** Insert the following equation into the formulae sheet:

a1 =

i mi mi0

Section A. Physical Chemistry. (Total of 60 marks) Part 1: Kinetics (20 marks) Question 1 (3 + 2 = 5 marks)

A set of experiments were performed to determine the rate law for the reaction of NO and O2, according to the following equation: 2 NO(g) + O2(g) 2 NO2 (g)

Expt 1 2 3 4 5

[NO] (mol L-1) 0.020 0.020 0.020 0.040 0.010

[O2] (mol L-1) 0.010 0.020 0.040 0.020 0.020

Initial Rate (mol L-1 s-1) 0.028 0.057 0.114 0.227 0.014

a) What is the rate law for this reaction? (3 marks) Look at each reactants effect on rate, in turn: Comparison of Expts 1, 2 & 3 shows that as [O2] doubles, the rate doubles, hence first order in O2. Comparison of Expts 2, 4 & 5 shows that as [NO] doubles, rate increases by a factor of 4, hence second order in NO. Hence rate law is Rate = k [O2] [NO]2 (1 mark for determining the reaction order of each component and 1 mark for the rate law or if just the correct rate law given, all 3 marks) b) What is the value of the rate constant, k? Ensure you include the appropriate unit for k. (2 marks) Choose one experiment and use the info to deduce the rate constant according to k = rate/([O2] [NO]2) e.g. from expt 1 k = 0.028 mol L-1 s-1 / (0.010 mol L-1 x (0.020 mol L-1)2) = 7.0 x 103 L2 mol-2 s-1.

(1 mark for the correct numerical value, 1 mark for the correct units (standard units for 3rd order reactions)) Note that because these are real data, slight differences in the value of the rate constant will be found (e.g. expt 4 gives 7.1 x 103 rather than 7.0 x 103) Question 2 (3 marks)

The first-order rate constant for the decomposition of the insecticide, Killemquick, in the environment = 3.43 x 10-2 day-1. Calculate how long it takes for the concentration of Killemquick to fall to 10% of its initial value. Use ln[A]t = ln[A]o k t. (1 mark) Rearrange this to ln[A]t - ln[A]o = k t. Or ln[A]0 - ln[A]t = k t. which equals ln ([A]0 / ln[A]) = k t (1 mark) Given that [A]t = [A]o x 0.1, we then have ln(10) = k t So t = 2.303/3.43 x 10-2 day-1 = 67.1 days (1 mark)

Question 3

(3 marks)

The rate constant for the reaction of iodide with methyl bromide is 7.70 x 10-3 L mol-1 s-1 at 50C and 4.25 x 10-5 L mol-1 s-1 at 0C. Calculate the activation energy for this reaction. Use the form of the Arrhenius equation with two rate constants and two temps: (1 mark)

So ln(7.70 x 10-3/4.25 x 10-5) = - Ea/8.314 x (1/323 1/273) (1 mark for inserting values in right places) So Ea = 76237 J mol-1 = 76.2 kJ mol-1. (1 mark) (certainly accept 76.3 if temps given as 273.15 & 323.15) Question 4 (1 + 1 + 2 = 4 marks)

The catalysed oxidation of the thallium(I) ion by cerium(IV) in aqueous solution is described by the overall equation: 2 Ce4+ + Tl+ 2 Ce3+ + Tl3+ The accepted mechanism for this reaction is: Step 1: Step 2: Step 3: Ce4+ + Mn2+ Ce4+ + Mn3+ Mn4+ + Tl+ Ce3+ + Mn3+ Ce3+ + Mn4+ Mn2+ + Tl3+

a) Circle all of the intermediates in this mechanism (1 mark) Mn3+ & Mn4+ are the intermediates (1/2 mark each) b) Identify the catalyst in this reaction (1 mark) Mn2+ (1 mark). No other option is correct. c) Assuming that Step 1 is the rate determining step in the reaction, what is the rate law? (2 marks) Rate = k [Mn2+] [Ce4+] (can omit the Rate =). (2 marks) No other option is correct. Question 5 (1 + 2 + 2 = 5 marks)

