Chempocalypse Now! Chapter 17 —Kineties Paget Chapter 17 — Kinetics Topics 06 and 16 from the IB HL Chemistry Curriculum 6.1 _ Rates of reaction (2 Hours) Assessment Statement bj _Teacher’s Notes Gad _ | Define the term rote of reaction 1 642 _ | Describe suitable ewerimental procedures for | 2 | Alm: Data loggers can be used to collect data and produce eranhs. measuring rates of reactions TOK: The empirical nature ofthe tape should be emphasize6. Experimental results can support the theory but cannot prove it G3 _ | Analyze data from rate experiments 3 _| Students should be familiar with graphs of changes In concentration, volume, and mass against time, Pages 201-208 gomaz2 The reaction between excess calcium carbonate and hydrochloric acid can be followed by measuring the volume of carbon dioxide produced with time. The results of one such reaction are shown below. Volume of CO, Time How does the rate of this reaction change with time and what is the main reason for this change? A. The rate increases with time because the calcium carbonate particles get smaller. 8. The rate increases with time because the acid becomes more dilute. C. The rate decreases with time because the calcium carbonate particles get smaller. D, The rate decreases with time because the acid becomes more dilute. o3smi2i Which of the following is(are) important in determining whether @ reaction occurs? L._ Energy of the molecules Il, Orientation of the molecules A. Lonly B. llonly ©. Both land Il D. Neither I nor IlChempocalypse Now! Chapter 17 —Kineties Page? Consider the following reaction 2Mn0O, (aq) + 5C:0,"(aq) + 16 H'(aq) > 2Mn™(aq) + 10CO.(g) + 8 H.0(!) Describe three ways in which you could measure the rate of this reaction. The reaction between calcium carbonate and hydrochloric acid, carried out in an open flask, can be represented by the following equation: CaCOs{s) + 2HCaq) + CaCh{aq) + COug) + H-0(/) Which of the measurements below could be used to measure the rate of the reaction? the mass of the flask and contents Il, the pH of the reaction mixture IIl, the volume of carbon dioxide produced A. Land ilonly B. Land ill only ©. Hand ill only D. |, Hand tt Based on the definition for rate of reaction, which units are used for a rate? mol dev B. mol time” C. dm’ time D. mol dm time*Chempocalypse Now! Chapter 17 —Kineties Pages The following data were collected for the reaction 2H,0x(aq) > 2H,0(I) + Calg) at 390°C [H,0,}/mol dem? Time/s 0.200 ° 0.153 20 oz 40 0.104 60 0.090 20 0.078 100 0.070 120 0.083 140 0.058 160 0.053 180 0.049 200 Draw a graph of concentration against time and determine the reaction rate after 60 s and after 120s.Chempocalypse Now! Pages 6.2 Collision theory (3 Hours) Assessment Statement Obj _Teacher’s Notes G24 _ | Describe the kinetic theary in terme of the z ‘movement of particles whose average energy is proportional to temperature in kelvins. 2.2 _ | Define the term activation eneray, Ex 7 23 _ | Describe the collision theowy. 2 | Students should know that reaction rate depends on ‘© cellsion frequency ‘© number of particles with €2 E, ‘+ appropriate collision geometry or orientation 6.2.4 | Predict and explain, using the collision theory, | _3_| Aim7: Interactive simulations can be used to demonstrate this, the qualitative effects of particle size, temperature, concentration and pressure on the rate of a reaction, 625 _ | Sketch and explain qualtatively the Manwall 3_| Students should be able to explain why the area under the curves ‘Boltzmann energy distribution curve fora fixed constant and does not change with temperature. amount of gaat diferent temperatures andite ‘lm 7: Interactive simulations can be used to demonstrate this consequences for changes in reaction rat. 2.6 | Describe the eect of a catalat on achemical | 2 2.7 _| Sketch and explain Maxwell-Bokemann cues | 3 ‘for reactions with and without catalyst Pages 208-214 97N139 Which