IChO 1969 · Theory problem 1

Electrolysis of a potassium sulphate solution

An amount of 20 g of potassium sulphate was dissolved in 150 cm³ of water. The solution was then electrolysed. After electrolysis, the content of potassium sulphate in the solution was 15 % by mass.

Problem:

What volumes of hydrogen and oxygen were obtained at a temperature of 20 °C and a pressure of 101 325 Pa?

Official English text of the problem.

Answers

  • Problem 1: Hydrogen, \(\ce{H2}\) ([H][H]): \(\boxed{49.0\ \mathrm{dm^3}}\); oxygen, \(\ce{O2}\) (O=O): \(\boxed{24.5\ \mathrm{dm^3}}\).

Solution

Problem 1

Assume ordinary electrolysis with inert electrodes, a water density of \(1.00\ \mathrm{g\,cm^{-3}}\), negligible evaporation, and ideal gas behaviour.

Potassium sulphate, \(\ce{K2SO4}\) ([K+].[K+].[O-]S(=O)(=O)[O-]), acts as the electrolyte and remains in the solution. Water, \(\ce{H2O}\) (O), is decomposed into hydrogen and oxygen.

The electrode reactions, written using hydroxide ions, \(\ce{OH-}\) ([OH-]), are

\[ \begin{aligned} \text{Cathode:}\quad &\ce{2H2O + 2e- -> H2 + 2OH-},\\ \text{Anode:}\quad &\ce{4OH- -> O2 + 2H2O + 4e-}. \end{aligned} \]

Doubling the cathode reaction and adding gives

\[ \ce{2H2O(l) -> 2H2(g) + O2(g)}. \]

Thus, the solution loses mass as the gaseous products escape, while its potassium sulphate content remains \(20\ \mathrm{g}\).

The initial mass of solution is

\[ m_{\mathrm{initial}} =20\ \mathrm{g} +(150\ \mathrm{cm^3})(1.00\ \mathrm{g\,cm^{-3}}) =170\ \mathrm{g}. \]

Since the final solution contains \(15\%\) potassium sulphate by mass,

\[ 0.15=\frac{20\ \mathrm{g}}{m_{\mathrm{final}}}, \qquad m_{\mathrm{final}}=\frac{20}{0.15}=133.333\ldots\ \mathrm{g}. \]

The mass of water decomposed is therefore

\[ m(\ce{H2O})=170-133.333\ldots =36.666\ldots\ \mathrm{g}. \]

Using \(M(\ce{H2O})=18.0\ \mathrm{g\,mol^{-1}}\),

\[ n(\ce{H2O}) =\frac{36.666\ldots\ \mathrm{g}} {18.0\ \mathrm{g\,mol^{-1}}} =2.037\ldots\ \mathrm{mol}. \]

The overall reaction gives

\[ n(\ce{H2})=2.037\ldots\ \mathrm{mol}, \qquad n(\ce{O2})=1.0185\ldots\ \mathrm{mol}. \]

At \(T=293.15\ \mathrm{K}\) and \(p=101\,325\ \mathrm{Pa}\), apply \(V=nRT/p\), with \(R=8.314\ \mathrm{Pa\,m^3\,mol^{-1}\,K^{-1}}\):

\[ V(\ce{H2}) =\frac{(2.037\ldots)(8.314)(293.15)}{101\,325}\ \mathrm{m^3} =\boxed{49.0\ \mathrm{dm^3}}. \]

At the same temperature and pressure, oxygen occupies half the hydrogen volume:

\[ V(\ce{O2})=\frac12V(\ce{H2}) =\boxed{24.5\ \mathrm{dm^3}}. \]

The solution was checked against the official solution.