IChO 1975 · Theory problem 3

Composition of an Ag-Cu-Cr alloy

A sample of 1500 mg of an alloy that contains silver, copper, and chromium is dissolved and the solution containing \(\ce{Ag+}\), \(\ce{Cu^2+}\), and \(\ce{Cr^3+}\) ions, is diluted to exactly 500 \(\mathrm{cm^3}\). One tenth of the volume of that solution is taken for further procedure:

After elimination of silver and copper, chromium is oxidised in it according to the following unbalanced equation:

Figure 1

Then 25.00 \(\mathrm{cm^3}\) of a 0.100 molar Fe(II) salt solution are added. The following reaction (written in an unbalanced form) is taking place:

Figure 2

According to the unbalanced equation:

Figure 3

a volume of 17.20 \(\mathrm{cm^3}\) of a 0.020-molar \(\ce{KMnO4}\) solution is required for an oxidation of the Fe(II) salt which remains unoxidized in the solution.

In another experiment, a volume of 200 \(\mathrm{cm^3}\) of the initial solution is electrolysed. Due to secondary reactions, the efficiency of the electrolysis is 90 % for metals under consideration. All three metals are quantitatively deposited in 14.50 minutes by passing a current of 2 A through the solution.

Problem:

3.1 Balance the three chemical equations and calculate the composition of the alloy in % by mass.

Relative atomic masses: \(A_{\mathrm r}(\ce{Cu}) = 63.55;\quad A_{\mathrm r}(\ce{Ag}) = 107.87;\quad A_{\mathrm r}(\ce{Cr}) = 52.00\)

Official English text of the problem.

Answers

  • 3.1 The balanced equations are:

\[ \ce{10 OH- + 2 Cr^3+ + 3 H2O2 -> 2 CrO4^2- + 8 H2O} \]

\[ \ce{8 H+ + 3 Fe^2+ + CrO4^2- -> 3 Fe^3+ + Cr^3+ + 4 H2O} \]

\[ \ce{8 H+ + 5 Fe^2+ + MnO4- -> 5 Fe^3+ + Mn^2+ + 4 H2O} \]

The alloy composition by mass is:

\[ \boxed{\text{Silver: }30.6\%,\qquad \text{Copper: }60.4\%,\qquad \text{Chromium: }9.0\%.} \]

Solution

3.1 — Balancing the reactions

In the first reaction, chromium is oxidised from oxidation state \(+3\) to \(+6\), losing three electrons per chromium atom. Hydrogen peroxide accepts two electrons per molecule as its oxygen changes from oxidation state \(-1\) to \(-2\). Thus, two chromium ions react with three hydrogen peroxide molecules. Balancing oxygen, hydrogen, and charge in alkaline solution gives:

\[ \ce{10 OH- + 2 Cr^3+ + 3 H2O2 -> 2 CrO4^2- + 8 H2O}. \]

In the second reaction, chromium is reduced from \(+6\) to \(+3\), accepting three electrons, while each iron(II) ion loses one electron. Consequently, one chromate ion consumes three iron(II) ions:

\[ \ce{8 H+ + 3 Fe^2+ + CrO4^2- -> 3 Fe^3+ + Cr^3+ + 4 H2O}. \]

In the third reaction, manganese is reduced from \(+7\) to \(+2\), accepting five electrons. One permanganate ion therefore oxidises five iron(II) ions:

\[ \ce{8 H+ + 5 Fe^2+ + MnO4- -> 5 Fe^3+ + Mn^2+ + 4 H2O}. \]

Chromium content from the back titration

The analysed aliquot has volume

\[ V_{\mathrm{aliquot}}=\frac{500}{10}=50.0\ \mathrm{cm^3}. \]

Keeping guard digits until the final percentages, the amount of iron(II) initially added is

\[ n_{\mathrm{Fe,added}} =(25.00\times10^{-3}\ \mathrm L) (0.100\ \mathrm{mol\,L^{-1}}) =2.500\times10^{-3}\ \mathrm{mol}. \]

The amount of permanganate used in the back titration is

\[ n_{\mathrm{permanganate}} =(17.20\times10^{-3}\ \mathrm L) (0.020\ \mathrm{mol\,L^{-1}}) =3.440\times10^{-4}\ \mathrm{mol}. \]

Since each permanganate ion consumes five iron(II) ions, the remaining iron(II) amounted to

\[ n_{\mathrm{Fe,remaining}} =5(3.440\times10^{-4}) =1.720\times10^{-3}\ \mathrm{mol}. \]

Hence the amount consumed by chromate was

\[ n_{\mathrm{Fe,consumed}} =2.500\times10^{-3}-1.720\times10^{-3} =7.80\times10^{-4}\ \mathrm{mol}. \]

Three iron(II) ions reduce one chromate ion, so the chromium content of the aliquot is

\[ n_{\mathrm{Cr,aliquot}} =\frac{7.80\times10^{-4}}{3} =2.60\times10^{-4}\ \mathrm{mol}. \]