Experiments to determine the rate law for the reaction below show that the kinetics are very complex. As a result, it has been suggested that the pseudo-first order approach should be used. S2O82- + I- products with a rate constant, k

a) Explain what is meant by pseudo-first order. (1 mark) The concentration of one of the reactants is in vast excess (so its concentration remains effectively constant) and the rate of reaction then depends just on the concentration of one reactant. Or suitable paraphrasing of this. b) Explain how you would manipulate the concentrations of S2O82- and I- to work out the pseudofirst order rate constant k. (2 marks) Make [S2O82-] to be in vast excess of [I-] (e.g. 100-fold), then measure the rate of the first-order reaction (follow product form) as a function of [I-] to get the pseudo-first order rate constant, k. (as rate = k [I-] ). 1 mark for having one named reactant in vast excess and the second mark for how to determine k. c) Then explain how you would again manipulate concentrations of S2O82- and I- to determine the rate constant k. (2 marks) Repeat the determination of k at several different [S2O82-] (1 mark). k = k[S2O82-]. So plot k vs [S2O82-]. (1 mark) For the answers to b) and c), [S2O82-] could be the reactant in excess, so swap the reactants in these answers

Part 2: Equilibria (20 marks) Question 1 (2 marks)

Solid PbCrO4 is added to an aqueous sample which already contains solid PbCrO4 and Pb2+ and CrO42in equilibrium, according to the equation below. Briefly explain what will happen to the position of the equilibrium.

There will be no change in the position of the equilibrium (the solution is already saturated with Pb2+ and CrO42-) (2 marks). It is incorrect to say that the equilibrium will shift towards the soluble products (i.e. to the right) Question 2 (5 marks)

The water-gas shift reaction:

is an important industrial reaction used for producing high purity hydrogen used in the synthesis of ammonia. If 0.250 mol of CO(g) and 0.250 mol of H2O(g) are placed in a 0.125 L flask at 900 K, what is the composition of the equilibrium mixture, if K = 1.56. Show all calculations and justify any approximations: Complete the table below: Concentration Initially Change Equilibrium [CO(g)] 0.250/0.125 =2.00 -x 2.00-x [H2O(g)] 0.250/0.125 =2.00 -x 2.00-x [CO2(g)] 0 +x x [H2(g)] 0 +x x

K =

C O H [ ] [ ] x = = 1.56 C O H O [ ] [ ][ 2.00 x ]
2 2 2 2 2 2 x

2.00 x [ ]
2

= 1.56

x = 2.50 1.25x a n d h e n c e 2.25x = 2.50

x = 1.25 2.00 x

x =1.11 M

Hence at equilibrium:

[CO(g)] [H2O(g)] [CO2(g)] [H2(g)]

= = = =

2.00 x = 0.89 M 2.00 x = 0.89 M 1.11 M 1.11 M

Question 3

(3 marks)

An aqueous suspension of Mg(OH)2 is (Milk of Magnesia) has traditionally been used as a treatment of minor gastric disorders by neutralizing stomach acid. If the Ksp of Mg(OH)2 is 6.3 x 10-10, calculate its solubility (S) in pure water. Concentration [M] Initially Change Equilibrium S 2S +S +2S Mg(OH)2 (s) [Mg2+] 0 [OH-] 0

2+ 3 10 K = M g O H = S 2S= 4S = 6.3 10 s p

] [] [ ] [ ][
2 2

6.3 1010 S= = 5.40 104 M 4

Solubility of Mg(OH)2 =

5.40 x 10 -4

Question 4

(4 + 1 + 1 + 1 = 7 marks)

(a)

