\ce{AgCl}\), [Ag+].[Cl-]:

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

Each mole of either salt therefore consumes one mole of silver nitrate. The ionic SMILES specify composition; they do not depict the solid crystal lattices.

The amount of silver nitrate initially added is

\[ n_0(\ce{AgNO3}) =(0.840\ \mathrm{dm^3})(0.5\ \mathrm{mol\,dm^{-3}}) =0.420\ \mathrm{mol}. \]

After filtration, the excess silver ions react with copper, \(\ce{Cu}\), [Cu], producing copper(II) ions, \(\ce{Cu^2+}\), [Cu+2], and depositing silver, \(\ce{Ag}\), [Ag]:

\[ \ce{Cu(s) + 2Ag+(aq) -> Cu^2+(aq) + 2Ag(s)} \]

The strip gains silver but loses copper. Thus its net mass gain is

\[ \Delta m=101.52-100.00=1.52\ \mathrm{g}. \]

Using standard molar masses, since none are supplied,

\[ \begin{aligned} M(\ce{Ag})&=107.87\ \mathrm{g\,mol^{-1}},& M(\ce{Cu})&=63.55\ \mathrm{g\,mol^{-1}},\\ M(\ce{NaCl})&=58.44\ \mathrm{g\,mol^{-1}},& M(\ce{KCl})&=74.55\ \mathrm{g\,mol^{-1}}. \end{aligned} \]

If \(t\) moles of copper dissolve, \(2t\) moles of silver deposit:

\[ \Delta m=t\left[2M(\ce{Ag})-M(\ce{Cu})\right]. \]

Hence

\[ t=\frac{1.52\ \mathrm{g}} {(2\times107.87-63.55)\ \mathrm{g\,mol^{-1}}} =0.0099875\ \mathrm{mol}. \]

Assuming all excess silver ions have reacted and the deposited silver remains on the strip,

\[ n_{\mathrm{excess}}(\ce{Ag+})=2t=0.019975\ \mathrm{mol}. \]

The amount of chloride originally present is therefore

\[ n(\ce{Cl-})=0.420-0.019975=0.400025\ \mathrm{mol}. \]

Let \(x=n(\ce{NaCl})\) and \(y=n(\ce{KCl})\). The chloride balance and sample mass give

\[ x+y=0.400025\ \mathrm{mol}, \]

\[ (58.44\ \mathrm{g\,mol^{-1}})x +(74.55\ \mathrm{g\,mol^{-1}})y =25\ \mathrm{g}. \]

Solving,

\[ x\approx0.29931\ \mathrm{mol}, \qquad y\approx0.10072\ \mathrm{mol}. \]

Consequently,

\[ m(\ce{NaCl})\approx17.49\ \mathrm{g}, \qquad m(\ce{KCl})\approx7.51\ \mathrm{g}, \]

and the mass percentages are

\[ \boxed{ w(\ce{NaCl})=\frac{17.49}{25}\times100\%\approx70\% } \]

\[ \boxed{ w(\ce{KCl})=\frac{7.51}{25}\times100\%\approx30\% } \]

The solution was checked against the official solution.