graph best represents the change in reaction rate that accompanies a change in temperature? A B, c. D. Rate va Rate N Rate | Rate ly > > > > ‘Temperature Temperature Temperature TemperatureChempocalypse Now! Chapter 17 —Kineties Pages 98122 Calcium carbonate and hydrochloric acid react according to the equation below: CaCOs(s) + 2HCl(aq) —+ CaClslag) + COAg) + H:01l) Which conditions will produce the fastest rate of reaction? mol dm? HC! and CaCO: pieces 2 mol dm” HCl and CaCOs pieces mol dm” HCI and CaCO; powder 2 mol dm” HCl and CaCOs powder poe, 97M137 The rate of a particular chemical reaction is known to double for a 10°C increase in temperature. At 40°C the reaction is complete after 8 minutes. In a second experiment, it was found to be complete in 2 minutes. At what temperature was the second experiment carried out? sore 70°C c 80 D. 90°C PP o2mi23 Which statement(s) about the following reaction at 100°C is/are correct? Nog) + 3H.(g) > 2NHa(g) 1. Every collision between N; and H» molecules is expected to produce NH:, Il, This reaction must involve a collision between one N, and three H; molecules. A. Lonly B. llonly C. Both land it D. Neither I nor IlChempocalypse Now! Chapter 17 —Kineties Pages. o2aza The rate of a chemical reaction increases with increasing temperature. This increase in reaction rate is due to |. anincrease in the collision rate. II, a decrease in the activation energy. Ill, an increase in the number of molecules that react, A. Lonly B. tlonly © Landill only D. Il, andl oum10 The reaction between nitrogen and oxygen in the atmosphere under normal conditions is extremely slow. Which statement best explains this? ‘A. The concentration of oxygen is much lower than that of nitrogen. The molar mass of nitrogen is less than that of oxygen. C._ The frequency of collisions between nitrogen and oxygen molecules is lower than that between nitrogen molecules themselves. D. Very few nitrogen and oxygen molecules have sufficient energy to react. oon122 Volume of CO, Time The curve above is obtained for the reaction of an excess of CaCO, with hydrochloric acid. How and why does the rate of reaction change with time? Rate of reaction Reason A Decreases The HCl becomes more dilute 8, Decreases ‘The pieces of CaCO, become smaller c Increases ‘The temperature increases D, Increases ‘The CO; produced acts as a catalystChempocalypse Now! Chapter 17 —Kineties Page? 98Ni24 Which of the following statements regarding activation energy is{are) correct? copy In an endothermic reaction the activation energy for the reverse reaction is smaller than that for the forward reaction Increasing temperature increases the rate of a chemical reaction by lowering the activation energy. only only Both | and Il Neither | nor I Which statement is correct for a collision between reactant particles leading to a reaction? poe, Colliding particles must have different energy. Al reactant particles must have the same energy. Colliding particles must have a kinetic energy higher than the activation energy. Colliding particles must have the same velocity. Which of the following is (are) important in determining whether a reaction occurs? po ey energy of the molecules orientation of the molecules only only both | and Il neither | nor I Which change of condition will decrease the rate of the reaction between excess zinc granules and dilute hydrochloric acid? A 8 c D. increasing the amount of zinc increasing the concentration of the acid pulverizing the zine granules into powder decreasing the temperatureChempocalyose Now! Chapter 17 —Kinetes Pages Catalytic converters are now used in most cars to convert some components of exhaust gases into less environmentally damaging molecules. One of these reactions converts carbon monoxide and nitrogen monoxide into carbon dioxide and nitrogen. The catalyst usually consists of metals such as platinum or rhodium (a) Write an equation