You are asked to prepare one (1.0) litre of a carbonate buffer solution with a pH of 10.0. How many grams of Na2CO3 must be dissolved in 1.0 L of 0.20 M NaHCO3 to prepare a buffer of this pH. Data: H2CO3* + H2O H3O+ + HCO 2 HCO+ H2O H3O+ + CO 3 Formula weight (Na2CO3) = 106.0 g/mol Show all calculations pH = 10.0. pKa (HCO3-) = -log(4.68 x 10-11) = 10.32
p H = 10.33 + log C O] C O] [ [ = 10.33 + log 0.20 H C O] [
2 3 2 3 3

K1 = 4.47 x 10-7 at 25C K2 = 4.68 x 10-11 at 25C

[CO ] 10.00 = 10.33 + log

2 O = 0.20 x10(10.00-10.33) 3 0.20 and hence C

[ ]

Therefore

C O ] = 0.20 x10 [
2 3

(-0.33)

= 0.20 x 0.468 = 9.36 x 10-2 M

Mass Na2CO3 = 9.36 x 10-2 x 106.0 = 9.92 g Mass of Na2CO3 added per litre = 9.92..................... g (4 marks) (b) The diagram below shows the curve for titration of a 20 mL aliquot of 0.10 M propanoic acid with 0.10 M NaOH.

14.0 12.0 10.0 8.0 pH 6.0 4.0 2.0 0.0 0.0 5.0 10.0 15.0 20.0 25.0 30.0 35.0 40.0 45.0 Volume of titrant (mL)

pKa Typical buffered titration curve

Titration mid-point

(i)

Mark on the titration curve the position that corresponds to the value of pKa (Propanoic acid), and record this value below. pKa (Propanoic acid) 4.8 - 4.9....................... (1 mark)

(ii)

Mark on the diagram the approximate shape of the titration curve if the original propanoic acid solution also contained 1 M propanoate ions. (1 mark)

(c)

Could a buffer solution be prepared using a mixture of 1 M lactic acid and 1 M sodium lactate? If so, what would be the pH of this buffer? pKa (Lactic acid) = 3.86 Explain your answer (1 mark) Yes, weak acid (pKa = 3.86). pH = pKa + log (1/1) = 3.86 + 0 = 3.86.

Question 5

(1 + 2 = 3 marks)

a) Briefly define the activity coefficient, . (1 mark) Would accept phrases like : the activity coefficient allows for the no-ideality of the solution, or, it accounts for the effect of additional ions on the reactivity (strictly speaking chemical potential but we didnt cover this). Or similar paraphrasing. Would also accept that it is the mathematical correction to relate activity to concentration.

b) Equilibrium constants are unitless. Briefly explain why this is so. (2 marks) Equilibrium constants are made up of activities of the various species and activities are unitless (1 mark). Activities are unitless as they are a ratio: (The ratio is of the molality of the species in solution and at infinite dilution) (1 mark for showing how activity is unitless) Students are given this equation in the formula sheet

Part 3: Thermodynamics (20 marks) Question 1 (1 + 1 + 1 = 3 marks)

Answer True or False to the following statements. a) An increase in atmospheric pressure compresses a gas in a frictionless piston container. The work done on the system is positive. TRUE b) c) The only two means by which energy can be transferred are through heat or work. TRUE If a reaction is very exothermic, it must be spontaneous. FALSE

Question 2

(1 + 1 = 2 marks)

Choose the member with the higher entropy in each of the following pairs, and briefly justify your choice (assume constant temperature): a. 1 mol of O2 (g) or 1 mol of O2 (aq) 1 mol of O2(g) as gases dissolved in liquids are more constrained in their movement than in the gaseous phase, 1 mark b. 3 mol of CH3CH2CH2CH3 (g) or 3 mol of CH3CH3 (g) 3 mol of CH3CH2CH2CH3 (g) as larger, more complex molecules have higher entropy

than smaller molecules, 1 mark (might mention more vibrational and rotational states, but this is not necessary)

