IChO 1970 · Theory problem 5

Crystallisation of copper(II) sulphate pentahydrate

An amount of 20 g of cooper (II) oxide was treated with a stoichiometric amount of a warm 20% sulphuric acid solution to produce a solution of copper (II) sulphate.

Problem:

How many grams of crystalline copper(II) sulphate (\(\ce{CuSO4 . 5H2O}\)) have crystallised when the solution is cooled to \(20\,^\circ\mathrm{C}\)?

Relative atomic masses: \(A_\mathrm{r}(\ce{Cu}) = 63.5;\quad A_\mathrm{r}(\ce{S}) = 32;\quad A_\mathrm{r}(\ce{O}) = 16;\quad A_\mathrm{r}(\ce{H}) = 1\)

Solubility of \(\ce{CuSO4}\) at \(20\,^\circ\mathrm{C}\): \(s = 20.9\) g of \(\ce{CuSO4}\) in 100 g of \(\ce{H2O}\).

Official English text of the problem.

Answers

  • Problem 5: \(\boxed{32.9\ \mathrm{g}}\) of copper(II) sulphate pentahydrate, \(\ce{CuSO4 . 5H2O}\), crystallises. SMILES: [Cu+2].[O-]S(=O)(=O)[O-].O.O.O.O.O.

Solution

Copper(II) oxide ([Cu+2].[O-2]) reacts with sulphuric acid (OS(=O)(=O)O) to produce copper(II) sulphate ([Cu+2].[O-]S(=O)(=O)[O-]) and water (O):

\[ \ce{CuO(s) + H2SO4(aq) -> CuSO4(aq) + H2O(l)}. \]

The SMILES for the ionic compounds specify formula-unit compositions; they do not encode crystal lattices or coordination geometries.

Using the given atomic masses, the molar masses are \[ \begin{aligned} M(\ce{CuO}) &= 79.5\ \mathrm{g\,mol^{-1}},\\ M(\ce{H2SO4}) &= 98\ \mathrm{g\,mol^{-1}},\\ M(\ce{H2O}) &= 18\ \mathrm{g\,mol^{-1}},\\ M(\ce{CuSO4}) &= 159.5\ \mathrm{g\,mol^{-1}},\\ M(\ce{CuSO4 . 5H2O}) &= 159.5+5(18) =249.5\ \mathrm{g\,mol^{-1}}. \end{aligned} \]

The amount of copper(II) oxide is \[ n=\frac{20\ \mathrm{g}}{79.5\ \mathrm{g\,mol^{-1}}} =0.251572\ \mathrm{mol}. \]

The reaction consumes this same amount of sulphuric acid and produces this amount of both copper(II) sulphate and water. Thus, \[ \begin{aligned} m(\ce{H2SO4})&=0.251572(98)=24.6541\ \mathrm{g},\\ m(\ce{CuSO4})&=0.251572(159.5)=40.1258\ \mathrm{g},\\ m(\text{reaction water})&=0.251572(18)=4.52830\ \mathrm{g}. \end{aligned} \]

The acid solution contains 20% sulphuric acid by mass, so its mass is \[ m(\text{acid solution})=\frac{24.6541}{0.20} =123.2704\ \mathrm{g}. \]

The total water present after reaction includes both the water supplied with the acid and the water formed: \[ m_{\mathrm{water},0} =0.80(123.2704)+4.52830 =103.1447\ \mathrm{g}. \]

On cooling, pentahydrate crystals form: \[ \ce{CuSO4(aq) + 5H2O(l) -> CuSO4 . 5H2O(s)}. \]

Crystallisation removes both dissolved salt and water from the solution. Let \(x\) be the mass of pentahydrate crystals. These crystals contain \[ \frac{159.5}{249.5}x \quad\text{of }\ce{CuSO4}, \qquad \frac{90}{249.5}x \quad\text{of }\ce{H2O}. \]

The remaining solution is saturated at \(20\,^\circ\mathrm{C}\), giving \[ \frac{40.1258\ \mathrm{g}-\dfrac{159.5}{249.5}x} {103.1447\ \mathrm{g}-\dfrac{90}{249.5}x} =\frac{20.9}{100}. \]

Therefore, \[ x= \frac{40.1258-0.209(103.1447)} {\dfrac{159.5}{249.5}-0.209\dfrac{90}{249.5}} \ \mathrm{g} =32.9295\ \mathrm{g}. \]

Hence the mass crystallised is \[ \boxed{m(\ce{CuSO4 . 5H2O})=32.9\ \mathrm{g}}. \]

The solution was checked against the official solution.