CHEM5. General Certificate of Education Advanced Level Examination June Unit 5 Energetics, Redox and Inorganic Chemistry

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Centre Number Surname Candidate Number For Examiner s Use Other Names Candidate Signature Examiner s Initials General Certificate of Education Advanced Level Examination June 2010 Question 1 2 Mark Chemistry Unit 5 Energetics, Redox and Inorganic Chemistry Monday 28 June 2010 9.00 am to 10.45 am For this paper you must have: the Periodic Table/Data Sheet provided as an insert (enclosed) a calculator. CHEM5 3 4 5 6 7 TOTAL Time allowed 1 hour 45 minutes Instructions Use black ink or black ball-point pen. Fill in the es at the top of this page. Answer all questions. You must answer the questions in the spaces provided. around each page or on blank pages. All working must be shown. Do all rough work in this book. Cross through any work you do not want to be marked. Information The marks for questions are shown in brackets. The maximum mark for this paper is 100. The Periodic Table/Data Sheet is provided as an insert. Your answers to the questions in Section B should be written in continuous prose, where appropriate. You will be marked on your ability to: use good English organise information clearly use accurate scientific terminology. Advice You are advised to spend about 1 hour 15 minutes on Section A and about 30 minutes on Section B. (JUN10CHEM501) CHEM5

2 Section A Answer all questions in the spaces provided. 1 Calcium fluoride occurs naturally as the mineral fluorite, a very hard crystalline solid that is almost insoluble in water and is used as a gemstone. Tables 1 and 2 contain thermodynamic data. Table 1 Process ΔH / kj mol 1 Ca(s) Ca(g) +193 Ca(g) Ca + (g) + e +590 Ca + (g) Ca 2+ (g) + e +1150 F 2 (g) 2F(g) +158 F(g) + e F (g) 348 Table 2 Name of enthalpy change ΔH / kj mol 1 Enthalpy of lattice dissociation for calcium fluoride +2602 Enthalpy of lattice dissociation for calcium chloride +2237 Enthalpy of hydration for F ions 506 Enthalpy of hydration for Cl ions 364 Enthalpy of hydration for Ca 2+ ions 1650 1 (a) Write an equation, including state symbols, for the process that occurs when the calcium fluoride lattice dissociates and for which the enthalpy change is equal to the lattice enthalpy. (02)

1 (b) (i) Define the term standard enthalpy of formation. 3 (Extra space)... 1 (b) (ii) Write an equation, including state symbols, for the process that has an enthalpy change equal to the standard enthalpy of formation of calcium fluoride. 1 (b) (iii) Use data from the Tables 1 and 2 to calculate the standard enthalpy of formation for calcium fluoride. (Extra space)... Question 1 continues on the next page Turn over (03)

4 1 (c) Explain why the enthalpy of lattice dissociation for calcium fluoride is greater than that for calcium chloride. 1 (d) Calcium chloride dissolves in water. After a certain amount has dissolved, a saturated solution is formed and the following equilibrium is established. CaCl 2 (s) Ca 2+ (aq) + 2Cl (aq) 1 (d) (i) Using data from Table 2, calculate the enthalpy change for this reaction. 1 (d) (ii) Predict whether raising the temperature will increase, decrease or have no effect on the amount of solid calcium chloride that can dissolve in a fixed mass of water. Explain your prediction. (If you have been unable to obtain an answer to part (d) (i), you may assume that the enthalpy change = 60 kj mol 1. This is not the correct answer.) Effect on amount of solid that can dissolve... Explanation... (04)

5 1 (e) Calcium fluoride crystals absorb ultra-violet light. Some of the energy gained is given out as visible light. The name of this process, fluorescence, comes from the name of the mineral, fluorite. Use your knowledge of the equation ΔE = hν to suggest what happens to the electrons in fluorite when ultra-violet light is absorbed and when visible light is given out. (Extra space)... 17 Turn over for the next question Turn over (05)

