IChO 1973 · Theory problem 4

Precipitate and dry residue from two unknown solutions

When solutions of two unknown substances are mixed together in stoichiometric ratio, 1.25 g of a precipitate are formed which contain a salt of a bivalent metal \(\ce{M}\). The precipitate when heated to 1100 °C is decomposed to 0.70 g of a solid metal oxide \(\ce{MO}\) and another gaseous oxide. After evaporation of the filtrate, a dry residue with a mass of 2.0 g remains which yields two products by thermal decomposition at 215 °C: a gaseous oxide and 0.90 g of water vapour. The total volume of the gaseous mixture is 1.68 dm³ (at STP).

Problem:

4.1 Determine the unknown compounds and write chemical equations for the above mentioned reactions.

Official English text of the problem.

Answers

  • 4.1 The original solutes are calcium nitrate and ammonium carbonate. The metal is calcium, the precipitate is calcium carbonate, and the dry residue is ammonium nitrate.
Role Compound Formula SMILES
Original solute Calcium nitrate \(\ce{Ca(NO3)2}\) [Ca+2].[O-][N+](=O)[O-].[O-][N+](=O)[O-]
Original solute Ammonium carbonate \(\ce{(NH4)2CO3}\) [NH4+].[NH4+].[O-]C(=O)[O-]
Precipitate Calcium carbonate \(\ce{CaCO3}\) [Ca+2].[O-]C(=O)[O-]
Solid decomposition product Calcium oxide \(\ce{CaO}\) [Ca+2].[O-2]
Gas from the precipitate Carbon dioxide \(\ce{CO2}\) O=C=O
Dry filtrate residue Ammonium nitrate \(\ce{NH4NO3}\) [NH4+].[O-][N+](=O)[O-]
Oxide from the dry residue Nitrous oxide \(\ce{N2O}\) N#[N+][O-]
Other decomposition product Water \(\ce{H2O}\) O

The disconnected SMILES specify the constituent ions of the salts; they do not encode their crystal lattices.

Solution

4.1

Use the conventional STP molar volume \(22.4\,\mathrm{dm^3\,mol^{-1}}\) and rounded atomic molar masses. Guard digits are retained in intermediate calculations.

Identification of the dry residue

Interpreting the stated volume as the equivalent STP volume of both products from the dry residue,

\[ n_{\text{total}} =\frac{1.68\,\mathrm{dm^3}} {22.4\,\mathrm{dm^3\,mol^{-1}}} =0.0750\,\mathrm{mol}. \]

The amount of water formed is

\[ n(\ce{H2O}) =\frac{0.90\,\mathrm g}{18.0\,\mathrm{g\,mol^{-1}}} =0.0500\,\mathrm{mol}. \]

Therefore, the gaseous oxide has

\[ n_{\text{oxide}}=0.0750-0.0500=0.0250\,\mathrm{mol}, \]

\[ m_{\text{oxide}}=2.0-0.90=1.1\,\mathrm g, \]

and hence molar mass

\[ M_{\text{oxide}} =\frac{1.1\,\mathrm g}{0.0250\,\mathrm{mol}} =44\,\mathrm{g\,mol^{-1}}. \]

The oxide-to-water mole ratio is \(1:2\). Decomposition at \(215\,^\circ\mathrm C\) into an oxide of molar mass \(44\,\mathrm{g\,mol^{-1}}\) and water in this ratio identifies ammonium nitrate, yielding nitrous oxide:

\[ \boxed{\ce{NH4NO3 ->[\Delta] N2O(g) + 2H2O(g)}}. \]

Its molar mass is \(80.0\,\mathrm{g\,mol^{-1}}\), so the residue contains

\[ n(\ce{NH4NO3}) =\frac{2.0\,\mathrm g}{80.0\,\mathrm{g\,mol^{-1}}} =0.0250\,\mathrm{mol}. \]

This gives \(0.0500\,\mathrm{mol}\), or \(0.90\,\mathrm g\), of water and a total equivalent gas volume of

\[ (0.0250+0.0500)\times22.4=1.68\,\mathrm{dm^3}, \]

as required.

Identification of the metal and precipitate

The soluble product is ammonium nitrate. Since nitrates and ammonium salts are soluble, the original solutes are a nitrate of the bivalent metal and an ammonium salt of the precipitating anion.

Each mole of metal nitrate supplies two nitrate groups and therefore produces two moles of ammonium nitrate. Thus,

\[ n(\ce{MO})=\frac{n(\ce{NH4NO3})}{2} =0.0125\,\mathrm{mol}. \]

The molar mass of the metal oxide is

\[ M(\ce{MO}) =\frac{0.70\,\mathrm g}{0.0125\,\mathrm{mol}} =56\,\mathrm{g\,mol^{-1}}. \]

Subtracting oxygen’s contribution gives

\[ M(\ce{M})=56-16=40\,\mathrm{g\,mol^{-1}}, \]

identifying the metal as calcium.

The precipitate’s mass per mole of calcium is

\[ \frac{1.25\,\mathrm g}{0.0125\,\mathrm{mol}} =100\,\mathrm{g\,mol^{-1}}. \]

This matches calcium carbonate:

\[ M(\ce{CaCO3})=40+12+3(16)=100\,\mathrm{g\,mol^{-1}}. \]

At \(1100\,^\circ\mathrm C\), it decomposes according to

\[ \boxed{\ce{CaCO3(s) ->[\Delta] CaO(s) + CO2(g)}}. \]

The predicted masses are

\[ m(\ce{CaO})=0.0125\times56=0.70\,\mathrm g, \]

\[ m(\ce{CO2})=0.0125\times44=0.55\,\mathrm g. \]

Their sum is \(1.25\,\mathrm g\), confirming the precipitate identification.

Original reaction

The two unknown compounds are consequently calcium nitrate and ammonium carbonate:

\[ \boxed{\ce{Ca(NO3)2(aq) + (NH4)2CO3(aq) -> CaCO3(s) + 2NH4NO3(aq)}}. \]

Evaporating the filtrate removes the solvent and leaves solid ammonium nitrate. The predicted residue mass is

\[ 2(0.0125\,\mathrm{mol})(80.0\,\mathrm{g\,mol^{-1}}) =2.0\,\mathrm g, \]

in agreement with the problem.

The solution was checked against the official solution.