for this reaction. (b) Suggest why it is important to reduce the concentrations of carbon monoxide and nitrogen monoxide released into the atmosphere. (c) Why do you think the converter sometimes consists of small ceramic beads coated with the catalyst? (d) Suggest why the converter usually does not work effectively until the car engine has warmed up. (e) Discuss whether the use of catalytic converters in cars solves the problem of pollution from cars. ouM131 What is the effect of adding a catalyst to a reaction mixture at equilibrium? A. It decreases the activation energy of the forward reaction and increases the activation energy of the reverse reaction, B. It decreases both the activation energy and the enthalpy change of the forward reaction, 9 It decreases the activation energies of both forward and reverse reactions. D. It decreases the activation energies and enthalpy changes of both forward and reverse reactions. s9on124 The addition of a catalyst to a chemical reaction alters the rate primarily by Changing the enthalpy of the reaction Increasing the number of collisions between the reactant molecules in @ given time Increasing the fraction of reactant molecules with a given kinetic energy Providing a different reaction pathway poe,Chempocalypse Now! 03119 The rate of a reaction between two gases increases when the temperature is increased and a catalyst is added. Which Chapter 17 —Kineties statements are both correct for the effect of these changes on the reaction? Increasing the temperature ‘Adding a catalyst A | Collision frequency increases Activation energy increases 8, | Activation energy increases Activation energy does not change C. | Activation energy does not change Activation energy decreases D. | Activation energy increases Collision frequency increases amis Which of the quantities in the enthalpy level diagram below is(are) affected by the use of a catalyst? A. only 8. Illonly ©. Land ilonly D. land Iilonly e8Mi25 A catalyst is used in the industrial manufacture of ammonia from hydrogen and nitrogen. The purpose of the catalyst is to PP Purify the nitrogen and hydrogen. C. Produce a higher yield of ammonia, D. Increase the rate of the reaction. Increase the value of the equilibrium constant.Chempocalypse Now! Page 10 16.1 Rate expression (3 Hours) Assessment Statement Obj _Teacher’s Notes TELA | Distinguish between the terme rate constant | 2 ‘overoll order of reaction and order of reaction with respact to a particular reactant. TEL | Deduce the rate expression fora reaction rom | 3 | Aim7: Virtual experiments can be used here experimental data TELS | Soive probleme invalving the rate expression 3 TELA | Sketch, ently and analyze graphical 3_| Students shouldbe familiar with both concentration time and rate representations for 2210, fitst- and second- concentration graphs. order resctions Pages 215-224 04m120 What is the definition of halflife for a first order reaction? copy ‘The time required for the quantity of a reactant to decrease by half. Half the time required for a reactant to be completely used up. Half the time required for @ reaction to reach its maximum rate. The time required for a reaction to reach half of its maximum rate. 03N120 ‘The rate expression for a reaction is shown below. rate = K(AY(B]? Which statements are correct for this reaction? ‘The reaction is second order with respect to both A and B. ‘The overall order of the reaction is 4. Doubling the concentration of A would have the same effect on the rate of reaction as doubling the concentration of B. Land it only Land ill only Wand Ill only ll, and titChempocalypse Now! 99N123 The rate constant for a certain reaction has the units concentration time”, What is the order of reaction? pop, 02N122 The following experimental data was obtained for the reaction X+Y — Products. What is the order of reaction with respect to X and the order of reaction with