6 2 Sodium, aluminium and silicon are solid elements with a silver colour. These elements react with oxygen to form oxides with high melting points. Aluminium is a reactive metal, but it resists corrosion in water because it has a surface coating of aluminium oxide. 2 (a) In terms of its structure and bonding, explain why silicon dioxide has a high melting point. (Extra space)... 2 (b) State the type of bonding in aluminium oxide. 2 (c) Write an equation for the reaction of aluminium with oxygen. 2 (d) Suggest one property of the aluminium oxide coating that causes aluminium to resist corrosion in water. 2 (e) Sodium metal is not resistant to corrosion in water, despite having a surface coating of sodium oxide. Write an equation to show how sodium oxide reacts with water. (06)

7 2 (f) Aluminium oxide is amphoteric. It reacts with acids and alkalis. 2 (f) (i) Write an equation for the reaction between aluminium oxide and hydrochloric acid. 2 (f) (ii) Write an equation for the reaction between aluminium oxide and an excess of aqueous sodium hydroxide. 2 (g) Silicon dioxide does not react with hydrochloric acid but it does react with sodium hydroxide. State one property of silicon dioxide that can be deduced from this information and write an equation for its reaction with sodium hydroxide. Property... Equation... Turn over for the next question 11 Turn over (07)

8 3 Transition metal ions can act as homogeneous catalysts in redox reactions. For example, iron(ii) ions catalyse the reaction between peroxodisulfate (S 2 O 8 2 ) ions and iodide ions. 3 (a) State the meaning of the term homogeneous. 3 (b) Suggest why ions from s block elements do not usually act as catalysts. 3 (c) Write an equation for the overall reaction that occurs, in aqueous solution, between S 2 O 8 2 ions and I ions. 3 (d) Give one reason why, in the absence of a catalyst, the activation energy for the reaction between S 2 O 8 2 ions and I ions is high. 3 (e) Write two equations to show how Fe 2+ ions can catalyse the reaction between S 2 O 8 2 ions and I ions. Suggest one reason why the activation energy for each of these reactions is low. Equation 1... Equation 2... Reason... (08)

9 3 (f) Explain why Fe 3+ ions are as effective as Fe 2+ ions in catalysing this reaction. 8 Turn over for the next question Turn over (09)

10 4 Transition elements form complex ions with a range of colours and shapes. 4 (a) By considering its electron arrangement, state how an element can be classified as a transition element. 4 (b) Explain the meaning of the term complex ion. 4 (c) In terms of electrons, explain why an aqueous solution of cobalt(ii) sulfate has a red colour. 4 (d) The ligand EDTA 4 is shown below. O O O O C C CH 2 CH 2 N CH 2 CH 2 H 2 C N H 2 C C C O O O O 4 (d) (i) Draw circles around the atoms of two different elements that link to a transition metal ion by a co-ordinate bond when EDTA 4 behaves as a ligand. 4 (d) (ii) Write an equation for the reaction between EDTA 4 and a [Co(H 2 O) 6 ] 2+ ion. Use the abbreviation EDTA 4 in your equation. (10)

11 4 (d) (iii) Explain why the complex ion, formed as a product of the reaction in part (d) (ii), is more stable than the [Co(H 2 O) 6 ] 2+ ion. 4 (e) The diagram below shows part of the structure of haemoglobin. N N Fe N N Haemoglobin contains an iron(ii) ion bonded to five nitrogen atoms and one other ligand. The fifth nitrogen atom and the additional ligand are not shown in this diagram. 4 (e) (i) In this diagram, bonds between nitrogen and iron are shown as N Fe and as N Fe. State the meaning of each of these symbols. Meaning of... Meaning of... 4 (e) (ii) State the function of haemoglobin in the blood. 4 (e) (iii) With reference to haemoglobin, explain why carbon monoxide is toxic. 16 Turn over (11)

12 5 The scheme below shows some reactions of copper(ii) ions in aqueous solution. W, X, Y and Z are all copper-containing species. W concentrated HCl Cu(s) scrap iron [Cu(H 2 O) 6 ] 2+ (aq) dilute NH 3 (aq) X an excess of NH 3 (aq) Y Na 2 CO 3 (aq) Z 5 (a) Identify ion W. Describe its appearance and write an equation for its formation from [Cu(H 2 O) 6 ] 2+ (aq) ions. Ion W... Appearance... Equation... 5 (b) Identify compound X. Describe its appearance and write an equation for its formation from [Cu(H 2 O) 6 ] 2+ (aq) ions. Compound X... Appearance... Equation... (12)

