Question 1: (/10) a) Define 'standard enthalpy of lattice dissociation' (2 marks) The standard enthalpy change to convert one mole

le of a solid ionic lattice into its gaseous, constituent ions

b) Explain the meaning of the term perfect ionic model (1 mark) Ions are perfect spheres, only electrostatic attraction/no covalent character c) Suggest two properties of ions that influence the value of a lattice enthalpy calculated using a perfect ionic model (2 marks) Size of the ion/ionic radius Charge on the ion

d) Calculate the lattice enthalpy of dissociation for AgBr (3 marks) +905 kJ/mol e) How would you expect your value to 1d) to differ with that calculated from the perfect ionic model. Explain (2 marks) Greater; as there is additional covalent character/bonding

Question 2 (/13) The enthalpy of hydration for the chloride ion is -364 kJ/mol and that for the bromide ion is 335 kJ/mol. a) By describing the nature of the attraction forces involved, explain why the value for the enthalpy of hydration for the chloride ion is more negative than that for the bromide ion (3 marks) Cl- ion is a smaller ion than Br- so its charge/size ratio is greater. Water is polar so contains a + H atom . Therefore Cl- attracts the + H atom on H2O more strongly than Br- so more energy is released when hydration happens.

b) The enthalpy of hydration for the potassium ion is -322 kJ/mol. The lattice enthalpy of dissociation for potassium bromide is +670 kJ/mol. Calculate the enthalpy of solution for potassium bromide (2 marks) H sol = hydration enthalpies + HL dissociation = -322 + -335 + 670 = +13 kJ/mol. c) i) The enthalpy of solution for potassium chloride is +17.2 kJ/mol. Explain why the freeenergy change for the dissolving of potassium chloride in water is negative, even though the enthalpy change is positive (3 marks) Increase in disorder and therefore entropy as 1 mole goes to 2 moles and a solid goes to the aqueous state. H is small and is less than TS. Therefore G<0 and the reaction is feasible.

c) ii) A solution is formed when 5.00g of potassium chloride are dissolved in 20.0g of water. The initial temperature of the water is 298K. Calculate the final temperature of the solution. In your calculation, assume that only the 20.0g of water changes in temperature and that the specific heat capacity of water in 4.18J/K/g (5 marks) Temperature change works out at 13.8. Final temperature = 298 13.8 = 284.2K. ???? Question 3 (/15) a) i) Explain in terms of molecules why the entropy is zero when the temperature is zero Kelvin (2 marks) All substances are completely ordered. Molecules do not vibrate as there is no kinetic energy. a) ii) Explain, in terms of molecules, why the first part of figure 1 is a line that slopes up (2 marks) As temperature increases entropy increases, molecules vibrate more violently as there is increasing kinetic energy, and therefore the molecules are becoming more disordered. a) iii) Mark the boiling point of X on the graph (1 mark) a) iv) Explain in terms of molecules why the first part of the graph in figure 1 is a line that slopes up from the origin (2 marks) Phase change causes a sudden increase in entropy. Boiling point has a greater increase in entropy than melting point as the difference in entropy between a gas and liquid is greater than the difference in entropy between a solid and liquid. Therefore, L2 is greater than L1. b) i) Explain with a thermodynamic equation why this graph obeys the mathematical equation y=mx+c. (2 marks) G=H-TS can be rearranged to G=-ST + H. S is m (gradient) H is the constant c. G is y and T is x. therefore follows the same equation. S is negative due to negative gradient. b) ii) Explain why the magnitude of G decreases as temperature increases (1 mark) As T increases, so does TS. Since H is constant, and TS is negative, G decreases. b) iii) State what you can deduce about the feasibility at temperatures below 500K (1 mark). The reaction becomes feasible This reaction becomes feasible at temperatures above 5440K: H 2O (g) H2 (g) + 0.5 O2 (g). c) i) Calculate the entropy change for this reaction (1 mark) +44.5 J/K/mol c) ii) Work out the enthalpy change at 5440k (3 marks) +242.08 kJ/mol Question 4 (/12) a) What is the bonding in MgO. How could you prove that MgO has this bonding (3 marks) Ionic

