International Chemistry Olympiad

IChO 1974

Bucharest, Romania · 5 theory problems with complete solutions

  1. Problem 1: From electrolytic hydrogen to methyl orange

    By electrochemical decomposition of water, there are in an electric circuit a voltmeter, platinum electrodes and a battery containing ten galvanic cells connected in series, each of it having the voltage of 1.5 V and internal resistance of 0.4 Ω. The resistance of the voltmeter is 0.5 Ω and the polarisation voltage of the battery is 1.5 V. Electric current flows for 8 hours, 56 minutes and 7 seconds through the electrolyte. Hydrogen obtained in this way was used for a synthesis with another substance, thus forming a gaseous substance A which can be converted by oxidation with oxygen via oxide to substance B.

    By means of substance B it is possible to prepare substance C from which after reduction by hydrogen substance D can be obtained. Substance D reacts at 180 °C with a concentration solution of sulphuric acid to produce sulphanilic acid. By diazotization and successive copulation with p-N,N-dimethylaniline, an azo dye, methyl orange is formed.

    Problems:

    1. Write chemical equations for all the above mentioned reactions.
    2. Calculate the mass of product D.
    3. Give the exact chemical name for the indicator methyl orange. Show by means of structural formulas what changes take place in dependence on concentration of \(\ce{H3O+}\) ions in the solution.

    Relative atomic masses: \(A_\mathrm{r}(\ce{N}) = 14;\quad A_\mathrm{r}(\ce{O}) = 16;\quad A_\mathrm{r}(\ce{C}) = 12;\quad A_\mathrm{r}(\ce{H}) = 1.\)

    Official English text of the problem.

  2. Problem 2: Reaction scheme leading to substance G

    Substance G can be prepared by several methods according to the following scheme:

    Figure 1

    Compound A is 48.60 mass % carbon, 8.10 % hydrogen, and 43.30 % oxygen. It reacts with a freshly prepared silver(I) oxide to form an undissolved salt. An amount of 1.81 g of silver(I) salt is formed from 0.74 g of compound A.

    Compound D contains 54.54 mass % of carbon, 9.09 % of hydrogen, and 36.37 % of oxygen. It combines with \(\ce{NaHSO3}\) to produce a compound containing 21.6 % of sulphur.

    Problems:

    1. Write summary as well as structural formulas of substances A and D.
    2. Write structural formulas of substances B, C, E, F, and G.
    3. Classify the reactions in the scheme marked by arrows and discuss more in detail reactions B → G and D → E.
    4. Write structural formulas of possible isomers of substance G and give the type of isomerism.

    Relative atomic masses:

    \[ A_r(\ce{C})=12;\quad A_r(\ce{H})=1;\quad A_r(\ce{O})=16;\quad A_r(\ce{Ag})=108;\quad A_r(\ce{Na})=23;\quad A_r(\ce{S})=32. \]

    Official English text of the problem.

  3. Problem 3: Acid-base reactions of 0.2 M solutions A-H

    The following 0.2 molar solutions are available:

    A: \(\ce{HCl}\) B: \(\ce{HSO4-}\) C: \(\ce{CH3COOH}\) D: \(\ce{NaOH}\)
    E: \(\ce{CO3^2-}\) F: \(\ce{CH3COONa}\) G: \(\ce{HPO4^2-}\) H: \(\ce{H2SO4}\)

    Problems:

    1. Determine the concentration of \(\ce{H3O+}\) ions in solution C.
    2. Determine pH value in solution A.
    3. Write an equation for the chemical reaction that takes place when substances B and E are allowed to react and mark conjugate acid-base pairs.
    4. Compare acid-base properties of substances A, B, and C and determine which one will show the most basic properties. Explain your decision.
    5. Write a chemical equation for the reaction between substances B and G, and explain the shift of equilibrium.
    6. Write a chemical equation for the reaction between substances C and E, and explain the shift of equilibrium.
    7. Calculate the volume of D solution which is required to neutralise 20.0 \(\mathrm{cm^3}\) of H solution.
    8. What would be the volume of hydrogen chloride being present in one litre of A solution if it were in gaseous state at a pressure of 202.65 kPa and a temperature of 37 °C?

    Ionisation constants:

    Figure 1

    Relative atomic masses:

    \(A_{\mathrm r}(\ce{Na})=23;\quad A_{\mathrm r}(\ce{S})=32;\quad A_{\mathrm r}(\ce{O})=16.\)

    Official English text of the problem.

  4. Problem 4: Mixture of two oxygen-containing organic compounds

    A mixture contains two organic compounds, A and B. Both of them have in their molecules oxygen and they can be mixed together in arbitrary ratios. Oxidation of this mixture on cooling yields the only substance C that combines with \(\ce{NaHSO3}\). The ratio of the molar mass of the substance being formed in the reaction with \(\ce{NaHSO3}\) to that of substance C, is equal to 2.7931.

    The mixture of substances A and B is burned in the presence of a stoichiometric amount of air (20 % \(\ce{O2}\) and 80 % of \(\ce{N2}\) by volume) in an eudiometer to produce a mixture of gases with a total volume of \(5.432\ \mathrm{dm^3}\) at STP. After the gaseous mixture is bubbled through a \(\ce{Ba(OH)2}\) solution, its volume is decreased by 15.46 %.

    Problems:

    4.1 Write structural formulas of substance A and B.

    4.2 Calculate the molar ratio of substances A and B in the mixture.

    \[ A_{\mathrm r}(\ce{C})=12;\qquad A_{\mathrm r}(\ce{O})=16;\qquad A_{\mathrm r}(\ce{S})=32;\qquad A_{\mathrm r}(\ce{Na})=23. \]

    Official English text of the problem.

  5. Problem 5: Mixture of two metals: hydrides, hydroxides and a precipitate

    A mixture of two metals found in Mendelejev's periodical table in different groups, reacted with 56 cm³ of hydrogen on heating (measured at STP conditions) to produce two ionic compounds. These compounds were allowed to react with 270 mg of water but only one third of water reacted. A basic solution was formed in which the content of hydroxides was 30 % by mass and at the same time deposited a precipitate with a mass that represented 59.05 % of a total mass of the products formed by the reaction. After filtration the precipitate was heated and its mass decreased by 27 mg.

    When a stoichiometric amount of ammonium carbonate was added to the basic solution, a slightly soluble precipitate was obtained, at the same time ammonia was liberated and the content of hydroxides in the solution decreased to 16.81 %.

    Problem:

    5.1 Determine the metals in the starting mixture and their masses.

    Official English text of the problem.