13 5 (c) Identify ion Y. Describe its appearance and write an equation for its formation from X. Ion Y... Appearance... Equation... 5 (d) Identify compound Z. Describe its appearance and write an equation for its formation from [Cu(H 2 O) 6 ] 2+ (aq) ions. Compound Z... Appearance... Equation... 5 (e) Copper metal can be extracted from a dilute aqueous solution containing copper(ii) ions using scrap iron. 5 (e) (i) Write an equation for this reaction and give the colours of the initial and final aqueous solutions. Equation... Initial colour... Final colour... 5 (e) (ii) This method of copper extraction uses scrap iron. Give two other reasons why this method of copper extraction is more environmentally friendly than reduction of copper oxide by carbon. Reason 1... Reason 2... 17 Turn over (13)

14 Section B Answer all questions in the spaces provided. 6 Methanol can be regarded as a carbon-neutral fuel because it can be synthesised from carbon dioxide as shown in the equation below. CO 2 (g) + 3H 2 (g) CH 3 OH(g) + H 2 O(g) Standard enthalpy of formation and standard entropy data for the starting materials and products are shown in the following table. CO 2 (g) H 2 (g) CH 3 OH(g) H 2 O(g) ΔH f / kj mol 1 394 0 201 242 S /JK 1 mol 1 214 131 238 189 6 (a) Calculate the standard enthalpy change for this reaction. 6 (b) Calculate the standard entropy change for this reaction. (14)

15 6 (c) Use your answers to parts (a) and (b) to explain why this reaction is not feasible at high temperatures. Calculate the temperature at which the reaction becomes feasible. Suggest why the industrial process is carried out at a higher temperature than you have calculated. (If you have been unable to calculate values for ΔH and ΔS you may assume that they are 61 kj mol 1 and 205 J K 1 mol 1 respectively. These are not the correct values.) (6 marks) (Extra space)... Question 6 continues on the next page Turn over (15)

16 6 (d) Write an equation for the complete combustion of methanol. Use your equation to explain why the combustion reaction in the gas phase is feasible at all temperatures. (4 marks) (Extra space)... 6 (e) Give one reason why methanol, synthesised from carbon dioxide and hydrogen, may not be a carbon-neutral fuel. 17 (16)

17 Turn over for the next question DO NOT WRITE ON THIS PAGE ANSWER IN THE SPACES PROVIDED Turn over (17)

18 7 The electrons transferred in redox reactions can be used by electrochemical cells to provide energy. Some electrode half-equations and their standard electrode potentials are shown in the table below. Half-equation E /V Cr 2 O 7 2 (aq) + 14H + (aq) + 6e 2Cr 3+ (aq) + 7H 2 O(l) +1.33 Fe 3+ (aq) + e Fe 2+ (aq) +0.77 2H + (aq) + 2e H 2 (g) 0.00 Fe 2+ (aq) + 2e Fe(s) 0.44 Li + (aq) + e Li(s) 3.04 7 (a) Describe a standard hydrogen electrode. (4 marks) (18)

19 7 (b) A conventional representation of a lithium cell is given below. This cell has an e.m.f. of +2.91 V Li(s) Li + (aq) Li + (aq) MnO 2 (s), LiMnO 2 (s) Pt(s) Write a half-equation for the reaction that occurs at the positive electrode of this cell. Calculate the standard electrode potential of this positive electrode. 7 (c) Suggest what reactions occur, if any, when hydrogen gas is bubbled into a solution containing a mixture of iron(ii) and iron(iii) ions. Explain your answer. Question 7 continues on the next page Turn over (19)

20 7 (d) A solution of iron(ii) sulfate was prepared by dissolving 10.00 g of FeSO 4.7H 2 O (M r = 277.9) in water and making up to 250 cm 3 of solution. The solution was left to stand, exposed to air, and some of the iron(ii) ions became oxidised to iron(iii) ions. A 25.0 cm 3 sample of the partially oxidised solution required 23.70 cm 3 of 0.0100 mol dm 3 potassium dichromate(vi) solution for complete reaction in the presence of an excess of dilute sulfuric acid. Calculate the percentage of iron(ii) ions that had been oxidised by the air. (6 marks) (Extra space)... 14 END OF QUESTIONS Copyright 2010 AQA and its licensors. All rights reserved. (20)