respect to Y? 9 02N123 2ando Oand2 and 1 tando Chapter 17 —Kineties [XI/mol dm? | [XI/mol dev 0.10 0.50 0.20 0.20 050 0.50 0.50 050 Page 11 The rate of a gaseous reaction is given by the expression rate = KIPI[QI. if the volume of the reaction vessel is reduced to % of the initial volume, what will be the ratio of the new rate to the original rate? oom, a4 1:16 a 16:2Chempocalypse Now! Chapter 17 —Kineties Page 12 oum130 ‘The reaction 3M+Q > MQ is first order with respect to M and second order with respect to. Q. When [M] = 0.100 mol dm”? and [Q] = 0.020 mol dm, the rate is 0.010 mol dm™*s*, What is the value of the rate constant, in mol? dm® “7 10 100 280 00 poe, 00N123 ‘The rate equation for the reaction between O; and NO is Rate = k[O.][NO]” both doubled? 10 if the concentrations of 0) and NO By what factor would the rate of this reaction incr 18 oo ey 01122 Use the information below to deduce the rate equation for the hypothetical reaction: X+Y¥o2 ix] ™ Relative moldm? | mol dm? Rate 0.01 0.01 1 0,02 0.01 4 0.02 0.02 4 A. Rate = KIXILV] B. Rate = Kix] C Rete = KV? D. Rate = KIX]?Chempocalypse Now! Chapter 17 —Kineties Page 13 97M138 Which of the following graphs represents a first-order reaction? A B. + ‘Cone Cone ——____, Time . Time c D. 4 Cone Cone Time Time soma The reaction between nitrogen dioxide and carbon monoxide is given by the equstion below: NO(g) + CO(g) —* NO(g) + CO3(8) According to the following experimental data, what is the rate equation? INO] [coy Rate moldm® | moldm? | moldm”s 0.10 0.10 1.010" 0.30 0.10 9.010" 0.30 0.30 9.0% 10" A. Rate = KINO:IICO] B. Rete = kICOl? Rete = KINO]? D. Rate = KINO.Chempocalypse Now! Chapter 17 —Kineties Page 14 The reaction CH,Cl(aq) + OH'(aq) —> CH.OH(aq) + CI'(aq) is found to be second order overall. Give three possible rate expressions consistent with this finding Give the units of k in each of the rate expressions below: (a) rate =kINO.? (b) rate =K[CH.CH.Er] (c) rate = kINH, — es (d) rate = k[NO}'[Br.] (e) rate = k(HzJ{l:] The reaction: 2N,0s(g) — 4NO2\g) + O2() has a value of k = 6.9% 10s* at a certain temperature. Deduce the rate expression for this reaction. A reaction involving A and B is found to be zero order with respect to A and second order with respect to B. When the initial concentrations of A and B are 1.0 x 10° mol dm and 2.0 x 10° mol dm’*, respectively, the initial rate of the reaction is 4.5 x 10“ mol dm? min“, Calculate the value of the rate constant for the reaction,Chempocalypse Now! 16.2 Reaction mechanism (1 Hour) Assessment Statement Chapter 17 —Kineties Page 15 obj Teacher's Nates TERA | Explain that reactions can accur by more than ‘one step and that the slowest step determines ‘the rate of reaction (rate-determining stp). 622 | Describe the relationship between reaction ‘mechanism, order of reaction and rate- determining step. ‘Only examples with one- oF tworstep reactions where the mechanism 5 iven will be assessed. TOK: Agreement between rate equation and a suggested mechanism only provides evidence to suppart a reaction mechanism. Disagreement dlsproves the mechanism, Pages 225-227 o3Mi23 Which step in a multi-step reaction is the rate determining step? A. The first step B. The last step ._ The step with the lowest activation energy D. The step with the highest activation energy oani23 ‘The reaction between NO, and CO to give NO and CO, is thought to occur by the following mechanism: NO: +NO2 > NO, + CO — NO, + CO; fast What is the rate equation? Rete = K{NO:IICO] Rate = KINOJICO] Rate = kINO;]'[CO] Rate = k[NO2]? poe, Ifthe reaction NO.(g) + CO(g) — NO(g) + CO.(g) rate expression for the reaction? NO + NO; slow ‘occurs by a one-step collision process, what is the expectedChempocalypse Now! Chapter 17 —Kineties Page 16 The reaction 2NO; —> 2NO +0, isshown experimentally to be second order with respect to NO.. Is this consistent with the mechanism shown below? NO; + NO; — NO + NO; slow NO, +NO + 2NO+0, fast Which statement about the following reaction at 450°C is correct? 