Heat until molten Conducts electricity/gives a current when being electrolysed

b) With reference to structure and bonding, why is SiO2 insoluble in water (3 marks) large macromolecule many, strong covalent bonds lots of energy needed to be supplied to break bonds/ enthalpy of solution is very large

c) What has a higher melting point - SiO2 or P4O10? Explain (3 marks) P4O10 is a simple covalent molecule Weak VdWs (and dipole-dipole) IM forces Less energy needed to be supplied to break VdWs forces

d) Write an equation with a reagent to show MgO acting as a base (2 marks) e.g. MgO + 2HCl MgCl2 + H2O, MgO + H2SO4 MgSO4 + H2O. e) Write an equation for the reaction of P4O10 with sodium hydroxide (1 mark) P4O10 + 12NaOH 4Na3(PO4) + 6H2O Question 5 (/9) a) Explain how the salt bridge provides an electrical connection between electrodes (1 mark) Allows the ions in solution to pass through it and move. b) Suggest why KCl cannot be used as a salt bridge (1 mark) It is not inert/it reacts with the cell reagents/Cl- oxidized to Cl2 by Cu2+ c) Why do the electrons flow from right to left (2 marks) LHS has a higher conc. of Cu2+ / LHS is positive electrode Equilibrium Cu2+ + 2e- => Cu lies more to right at the left hand electrode (or converse) *** ??? d) Why does the current fall to zero after some time (1 mark) Cu2+ concentration is the same in both half cells *** ??? e) i) Calculate the electrode potential (1 mark) -3.05V e) ii) Write the equation for the cell when it is being recharged (2 marks) LiMnO2 Li + MnO2 e) ii) Give one reason why this cell produces CO2 (1 mark) CO2 released generating the electricity needed to recharge the cell Question 6 (/9) a) Calculate the frequency of visible light absorbed and state the units (2 marks)

4.28x10 s or Hz b) Why does this compound appear blue (2 marks) d-orbital electrons absorb visible light energy and are promoted/excited to a higher energy level; We observe the blue colour that is not absorbed; c) Red/blue complex. What is E of a red solution in comparison with a blue one? (2 marks) Larger; Absorbs blue light which is of a higher frequency; d) State 3 factors that affect the frequency of visible light absorbed (3 marks) Change in: oxidation state, ligands, coordination number Question 7 (/17) State the original colours, final observation and equations for each reaction a) [Fe(H2O)6]2+ and [Fe(H2O)6]3+ with sodium carbonate (5 marks) [Fe(H2O)6]2+ = pale green solution. Observation = green precipitate. [Fe(H2O)6]3+ = violet/yellow/brown solution. Observation = brown precipitate and effervescence. [Fe(H2O)6]2+ + CO32- => FeCO3 + 6H2O 2[Fe(H2O)6]3+ + 3CO32- => 2[Fe(OH)3(H2O)3] + 3CO2 + 3H2O b) [Cu(H2O)6]2+ and [Co(H2O)6]2+ with HCl (4 marks) [Cu(H2O)6]2+ = pale blue solution. Observation = yellow/green solution. [Co(H2O)]2+ = pink solution. Observation = blue solution [Cu(H2O)6]2+ + 4Cl- => [CuCl4]2- + 6H2O [Co(H2O)6]2+ + 4Cl- => [CoCl4]2- + 6H2O c) [Cr(H2O)6]3+ and [Fe(H2O)6]2+ with excess OH- (4 marks) [Cr(H2O)6]3+ = green or ruby solution. observation = dark green solution. [Fe(H2O)6]2+ = pale green solution. observation = green ppt. [Cr(H2O)6]3+ + 6OH- => [Cr(OH)6]3- + 6H2O. [Fe(H2O)6] + 2OH- => [Fe(OH)2(H2O)4] + 2H2O d) [Al(H2O)6]3+ and [Ag(H2O)2]+ with excess NH3 (4 marks) [Al(H2O)6]3+ = colourless soln. observation = white precipitate. [Ag(H2O)2]+ = colourless soln. observation = colourless solution/no visible change.

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[Al(H2O)6]3+ + 3NH3 => [Al(OH)3(H2O)3] + 3NH4+. [Ag(H2O)2]+ + 2NH3 => [Al(NH3)2]+ + 2H2O Question 8 (/15) 8a) Ethanal can be oxidised to ethanoic acid by O2. Explain why Co2+ ions can increase the rate of this oxidation. Write 2 equations showing how Co2+ does this. (4 marks) Provides alternative mechanism/route with a lower Ea; as has variable oxidation states; 2Co3+ + CH3CHO + H2O -> 2Co2+ + CH3COOH + 2H+ 4Co2+ + O2 + 4H+ -> 4Co3+ + 2H2O or multiples; b) [Co(H2O)6] reacts with an excess of ethane-1,2-diamine. Write an equation for this reaction. In terms of the chelate effect, explain why ethane-1,2-diamine complex is formed in preference to the hexaaqua complex (3 marks) more moles of products than reactants Increase in disorder Entropy change large and positive

c) Draw a diagram that shows the shape of the complex ion that shows the type of bond between the molecules of ethane-1,2-diamine molecules and the cobalt. (3 marks) arrows showing coordinate bonds from N atom to Co; octahedral arrangement; 2+ charge;

d) Cobalt ratio question (5 marks) Ratio is 3:1 [Co(NH3)6]3+ ?