Question 3

(4 + 1 = 5 marks)

Decomposition of solid silver oxide (Ag2O) to silver metal and oxygen gas requires heating. The necessary thermodynamic information for this question is provided in the table below. Compound Ag2O O2 Ag Hfo, kJ mol-1 -31.05 0 0 So, J mol-1 K-1 121.3 205.1 42.6

a) Calculate whether this reaction occurs spontaneously at 200C. (4 marks) 2Ag2O 4 Ag + O2 (1 mark) For a reaction to be spontaneous, Gr must be < 0. Gr = Hr - TSr Hro = 4 x Hfo(Ag) + Hfo(O2) - 2Hfo(Ag2O) = 4 x 0 + 2 x 0 - 2 x (-31.05) = 62.10 kJ mol-1 Sro = 4 x So(Ag) + So(O2) - 2 So(Ag2O) = 4 x 42.6 + 205.1 - 2 x 121.3 = 132.9 J K-1 mol-1 So Gro = 62.1 ((200+273) x 132.9/1000) = -0.8 kJ mol-1 (2 marks) Hence it is spontaneous (just!) (1 mark) If the stoichiometry of the equation is wrong, but the rest of the answer is consistent, then up to 3 of the 4 marks can still be given. Also, subtract a mark if they forget to convert T to Kelvin, but the rest of the answer is consistent - will end up with a non-spontaneous reaction in this case (i.e. 35 kJ mol-1). b) Calculate the Gibbs free energy, Gr, for this reaction at equilibrium. (1 mark) At equilibrium, Gr = 0 (1 mark) Question 4 (4 marks)

Ethene (CH2=CH2) reacts with hydrogen (H2) at 25C to produce ethane (CH3-CH3) in a reversible reaction. Use the thermodynamic data provided to calculate the equilibrium constant for this reaction. Compound CH2=CH2 (g) H2 (g) Hfo, kJ mol-1 52.26 0 So, J mol-1 K-1 219.6 130.7

CH3-CH3 (g) CH2=CH2 + H2

-84.68 CH3-CH3 (1 mark)

229.6

Gr = Hr - TSr Hro = Hfo(CH3-CH3) - Hfo(H2) - Hfo(CH2=CH2) = -84.68 - 0 - 52.26 = -136.94 kJ mol-1 Sro = So(CH3-CH3) - So(H2) - So(CH2=CH2) = 229.6 130.7 219.6 = -120.7 J K-1 mol-1 So Gro = -136.94 ((25+273) x (-120.7)/1000) = -100.97 kJ mol-1 (2 marks) Gro = -RTln(K) so K = e^(-Gro/RT) = e^(100970/(8.314 x 298)) = 5.0 x 1017 (1 mark) Question 5 (6 marks)

For the ammonia synthesis reaction at 25C, calculate the change in Gibbs Free Energy (Gr) if 1.00 mol N2(g) at 0.23 atm pressure and 3.00 mol H2(g) at 0.42 atm are converted to 2.00 mol NH3 (g) at 1.45 atm. Gf(NH3)(g) = -16.45 kJ mol-1. N2(g) + 3H2(g) 2NH3(g)

Gr = 2 x Gfo(NH3) - Gfo(N2) 3 x Gfo(H2) = 2 x (-16.45) 0 3 x 0 = -32.90 kJ mol-1. (1 mark) Not at equilibrium so calculate Q. (1 mark) Q = p(NH3) /(p(N2) x p(H2)3) = 1.452/(0.23 x 0.423) = 123.4 (2 marks)
2

Gr = Gr + RT ln Q = -32.90 kJ mol-1 + 8.314 x 298 x ln (123.4) J mol-1 (1 mark) =-32.90 + 11.94 kJ mol-1 = -20.96 kJ mol-1 (1 mark) Note: conditional marks can be given if an earlier stage is wrong but the answers are consistent from that point on.