IChO 1970 · Theory problem 1

Structure of a gas from its combustion products

An amount of 23 g of gas (density \(\rho = 2.05\ \mathrm{g\,dm^{-3}}\) at STP) when burned, gives 44 g of carbon dioxide and 27 g of water.

Problem:

What is the structural formula of the gas (compound)?

Official English text of the problem.

Answers

  1. Dimethyl ether (methoxymethane), \(\ce{CH3-O-CH3}\), with molecular formula \(\ce{C2H6O}\). SMILES: COC.

Solution

1. Determine the composition and molecular formula.

The combustion products are carbon dioxide (O=C=O) and water (O). Using the conventional atomic masses \(12\), \(1\), and \(16\) for carbon, hydrogen, and oxygen:

\[ n(\ce{CO2})=\frac{44\ \mathrm{g}}{44\ \mathrm{g\,mol^{-1}}} =1.0\ \mathrm{mol}, \] \[ n(\ce{H2O})=\frac{27\ \mathrm{g}}{18\ \mathrm{g\,mol^{-1}}} =1.5\ \mathrm{mol}. \]

Thus the sample contains \(1.0\ \mathrm{mol}\) of carbon atoms and \(2(1.5)=3.0\ \mathrm{mol}\) of hydrogen atoms, corresponding to \(12\ \mathrm{g}\) of carbon and \(3\ \mathrm{g}\) of hydrogen.

The remaining mass is oxygen:

\[ m_{\mathrm O}=23-12-3=8\ \mathrm{g}, \qquad n_{\mathrm O}=\frac{8\ \mathrm{g}}{16\ \mathrm{g\,mol^{-1}}} =0.50\ \mathrm{mol}. \]

The atomic ratio is therefore

\[ n_{\mathrm C}:n_{\mathrm H}:n_{\mathrm O} =1.0:3.0:0.50=2:6:1, \]

giving the empirical formula \(\ce{C2H6O}\), with empirical formula mass \(46\ \mathrm{g\,mol^{-1}}\).

Using the ideal-gas molar volume at conventional STP, \(V_m=22.4\ \mathrm{dm^3\,mol^{-1}}\),

\[ M=\rho V_m =(2.05\ \mathrm{g\,dm^{-3}}) (22.4\ \mathrm{dm^3\,mol^{-1}}) =45.9\ \mathrm{g\,mol^{-1}}. \]

This agrees with the empirical formula mass, so the molecular formula is \(\ce{C2H6O}\).

There are two constitutional isomers:

  • Dimethyl ether, \(\ce{CH3-O-CH3}\), SMILES COC.
  • Ethanol, \(\ce{CH3-CH2-OH}\), SMILES CCO.

Dimethyl ether is gaseous at STP, whereas ethanol is liquid. The stated gaseous state therefore identifies dimethyl ether, whose oxygen atom is bonded to two methyl groups.

Its balanced combustion equation, using dioxygen (O=O), is

\[ \boxed{\ce{CH3-O-CH3 + 3O2 -> 2CO2 + 3H2O}}. \]

Indeed, \(23\ \mathrm{g}\) is \(0.50\ \mathrm{mol}\) of dimethyl ether, producing \(1.0\ \mathrm{mol}\) (\(44\ \mathrm{g}\)) of carbon dioxide and \(1.5\ \mathrm{mol}\) (\(27\ \mathrm{g}\)) of water.

The solution was checked against the official solution.