ZAHID IQBAL WARRAICH

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Q1 (a) What do you understand by the term standard electrode potential? (b) The following cell was set up between a copper electrode and an unknown metal electrode M2+(aq) /M(s). The standard cell potential was found to be 0.76 V, and the copper foil was the positive electrode. (i) Use the Data Booklet to calculate the standard electrode potential of the M2+(aq) /M(s) system. (ii) Draw an arrow over the voltmeter symbol in the above diagram to show the direction of electron flow through the voltmeter. (iii) Predict the outcomes of the following situations. Describe what you might see and write ionic equations for any reactions that occur. I A rod of metal M is dipped into a solution of 1 moldm 3 CuSO4. II Dilute sulphuric acid is added to a beaker containing a powdered sample of metal M. (c) Because of its increased scarcity, cheaper copper ornaments are no longer made from the solid metal, but from iron that has been copper plated. (i) Complete the following diagram showing the set-up for a copper electroplating process. Show clearly the polarity (+/ ) of the power source, and suggest a suitable electrolyte. ZAHID IQBAL WARRAICH 0333-4200541 1

(ii) A current of 0.500 A is passed through the electroplating cell. Calculate the time required to deposit a mass of 0.500 g of copper on to the ornament. (June 2003) Q2 Although standard electrode potentials are measured for solutions where the concentrations of ions are 1.0 mol dm 3, cells used as sources of battery power tend to operate with more concentrated solutions. This question concerns the electrode reactions involved in the hydrogen-oxygen fuel cell and the lead-acid car battery. (a) In the hydrogen-oxygen fuel cell, H2(g) and O2(g) are fed onto two inert electrodes dipping into NaOH(aq). (i) Use the Data Booklet to calculate E o cell for this reaction. (ii) Construct an equation for the overall reaction. (iii) By using one of the phrases more positive, more negative or no change, deduce the effect of increasing [OH (aq)] on the electrode potential of the left hand electrode... the right hand electrode... (iv) Hence deduce whether the overall Ecell is likely to increase, decrease or remain the same, when [OH (aq)] increases. Explain your answer. (v) Suggest one other reason why a high [NaOH(aq)] is used in the fuel cell. ZAHID IQBAL WARRAICH 0333-4200541 2

(b) In the cells of a lead-acid car battery the following reactions take place. (i) Use the Data Booklet to calculate E o cell for this reaction. (ii) Construct an equation for the overall reaction. The electrolyte in a lead-acid cell is H2SO4(aq). Most of the Pb2+(aq) ions that are produced at the electrodes are precipitated as the highly insoluble PbSO4(s). (iii) Construct an equation for the overall cell reaction in the presence of H2SO4. (iv) By considering the effect of decreasing [Pb2+(aq)] on the electrode potentials of the cathode and the anode, deduce the effect of the presence of H2SO4(aq) in the electrolyte on the overall Ecell. State whether the Ecell will increase, decrease or remain the same. Overall Ecell will... Explain your answer. (June 2010 P41) Q3 The electrolytic purification of copper can be carried out in an apparatus similar to the one shown below. The impure copper anode contains small quantities of metallic nickel, zinc and silver, together with inert oxides and carbon resulting from the initial reduction of the copper ore with coke. The copper goes into solution at the anode, but the silver remains as the metal and falls to the bottom as part of the anode sludge. The zinc also dissolves. (a) (i) Write a half equation including state symbols for the reaction of copper at the anode. (ii) Use data from the Data Booklet to explain why silver remains as the metal. (iii) Use data from the Data Booklet to predict what happens to the nickel at the anode. ZAHID IQBAL WARRAICH 0333-4200541 3

(iv) Write a half equation including state symbols for the main reaction at the cathode. (v) Use data from the Data Booklet to explain why zinc is not deposited on the cathode. (vi) Suggest why the blue colour of the electrolyte slowly fades as the electrolysis proceeds. (b) Most of the current passed through the cell is used to dissolve the copper at the anode and precipitate pure copper onto the cathode. However, a small proportion of it is wasted in dissolving the impurities at the anode which then remain in solution.when a current of 20.0 A was passed through the cell for 10.0 hours, it was found that 225 g of pure copper was deposited on the cathode. (i) Calculate the following, using appropriate data from the Data Booklet. number of moles of copper produced at the cathode number of moles of electrons needed to produce this copper number of moles of electrons that passed through the cell (ii) Hence calculate the percentage of the current through the cell that has been wasted in dissolving the impurities at the anode. (c) Nickel often occurs in ores along with iron. After the initial reduction of the ore with coke, a nickel-iron alloy is formed.use data from the Data Booklet to explain why nickel can be purified by a similar electrolysis technique to that used for copper, using an impure nickel anode, a pure nickel cathode, and nickel sulfate as the electrolyte. Explain what would happen to the iron during this process. (Nov 2010 P41) ZAHID IQBAL WARRAICH 0333-4200541 4

Q4 (a) What is meant by the term standard electrode potential, SEP? (b) Draw a fully labelled diagram of the apparatus you could use to measure the SEP of the Fe3+ / Fe2+ electrode. (c) The reaction between Fe3+ ions and I ions is an equilibrium reaction. (i) Use the Data Booklet to calculate E CELL the for this reaction. (ii) Hence state, with a reason, whether there will be more products or more reactants at equilibrium. (iii) Write the expression for Kc for this reaction, and state its units. An experiment was carried out using solutions of Fe3+(aq) and I (aq) of equal concentrations. 100 cm3 of each solution were mixed together, and allowed to reach equilibrium. The concentrations at equilibrium of Fe3+(aq) and I2(aq) were as follows. (iv) Use these data, together with the equation given in (c), to calculate the concentrations of Fe2+(aq) and I (aq) at equilibrium. (v) Calculate the Kc for this reaction. ZAHID IQBAL WARRAICH 0333-4200541 5 (June 2013 P43)

Q5 (a) The diagram below shows an incomplete experimental set-up needed to measure the Ecell of a cell composed of the standard Cu2+/Cu electrode and an Ag+/Ag electrode. (i) State the chemical composition of solution A,... electrode B.... (ii) Complete the diagram to show the whole experimental set-up. (b) The above cell is not under standard conditions, because the [Ag+] in a saturated solution of AgCl is much less than 1.0 mol dm 3. The Eelectrode is related to [Ag+] by the following equation. (i) Use the Data Booklet to calculate the E cell if the cell was operating under standard conditions. In the above experiment, the Ecell was measured at +0.17V. (ii) Calculate the value of Eelectrode for the Ag+/Ag electrode in this experiment. (iii) Use equation 1 to calculate [Ag+] in the saturated solution. (c) (i) Write an expression for Ksp of silver sulfate, Ag2SO4, including units. Ksp =... units... Using a similar experimental set-up to that illustrated opposite, it is found that [Ag+] in a saturated solution of Ag2SO4 is 1.6 10 2 mol dm 3. (ii) Calculate the value of Ksp of silver sulfate. (Nov 2012 P42) ZAHID IQBAL WARRAICH 0333-4200541 6