IChO 1973 · Theory problem 2

Combustion of a gaseous hydrocarbon in a closed vessel

A mixture of a gaseous hydrocarbon and oxygen is in a vessel of a volume of 1 dm³ at a temperature of 406.5 K and a pressure of 101 325 Pa. There is twice as much oxygen in the mixture as is needed for the reaction with the hydrocarbon. After combustion of the hydrocarbon the pressure in the vessel (at the same temperature) is increased by 5 %.

Problem:

2.1 What hydrocarbon was in the mixture when the mass of water formed by the combustion was 0.162 g.

Official English text of the problem.

Answers

  • 2.1 The molecular formula is \(\ce{C3H6}\). The hydrocarbon can be propene C=CC or cyclopropane C1CC1; the given data cannot distinguish these two isomers.

Solution

2.1

Let the hydrocarbon be \(\ce{C_xH_y}\), with \(a\) moles initially present. Its complete combustion consumes oxygen O=O and produces carbon dioxide O=C=O and water O:

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

At \(406.5\ \mathrm{K}\) and the stated pressures, the water formed remains gaseous. Treating the gases as ideal, pressure is proportional to total gas amount at fixed temperature and volume.

The initial total amount is

\[ n_i=\frac{pV}{RT} =\frac{(101325\ \mathrm{Pa})(1.00\times10^{-3}\ \mathrm{m^3})} {(8.314\ \mathrm{Pa\,m^3\,mol^{-1}\,K^{-1}})(406.5\ \mathrm{K})} \approx 3.00\times10^{-2}\ \mathrm{mol}. \]

The amount of water formed is

\[ n_{\mathrm{water}} =\frac{0.162\ \mathrm{g}}{18.0\ \mathrm{g\,mol^{-1}}} =9.00\times10^{-3}\ \mathrm{mol} =\frac{ay}{2}. \]

Because the initial oxygen amount is twice the amount required for combustion,

\[ n_{\mathrm{oxygen},i}=2a\left(x+\frac y4\right). \]

Thus,

\[ n_i=a+2a\left(x+\frac y4\right) =a\left(1+2x+\frac y2\right). \]

After combustion, half the initial oxygen remains. Adding this excess oxygen to the carbon dioxide and water gives

\[ n_f=ax+\frac{ay}{2}+a\left(x+\frac y4\right) =a\left(2x+\frac{3y}{4}\right). \]

Consequently,

\[ n_f-n_i=a\left(\frac y4-1\right) =\frac{n_{\mathrm{water}}}{2}-a. \]

The pressure increase of \(5\%\) gives

\[ n_f-n_i=0.05n_i \approx1.50\times10^{-3}\ \mathrm{mol}. \]

Therefore, the initial hydrocarbon amount was

\[ a=\frac{9.00\times10^{-3}}{2}-1.50\times10^{-3} =3.00\times10^{-3}\ \mathrm{mol}. \]

The hydrogen subscript follows from the water yield:

\[ y=\frac{2n_{\mathrm{water}}}{a} =\frac{2(9.00\times10^{-3})}{3.00\times10^{-3}} =6. \]

Using the initial total amount,

\[ 1+2x+\frac y2=\frac{n_i}{a}\approx10, \]

so

\[ 1+2x+3=10 \quad\Longrightarrow\quad x=3. \]

Hence the molecular formula is \(\boxed{\ce{C3H6}}\), and its balanced combustion equation is

\[ \boxed{\ce{2C3H6 + 9O2 -> 6CO2 + 6H2O}}. \]

As a check, per mole of hydrocarbon the initial mixture contains \(1+9=10\) moles of gas. After combustion it contains \(3+3+4.5=10.5\) moles, giving exactly the stated \(5\%\) pressure increase.

Both propene C=CC and cyclopropane C1CC1 have this formula and satisfy the conditions.

The solution was checked against the official solution.