280: +0; + 250; The reaction must involve a collision between one O; and two $0; molecules. Il, Every collision between SO, and 0, will produce SOs. Ill, The rate-determining step is the slowest step of the reaction. A. Landill B. only ©. Ilonly D. None of the statements is correct. If the mechanism of a reaction is: AB, + AB, > A,Bs slow ABe = Ar+2B: fast (a) What is the overall equation for the reaction? (b) What is the rate expression for this reaction? (c) What units will the rate constant have in this expression?Chempocalypse Now! Chapter 17 —Kineties Page 17 16.3. Activation energy (2 Hours) Assessment Statement Obj _Teacher’s Notes 1631 | Describe qualitatively the relationship between | 2 the rate constant (k] and temperature (7), TES2_| Determine activation energy (ey values from | 2 | The Arthenius equation and is logarthariTorm are provided in the the Arrhenius equation by graphical method. Chemistry data booklet. The use of simultaneous equations will nt be assessed, Pages 228-232 o4mi2i Values of a rate constant, k, and absolute temperature, T, can be used to determine the activation energy of a reaction by a graphical mathod. Which graph produces a straight line? A. k versus T B. kversus 1/T ©. Inkversus T D. Inkversus 1/T e7N138 For a first order reaction, which of the following changes as the concentration of the reactant changes? lL Rete I. Rate constant I, Hallie A. Loniy 8. llonly ©. Illenly D. Land il only Consider the following statements: |. The rate constant of a reaction increases with increase in temperature, Il, Increase in temperature decreases the activation energy of the reaction. Ill, The term A in the Arrhenius equation (k = Ae”) ) relates to the energy requirements of the collisions. Which statement(s) is/are correct? A. Lenly B. only © Landill only D. Handi onlyChempocalypse Now! Chapter 17 —Kineties Page 18 To what does A refer in the Arrhenius equation, k= Ae“? ‘A. activation energy B. rate constant C. gas constant D. collision geometry 12 of a chemical reaction increases with increasing temperature. This increase in rate is due to: L._anincrease in the collision rate II, an increase in the activation energy IIL an increase in the rate constant A. Land l only B. Land ill only © Mand tll only D. Llland itChempocalypse Now! Chapter 17 —Kineties Page 19 Solve each of the following Paper 2 problems. Show any work in the space provided or on a separate piece of paper. 03N208 @ (by © The following data were obtained for the reaction of nitrogen monoxide gas, NO(g), with oxygen gas to form nitrogen dioxide gas, NO, (g), at 25°C. Experiment INO} 10,7 Initial rate / moldm* mol dm mol dms* 1 oso | (020 30x10? 2 0.50 0.40 60x10 3 1.00 | 0.80 4.8x107 (@ Calculate the order with respect to the two reactants and write the rate expression for the reaction. Show your reasoning. . [3] (ii) Explain why the following mechanism is not consistent with the rate expression. By NO (g)+0,(g) > NO, () +0 ();slow step NO (g)+0(g) > NO, (g); fast step (ii) Explain why the following mechanism is consistent with the rate expression, but is unlikely. (2) 2NO (g)+0,(8) > 2NO; (g) (iv) Explain why the following mechanism is consistent NO (g) +0, (g) > NO, (g); fast NO, (g) +NO (g)> 2NO, (g);slow the rate expression. By (v) Suggest, giving a reason, one other mechanism that would be consistent with the rate expression. GB) ‘The following equilibrium is established at 1700°C CO, (8) +H, (g) = H,0 (g) + CO (e) If only carbon dioxide gas and hydrogen gas are present initially, sketch on a graph a line representing rate against time for * the forward reaction. «the reverse reaction until shortly after equilibrium is established. Explain the shape of each line. 7 K, forthe equilibrium reaction is determined at two different temperatures. At 