IChO 1969 · Theory problem 3

Combustion analysis of a gaseous hydrocarbon

A 10 cm³ sample of an unknown gaseous hydrocarbon was mixed with 70 cm³ of oxygen and the mixture was set on fire by means of an electric spark. When the reaction was over and water vapours were liquefied, the final volume of gases decreased to 65 cm³. This mixture then reacted with a potassium hydroxide solution and the volume of gases decreased to 45 cm³.

Problem:

What is the molecular formula of the unknown hydrocarbon if volumes of gases were measured at standard temperature and pressure (STP) conditions?

Official English text of the problem.

Answers

  • 3. \(\boxed{\ce{C2H2}}\): ethyne (acetylene), SMILES C#C.

Solution

3. Let the hydrocarbon have molecular formula \(\ce{C_{$x$}H_{$y$}}\). Its complete combustion follows

\[ \ce{C_{$x$}H_{$y$} + ($x$ + $y$/4) O2 -> $x$ CO2 + ($y$/2) H2O}. \]

At the same temperature and pressure, gas volumes are proportional to amounts in moles.

After water, SMILES O, has condensed, the remaining gases are carbon dioxide, SMILES O=C=O, and excess oxygen, SMILES O=O.

Potassium hydroxide, SMILES [K+].[OH-], absorbs carbon dioxide. With excess alkali, this reaction is

\[ \ce{CO2 + 2KOH -> K2CO3 + H2O}, \]

forming potassium carbonate, SMILES [K+].[K+].[O-]C(=O)[O-].

Thus the volume of carbon dioxide produced is

\[ V_{\ce{CO2}}=(65-45)\ \mathrm{cm^3} =20\ \mathrm{cm^3}. \]

Each mole of hydrocarbon produces \(x\) moles of carbon dioxide, so

\[ x=\frac{20\ \mathrm{cm^3}}{10\ \mathrm{cm^3}}=2. \]

The gas remaining after absorption is unused oxygen. Therefore,

\[ V_{\ce{O2},\,\text{consumed}} =(70-45)\ \mathrm{cm^3} =25\ \mathrm{cm^3}. \]

The combustion equation then gives

\[ x+\frac{y}{4} =\frac{25\ \mathrm{cm^3}}{10\ \mathrm{cm^3}} =2.5. \]

Substituting \(x=2\),

\[ 2+\frac{y}{4}=2.5 \quad\Longrightarrow\quad y=2. \]

Hence the hydrocarbon is ethyne (acetylene), \(\ce{C2H2}\), SMILES C#C, whose balanced combustion equation is

\[ \boxed{\ce{2C2H2 + 5O2 -> 4CO2 + 2H2O}}. \]

As a check, \(10\ \mathrm{cm^3}\) of ethyne consumes \(25\ \mathrm{cm^3}\) of oxygen and produces \(20\ \mathrm{cm^3}\) of carbon dioxide. After condensation, the gas volume is \(45+20=65\ \mathrm{cm^3}\); carbon dioxide absorption leaves \(45\ \mathrm{cm^3}\), matching both observations.

The solution was checked against the official solution.