The entire sample therefore contains

\[ n_{\mathrm{Cr}}=10n_{\mathrm{Cr,aliquot}} =2.60\times10^{-3}\ \mathrm{mol}, \]

\[ m_{\mathrm{Cr}} =(2.60\times10^{-3}\ \mathrm{mol}) (52.00\ \mathrm{g\,mol^{-1}}) =0.1352\ \mathrm g. \]

Thus,

\[ w_{\mathrm{Cr}} =\frac{0.1352}{1.500}\times100\% =9.0133\ldots\%. \]

Silver and copper contents from electrolysis

The cathodic deposition reactions are

\[ \ce{Ag+ + e- -> Ag(s)}, \]

\[ \ce{Cu^2+ + 2 e- -> Cu(s)}, \]

\[ \ce{Cr^3+ + 3 e- -> Cr(s)}. \]

Thus, depositing one mole of silver, copper, or chromium requires respectively one, two, or three moles of electrons.

The total charge passed is

\[ Q=It =(2\ \mathrm A)(14.50\times60\ \mathrm s) =1740\ \mathrm C. \]

Only 90% of this charge deposits the metals:

\[ Q_{\mathrm{metals}}=0.90(1740)=1566\ \mathrm C. \]

Using the standard Faraday constant \(F=96485\ \mathrm{C\,mol^{-1}}\), the electron amount used for deposition from the \(200\ \mathrm{cm^3}\) portion is

\[ n_{e,200}=\frac{1566}{96485} =0.0162305\ \mathrm{mol}. \]

Let \(n_{\mathrm{Ag}}\), \(n_{\mathrm{Cu}}\), and \(n_{\mathrm{Cr}}\) denote the metal amounts in the entire original sample. Scaling from \(200\) to \(500\ \mathrm{cm^3}\),

\[ n_{\mathrm{Ag}}+2n_{\mathrm{Cu}}+3n_{\mathrm{Cr}} =\frac{500}{200}(0.0162305) =0.0405763\ \mathrm{mol}. \]

Substituting the chromium amount gives

\[ n_{\mathrm{Ag}}+2n_{\mathrm{Cu}} =0.0405763-3(0.002600) =0.0327763\ \mathrm{mol}. \]

The silver and copper together have mass

\[ m_{\mathrm{Ag}}+m_{\mathrm{Cu}} =1.500-0.1352 =1.3648\ \mathrm g. \]

Their mass equation is therefore

\[ (107.87\ \mathrm{g\,mol^{-1}})n_{\mathrm{Ag}} +(63.55\ \mathrm{g\,mol^{-1}})n_{\mathrm{Cu}} =1.3648\ \mathrm g. \]

Substituting \(n_{\mathrm{Ag}}=0.0327763\ \mathrm{mol}-2n_{\mathrm{Cu}}\) and solving gives

\[ n_{\mathrm{Cu}}\approx0.0142636\ \mathrm{mol}, \qquad n_{\mathrm{Ag}}\approx0.00424909\ \mathrm{mol}. \]

Consequently,

\[ m_{\mathrm{Cu}}\approx0.906451\ \mathrm g, \qquad m_{\mathrm{Ag}}\approx0.458349\ \mathrm g. \]

The mass percentages are

\[ w_{\mathrm{Ag}} =\frac{0.458349}{1.500}\times100\% \approx\boxed{30.6\%}, \]

\[ w_{\mathrm{Cu}} =\frac{0.906451}{1.500}\times100\% \approx\boxed{60.4\%}, \]

\[ w_{\mathrm{Cr}}\approx\boxed{9.0\%}. \]

The calculated masses sum to \(1.500\ \mathrm g\), and the reported percentages sum to \(100.0\%\).

Species names and SMILES

Species Name SMILES
\(\ce{Ag+}\) Silver(I) ion [Ag+]
\(\ce{Cu^2+}\) Copper(II) ion [Cu+2]
\(\ce{Cr^3+}\) Chromium(III) ion [Cr+3]
\(\ce{OH-}\) Hydroxide ion [OH-]
\(\ce{H2O2}\) Hydrogen peroxide OO
\(\ce{CrO4^2-}\) Chromate ion [O-][Cr](=O)(=O)[O-]
\(\ce{H2O}\) Water O
\(\ce{H+}\) Hydrogen ion (proton) [H+]
\(\ce{Fe^2+}\) Iron(II) ion [Fe+2]
\(\ce{Fe^3+}\) Iron(III) ion [Fe+3]
\(\ce{MnO4-}\) Permanganate ion [O-][Mn](=O)(=O)=O
\(\ce{Mn^2+}\) Manganese(II) ion [Mn+2]
\(\ce{KMnO4}\) Potassium permanganate [K+].[O-][Mn](=O)(=O)=O

The ion SMILES omit aqueous solvation. Chromate and permanganate have tetrahedral oxygen arrangements; these SMILES do not specify that geometry and show only one formal representation of their delocalized bonding.

The solution was checked against the official solution.