850°C, K, = 1. whereas at 1700°C, K, = 4.9 On the basis of these K, values explain whether the reaction is exothermic or endothermic. [3]Chempocalypse Now! Chapter 17 —Kineties 03M206 @ ®) © @ Gi) @ Gi) (iii Draw a graph to show the distribution of energies in a sample of gas molecules. Label the axes and label your curve T,. Using the same axes, draw a second curve to represent the distribution of energies at a higher temperature, Label this curve T, State and explain, with reference to your graph, what happens to the rate of a reaction when the temperature is increased. State and explain the effect of a catalyst on the rate of @ reaction. Distinguish between the terms heterogeneous and homogeneous catalyst. For each type of catalyst, state an example and write an equation for a reaction it catalyses. ‘The data below refer to a reaction between X and Y. Initial concentration / Initial rate of reaction / moldm™* moldm™ Experiment x Y 1 0.25 0.25 1.0%107 2 0.50 0.25 4.0x107 3 0.50 0.50 8.0x107 () Define the term order of reaction. (ii) Deduce the order of reaction with respect to both X and Y. Explain your reasoning. ii) Write the rate expression for the reaction and calculate the rate constant, including its units, (iv) Calculate the initial rate of reaction when the initial concentrations of X and Y are 0.40 mol dm™ and 0.60 mol dm™ respectively. Page 20 BI) 2] Bl 2] i] ay a Ay 2Chempocalypse Now! Chapter 17 —Kineties Page 21 (o0Nn203 Dinitrogen oxide decomposes to give nitrogen and oxygen according to the following equation: 2 O(g) + 2Nz(g) + O;12) AH® = -82 Ki mol” (a) The decomposition is a first order reaction in the presence of gold as a catalyst. The half-life of the catalysed reaction at 834 °C is 62X10" s, (i) Calculate the rate constant (velocity constant), &, fer the reaction at this temperature and give the units of & a Arrhenius (ii) Calculate the activation energy of the reaction at chis temperature. given d constant. A = 25s your 2 cataiyst is vimelecuiar. suction for ench step’ (itty Slow step: Fast step. (bd) Draw a labelled diagram showing the potential energy changes dur uncatalysed reaction given above,Chempocalypse Now! Chapter 17 —Kineties Page 22 oum205 ‘Magnesium reacts exothermically with dilute sulfuric acid according to the following equation’ Ma(s) ++ H,SO, (aq) > MgSO, (aq) +H, (g) (a) Outline an experimental procedure by which you could obtain a value for the rate of this reaction. (6) (b) From the results of such an experiment using excess magnesium ribbon and sulfuric acid of concentration 0.6 moldm”, the graph shown in Figure 1 was obtained. Describe how and explain why the slope of the curve changes with time. 22) Figure 1 60 50 40 Volume of hydrogen 30 gas /cm? 20 10 oO 0 10 20 30 40 50 60 70 80 90 Time /s (©) Sketch the graph shown in Figure 1 and label the curve A. (The experiment is repeated using the same mass of magnesium ribbon and the same volume of acid of concentration 0.3 moldm™. Show on the same sketch the curve you ‘would expect to obtain and label it B. Explain your choice at a molecular level. BI (ii) The experiment is repeated using the same mass of magnesium powder and the same volume of acid of concentration 0.6 moldm*. Show on the same sketch the curve you would expect to obtain and label it C. Explain your choice at a molecular level. B} This question continues on the next page.Chempocalypse Now! Chapter 17 —Kineties Page 23 (@) From the results of a series of experiments involving magnesium and sulfuric acid, a graph of rate against acid concentration was plotted (Figure 2). Use Figure 2 to deduce the order of reaction with respect to sulfuric acid. 2) Figure 2 0.01 a 0.008. a Rate / 0.006: “a 0 0.1 0.2 0.3 0.4 05 06 0.7 0.8 0.9 10 {H,S0,]/ moldm™ (©) Under the conditions used, the order of reaction with respect to magnesium is zero. Give the rate expression for this reaction, Calculate the value of