The following method was used to determine the percentage by mass of vanadium in a sample of ammonium vanadate(v).

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Q1. (a) Vanadium(V) oxide is used as a heterogeneous catalyst in the Contact Process. Explain what is meant by the terms heterogeneous and catalyst and state, in general terms, how a catalyst works. State the essential feature of vanadium chemistry which enables vanadium(v) oxide to function as a catalyst and, by means of equations, suggest how it might be involved in the Contact Process. (7) The following method was used to determine the percentage by mass of vanadium in a sample of ammonium vanadate(v). A solution was made up by dissolving 0.160 g of ammonium vanadate(v) in dilute sulphuric acid. The ammonium vanadate(v) formed an excess of zinc was added to this solution, the and the zinc was oxidised to Zn 2+ ions. ions in this solution. When ions were reduced to V 2+ ions After the unreacted zinc had been removed, the solution was titrated against a 0.0200 mol dm 3 solution of potassium manganate(vii). In the titration, 38.5 cm 3 of potassium manganate(vii) solution were required to oxidise all vanadium(ii) ions to vanadium(v) ions. Using half-equations, construct an overall equation for the reduction of to V 2+ by zinc in acidic solution. Calculate the percentage by mass of vanadium in the sample of ammonium vanadate(v). (8) Q2. (a) The ion can act as a bidentate ligand. Explain the meaning of the term bidentate ligand. Page 2

(ii) Sketch the structure of the octahedral complex ion formed by Fe 3+ ions which contains as the only ligand. Include the overall charge on the complex ion. (5) Explain the meaning of the term chelate effect....... (2) (c) The chloride ion can act as a monodentate ligand. Deduce the formula of the linear complex formed when an excess of concentrated hydrochloric acid is added to silver chloride. (ii) Explain why metal(ii) ions do not usually form octahedral complexes when chloride ions are the only ligands. (2) (d) The concentration of ions can be determined by titration in acidic solution using a standard solution of potassium manganate(vii). At room temperature, the reaction proceeds very slowly at first but becomes faster after some of the manganate(vii) ions have reacted. Suggest why this reaction is very slow at first. Page 3

(ii) This is an example of an autocatalytic reaction. State the meaning of the term autocatalytic and identify the catalyst. Meaning of the term autocatalytic... Catalyst... Suggest how this catalyst might be involved in the reaction. (5) (Total 14 marks) Q3. (a) The strength of adsorption onto the active sites on the surface of a heterogeneous catalyst helps to determine the activity of the catalyst. Explain how heterogeneous catalysts work, give one example of a reaction catalysed in this way and discuss why different catalysts have different activities. (8) Outline a plan of an experiment to determine the percentage of iron present as iron(iii) in a solution containing Fe 3+ (aq) and Fe 2+ (aq) ions. You are provided with zinc, a standard solution of potassium dichromate(vi) and dilute sulphuric acid. Zinc can reduce Fe 3+ (aq) to Fe 2+ (aq). Write equations for all the reactions that occur. Explain how you would use the zinc and how you would calculate the final answer. (7) Page 4

Q4. Summarised directions for recording responses to multiple completion questions A, (ii) and only B and only C (ii) and (iv) only D (iv) alone Which of the following statements about a catalyst is / are true? (iv) It speeds up the forward reaction and slows down the reversere action. It increases the proportion of molecules with higher energies. A homogeneous catalyst usually acts in the solid state. It does not alter the value of the equilibrium constant. (Total 1 mark) Q5. (a) The reaction between aqueous persulphate ions,, and iodide ions, I (aq), is catalysed by Fe 2+ (aq) ions. Suggest why this reaction has a high activation energy. Write equations to explain the catalytic action of Fe 2+ (aq) ions. Suggest why V 3+ (aq) ions will also act as a catalyst for this reaction but Mg 2+ (aq) ions will not. (6) Outline a mechanism for the reaction between benzene and ethanoyl chloride and explain why AlCl 3 acts as a Lewis acid catalyst for this reaction. Predict, with an explanation in each case, the suitability of FeCl 3 and of NH 4Cl to act as a catalyst for this reaction. (9) Page 5

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