IChO 1968 · Theory problem 1

Composition of an irradiated hydrogen-chlorine mixture

A mixture of hydrogen and chlorine kept in a closed flask at a constant temperature was irradiated by scattered light. After a certain time the chlorine content decreased by 20 % compared with that of the starting mixture and the resulting mixture had the composition as follows: 60 volume % of chlorine, 10 volume % of hydrogen, and 30 volume % of hydrogen chloride.

Problems:

1.1 What is the composition of the initial gaseous mixture?

1.2 How chlorine, hydrogen, and hydrogen chloride are produced?

Official English text of the problem.

Answers

  • 1.1 The initial mixture contained 75 volume % chlorine, \(\ce{Cl2}\), ClCl, and 25 volume % hydrogen, \(\ce{H2}\), [H][H].
  • 1.2 Representative preparations are:
  • Chlorine: oxidation of concentrated hydrochloric acid with manganese(IV) oxide; industrially, electrolysis of brine.
  • Hydrogen: reaction of zinc with dilute hydrochloric acid; industrially, steam reforming followed by the water-gas shift reaction, or as a coproduct of brine electrolysis.
  • Hydrogen chloride, \(\ce{HCl}\), [H]Cl: reaction of sodium chloride with concentrated sulfuric acid; industrially, direct combination of hydrogen and chlorine.

Solution

1.1 Initial composition

The light-induced reaction is

\[ \ce{H2 + Cl2 ->[light] 2HCl}. \]

For gases at the same temperature and pressure, volume fractions equal mole fractions. The reaction consumes two moles of gaseous reactants for every two moles of gaseous product formed, so the total amount of gas remains unchanged.

Take a basis of 100 mol of the final mixture:

\[ n(\ce{Cl2})=60\ \mathrm{mol},\qquad n(\ce{H2})=10\ \mathrm{mol},\qquad n(\ce{HCl})=30\ \mathrm{mol}. \]

The starting mixture contained only hydrogen and chlorine. Formation of \(30\ \mathrm{mol}\) of hydrogen chloride therefore consumed

\[ n_{\text{consumed}}(\ce{H2}) =n_{\text{consumed}}(\ce{Cl2}) =\frac{30}{2} =15\ \mathrm{mol}. \]

The material balance is:

Gas Initial amount Change Final amount
\(\ce{Cl2}\) \(75\ \mathrm{mol}\) \(-15\ \mathrm{mol}\) \(60\ \mathrm{mol}\)
\(\ce{H2}\) \(25\ \mathrm{mol}\) \(-15\ \mathrm{mol}\) \(10\ \mathrm{mol}\)
\(\ce{HCl}\) \(0\ \mathrm{mol}\) \(+30\ \mathrm{mol}\) \(30\ \mathrm{mol}\)
Total \(100\ \mathrm{mol}\) \(0\ \mathrm{mol}\) \(100\ \mathrm{mol}\)

Thus,

\[ \boxed{\text{Initial mixture: }75\text{ volume \% }\ce{Cl2} \text{ and }25\text{ volume \% }\ce{H2}.} \]

The relative decrease in chlorine is

\[ \frac{75-60}{75}\times100\%=20\%, \]

which agrees with the stated decrease.

1.2 Preparation of the gases

The question does not specify a production scale, so representative laboratory and industrial methods are given.

Chlorine

In the laboratory, warming manganese(IV) oxide with concentrated hydrochloric acid produces chlorine:

\[ \ce{MnO2 + 4HCl ->[\Delta] MnCl2 + Cl2 + 2H2O}. \]

Manganese is reduced from oxidation state \(+4\) to \(+2\), while chlorine is oxidized from \(-1\) to \(0\).

Industrially, concentrated aqueous sodium chloride—brine—is electrolysed:

\[ \ce{2NaCl + 2H2O ->[electrolysis] Cl2 + H2 + 2NaOH}. \]

Chlorine forms at the anode and hydrogen at the cathode. The electrode products are kept separate to permit collection of the gases and prevent their reaction with each other or with the sodium hydroxide solution.

Hydrogen

In the laboratory, zinc reacts with dilute hydrochloric acid:

\[ \ce{Zn + 2HCl -> ZnCl2 + H2}. \]

Zinc is oxidized from \(0\) to \(+2\), and hydrogen is reduced from \(+1\) to \(0\).

Hydrogen is also obtained industrially as the cathodic product of brine electrolysis, as shown above. Another major route is the catalytic reaction of methane with steam at high temperature:

\[ \ce{CH4 + H2O <=> CO + 3H2}. \]

The carbon monoxide is then reacted with further steam in the water-gas shift reaction:

\[ \ce{CO + H2O <=> CO2 + H2}. \]

After removal of carbon dioxide and other impurities, hydrogen is obtained.

Hydrogen chloride

In the laboratory, gentle heating of sodium chloride with concentrated sulfuric acid gives hydrogen chloride gas:

\[ \ce{NaCl + H2SO4 -> NaHSO4 + HCl ^}. \]

With stronger heating and sufficient sodium chloride, the overall reaction is

\[ \ce{2NaCl + H2SO4 ->[\Delta] Na2SO4 + 2HCl ^}. \]

The low volatility of sulfuric acid allows volatile hydrogen chloride to be expelled from the mixture.

Industrially, hydrogen chloride can be produced by controlled direct combination of hydrogen and chlorine:

\[ \ce{H2 + Cl2 -> 2HCl}. \]

Absorbing the resulting hydrogen chloride gas in water produces hydrochloric acid.

Names and SMILES for the additional substances used above

For salts and extended solids, the dot-separated representations below give formal ionic formula-unit compositions; they do not describe a discrete molecule, a crystal lattice, or solvation.

Formula Name SMILES
\(\ce{H2O}\) Water O
\(\ce{MnO2}\) Manganese(IV) oxide [Mn+4].[O-2].[O-2]
\(\ce{MnCl2}\) Manganese(II) chloride [Mn+2].[Cl-].[Cl-]
\(\ce{NaCl}\) Sodium chloride [Na+].[Cl-]
\(\ce{NaOH}\) Sodium hydroxide [Na+].[OH-]
\(\ce{ZnCl2}\) Zinc chloride [Zn+2].[Cl-].[Cl-]
\(\ce{CH4}\) Methane C
\(\ce{CO}\) Carbon monoxide [C-]#[O+]
\(\ce{CO2}\) Carbon dioxide O=C=O
\(\ce{H2SO4}\) Sulfuric acid OS(=O)(=O)O
\(\ce{NaHSO4}\) Sodium hydrogen sulfate [Na+].OS(=O)(=O)[O-]
\(\ce{Na2SO4}\) Sodium sulfate [Na+].[Na+].[O-]S(=O)(=O)[O-]

Zinc, \(\ce{Zn}\), is a metallic solid; [Zn] represents an individual zinc atom, not its metallic lattice.

The solution was checked against the official solution.