the rate constant and give its units. State how the value of the rate constant would change if the experiment were repeated at a higher temperature. (4 (Sketch an enthalpy level diagram for an exothermic reaction, showing the enthalpy change, (AH), the activation energy, (E,), and the activation energy for the catalysed reaction, (E,,). (3)Chempocolypse Now! chapter 17 Kinetics o1n208 “When steam is passed over heated carbon, the following equilibrium is established: C(s)+H,0(g) =H, (2) + CO(2) ‘The value of the equilibrium constant (K,) at various temperatures is given in the table below: Temperature / K 700 1000 =| ~—«1300 Equilibrium constant (K.) 4,88x10% 451x107 | 1.88 (a) Write the expression for the equilibrium constant and give its units. Deduce whether the forward reaction is endothermic or exothermic and state how you reached this conclusion. (6) Predict and explain the effect of an increase in temperature, total pressure and surface area of carbon on the: (i) rate of the forward reaction; i) (H,0]:[H,] ratio; iii) value of the equilibrium constant. (©) Im the above experiment, the surface of the carbon is sprayed with a catalyst. Draw an appropriate energy level diagram for the reaction, showing the effect of the catalyst. State the way in which the catalyst affects the rate of the forward reaction, the rate of the reverse reaction and the overall position of equilibrium. Page 24 . 4 6) OI 0) 6]Chempocalypse Now! Chapter 17 —Kineties Page 25 97N212 (a) Describe and explain the effect of increasing reactant concentration on the rate of a reaction. In your account, describe the difference between rate and rate constant and explain why the order of a reaction cannot be deduced from the balanced equation of the reaction. {6 marks] (b) The graph provided is a plot of Ink against 1x10? for a given reaction. Ink T HE r TE 5.0 + 5 : the t 15 16 17 18 19 2.0 21 pxle ‘Use the graph to determine the energy of activation of the reaction. {4 marks] (©) Explain why the rate of a reaction increases gradually with increasing temperature rather than changing suddenly at a certain temperature, {5 marks]Chempocalypse Now! Chapter 17 —Kineties 97M208 This question concerns the reaction; H,0,(aq) + 2HI(aq) = I,(aq) + 2H,00) (a) Im a particular series of experiments to determine the initial rate of this © © ) reaction, a fixed amount of sodium thiosulfate and a few drops of starch indicator were added to the solution. The time required for the formation of the blue-black starch-iodine colour was measured. With reference to the reactions involved, explain what is indicated by the appearance of the blue- black colour, why it does not appear immediately, and how the time required for its appearance is related to the rate of the reaction. ‘When the experiment was repeated using various concentrations of HI and constant H,O, concentrations, the following results were obtained; [HI] mol dm™ | 0.155 | 0.12 | 0.090 | 0.070 | 0.040 | 0.030 time s 10 30 50 68 109 130 Use a graphical method to determine the order with respect to HI. If the order for H,O, is the same as that of HI, write the rate equation for this reaction. The following three-step mechanism for this reaction has been proposed; 1. H,O, +1 OH- + HOI 2. HY +OH- HO 3, HOl+H' +r 31,+H,0 Show that this mechanism gives the equation for the overall reaction and discuss the relative speeds of steps 1-3 in terms of the reacti fie tee step: reaction orders for Page 26 [4 marks} {6 marks] [5 marks]Chempocalypse Now! Chapter 17 —Kineties 98M208 (@) The rate of a decomposition is studied by measuring the reactant concentration at certain times. ‘Time/min o | 20 | 40 | 6 | 80 | 100 | 120 conc/10 mol dm} 1 | 0.69 | 0.48 | 0.34 | 0.24 | 0.16 | O11 (i) Plot a graph of concentration against time. (ii) How could the rate be determined from the graph at any selected time? Explain the shape of the graph in terms of rate. (ii) What is meant by half life? Measure three half life values from the graph, Deduce the order of this reaction. (iv) Calculate a value of the rate constant from the half life and one from the initial rate of reaction. (b) The rates of most reactions are increased by (® increasing the concentration of the reactants. ii) increasing the temperature at which the reaction is carried out. Gi) the addition of a suitable catalyst. Explain these increases on a molecular basis. Page 27 [3 marks} [5 marks] [5 marks] [5 marks] [7 marks]Chempocalypse Now! Chapter 17 —Kineties 99206 @ ) © The rate constant, k, for any reaction is related to the activation energy, E,, by the Arhenius equation. @ ww, Explain the meaning of the terms: rate constant and-activation energy. A particular reaction is found to be second order overall. Specify the units for both the rate of reaction and the rate constant. Rates of reactions depend on temperature q@ «iy ii) Using the same sets of axe’, draw two clearly labelled curves to show the distribution of energies of the molecules of a fixed mass of gas at different temperatures, T, and T, where T, is the higher temperature. With reference to the curves in (j) explain why an increase in temperature increases the rate of a gaseous reaction. Explain briefly how a catalyst can increase the rate of a chemical reaction, The rate constant, k, was determined for the decomposition of hydrogen iodide at various temperatures, The results giving Ink for a range of temperatures are given below. (ii) (iii) Temperature T/K Ink TUKT 550 =15.6 | 182x107 600 =12.2 1.67 x10" 650 { 9.4 154x10" 700 =I 143x107 750) 49 133x10" Plota graph of Ink against T" (Take the Ink axis from -20 to 0 and the Taxis from 1.210” to L910" K") Calculate the gradient (slope) of your graph and use it to determine a value for the activation energy, B, , stating its units. Without obtaining the actual value, state two different ways in which the value of A in the Arhenius equation could be determined. Page 28 (4) 2) (4 2) 2} 4) i) 2Chempocalypse Now! Chapter 17 —Kineties 98204 Dinitrogen oxide, N,O, is a moderately stable compound that is used as an anaesthetic. However, at high temperatures it decomposes according to the following equation: N,0(@) > N,(@)+40,(8) AH =~76 kJ mol (@) The uncatalysed decomposition reaction is second order. @ @ ii) Gy) Give the rate expression for this reaction. At 1073 K the rate constant (velocity constant) for the reaction is 0.30 dm’ mol” s“. Calculate the rate of the reaction for 0.10 ‘mol dm? N,O at 1073 K specifying the units. At 1148 K the rate of the same reaction increases by a factor of 5.9 (590 %). Calculate the value for the rate constant at 1148 K. Explain qualitatively why the value for the rate constant increases as the temperature increases. Page 20 EI mark] [2 marks] [1 mark} 2 marks] This question continues on the next page.Chapter 17 —Kineties Chempocalypse Now! a (©) The decomposition of dinitrogen oxide using gold asa catalyst isa fast order reaction with an activation energy of 121 IJ mol”. ‘The activation energy of the uncatalysed reaction is 240 kJ mol”, @ In the space below, draw a diagram showing the potential energy changes during the uncatalysed and catalysed reaction using the same axes. Gi) Why is the half-life of the catalysed reaction constant? B marks] [1 mark} Page 30Chempocalypse Now! Chapter 17 —Kineties Page 31 9204 The following data were obtained for the reaction between A and B: Alag) + 2B(aq) — 3C(aq) + D(aq) Taitial concentration Initial Rate Experiment | of Reactants (moldm™) | of Reaction A B (mol dm” hr?) 1 0.200 0.200 0.50 2 0.400 0.200 2.00 3 0.400 0.800 8.00 (a) Give the order with respect to A. im (b) Give the order with respect to B. Uy (©) Write the rate expression for this reaction, ay (@)__ Using the data from the first experiment, calculate the value of the rate constant and give its units. oy