Topic 6 HIGHER Level Summer & Winter Papers Summer 1999 to Summer 2013 Name: Topic Exam Statistics (Paper 2): eeretae eescty rey WEL CE Lulu luce 132/1080 12% /160 % 227/2700 8% /400 % 359/3780 9% 1560 % Total number of papers represented here is 27, each with 40 marks of Section A and 100 marks of section 8 (4 questions from which you chose to answer only 2) Page 1 of 75 PBIB HL 6 EQ Paper 2 s99 to s13 incl W HL SECTION A 12w 1a (iv) Using a digital thermometer, the students discovered that the reaction was exothermic, State the sign of the enthalpy change of the reaction. AH. ny HLSECTION A 11w NOT with 1b Total amount of gas produced = 34.1dm* (4) Amairbag inflates very quickly. (@)__Ittakes just 0.0400 seconds to produce nitrogen gas in the simulation. Calculate the average rate of formation of nitrogen in (b) (iii) and state its units. iy (ii) The students also discovered that a small increase in temperature (e.g. 10°C) causes a large increase (e.g. doubling) in the rate of this reaction. State one reason for this. [I] HL SECTION A 115 Page 2 of 75 PB2. Consider the following graph of In k against 2 (temperoture in Kelvin) forthe second order decomposition of NO into N, and O. T N,O>N, +0 Ink PS 0.96 0.98 1.00 1.02 1.04 1.06 1.08 1.10 1.12 Ld 1.16 dio? Kt Tr (@)_ State how the rate constant, k-varies with temperate, T. wy (b) Determine the activation energy. E,, for this reaction. [3] Page 3 of 75 PB(©) The rate expression for this reaction is rate=k[N,OF and the rate constant is 0.244 dm? mol s* at 750°C. Asample of N,O of concentration 0.200 mol dm’ is allowed to decompose, Calculate the sate when 10% of the N,O has reacted. Ly HL SECTION A 10s Page 4 of 75 PB2, Alex and Hannah were asked to investigate the kineties involved in the iodination of propanone. ‘They were given the following equation by their teacher. CH,COCH, (aq) +1,(aq) "2 5 CH ICOCH, (aq) + Haq) Alex’s hypothesis was that the rate will be affected by changing the concentrations of the propanone and the iodine, as the reaction can happen withont a catalyst. Hannah’s hypothesis, ‘was that as the catalyst is involved in the reaction, the concentrations of the propanone. iodine and the hydrogen ions will all affect the rate. They carried out several experiments varying the concentration of one of the reactants or the catalyst whilst keeping other concentrations and conditions the same, and obtained the results below. ‘Composition by volume of mixture / em! . " _ ST] Initial rate Experiment | 1.00 mol dm™* | Water | 1.00 mol dav 500x107 | / mol ams? CH,COCH,aq) Haq) mol dm“ I, in KI 1 10.0 60.0 10.0 20.0 4.96x10°° 2 10.0 50.0 10.0 30.0 5.0410 3 5.0 65.0 10.0 20.0 247x10° 4 10.0 65.0 5.0 20.0 2.5107 (2) Explain why they added water to the mixnures i (b) @ Deduce the order of reaction for each substonce and the rate expression from the results. PI (@) Comment on whether Alex's or Hannah's hypothesis is comect. 77] Page 5 of 75 PB(©) Using the data from Experiment 1. determine the concentration of the substances used and the rate constant for the reaetion including its units BI (4) @ This reaction uses a catalyst. Sketch and annotate the Maxwell-Boltzmann energy distribution curve for a reaction with and without a catalyst on labelled axes below. [3] Gi) Describe how a catalyst works. ij HL SECTION A 08w Page 6 of 75 PB1. (a) The diagram shows the apparatus used to study the rate of reaction between calci carbonate and hydrochloric acid. CaCO, (s) + 2HCI(aq) — CaCl, (aq) +H,0 (1) +CO,(g) ‘The quantities of reactants added to the flask in one experiment carried out at r0 temperature were amass of single piece of CaCO,(s) = 5.00 volume of 1.00 moldm® HCI(aq) = 50.0 cm’ The balance was set to zero at the start of the experiment. The graph shows how the mass of the flask and contents changed daring Experiment 0.00 ‘Mass of flask and contents /g Time/min Page 7 of 75 PB@ Explain why the mass decreased. G@ Calculate the amount, in moles, of each reactant at the start of Experiment 1 (ii) Use your answers to (a) (ii), and the equation for the reaction, to deduce which reactant was added in excess Giv)_ The experiment was repeated with small pieces of calcium carbonate. Draw two lines (labelled 2 and 3) on the graph to show how the mass of the flask and contents changes in the following experiments at the same temperature. Experiment Mass of small pieces | Volume of 1.00 moldm™ oes of CaCO,(s)/g HCI(aq)/cm? 2 230 50.0 3 5.00 25.0 Page 8 of 75 fy LI fy cy PB() For the reaction between compounds A and B the initial rate was measured in a seties of reactions carried out at the same temperature. Experiment Initial [4] / Tnitial (B] / Initial rate /, mol dm mol dm moldm” min 1 42x10" 78x 107 88x10" 2 42x10? 39x107 22x10 3 84% 107 39x10" 22104 @ Deduce the order of reaction with respect to A and to B, giving a reason in each case, PI (i) Deduce the rate expression for the reaction. ay (iii) Use the data for Experiment 1 to determine the value, including units, of the rate constant for the reaction. 2 HL SECTION A 075 Page 9 of 75 PB1. Nitrogen(II) oxide reacts with bromine according to the following equation. 2NO(g)+ Br,(g) + 2NOBr(g) AH = negative The data below were obtained for the reaction between NO(g) and Br,(g) at a specified temperature and pressure. «= Initial [NO] Initial [Br] / ‘ apt Experiment aol dia” mol dv! Initial rate / mol dm’*s * 2.00 % 10 9.00 x 107 3.20 x 10? 2 2.00 x 107 2.50 X 107 1.60 x107 3 4.00 x 10* 5.00 x 107 1.30 x 107 (a) Determine, giving a reason, the order of reaction with respect to NO and the order of seaction with respect to Br, Py (b) Derive the rate expression for the reaction between NO and Br, Ay (©) Calculate the rate constant for the rate expression using experiment 1 and state its units. [27 Page 10 of 75, PB(4) Ifthe total volume of the reaction mixture was doubled at constant temperature, state the effect. if any, on (@ the rate constant, en ii) _ the rate of change of the Br,(g) concentration. lm (2) A heterogeneous catalyst may be used in this reaction, Outline how heterogeneous catalysts work. ey (© Draw a labelled enthalpy Level diagram for the reaction between NO(g) and Br,(g). with and without the use of a catalyst. BI HL SECTION AOSw Page 11 of 75 PB1. Anequation for the decomposition of substance A is 24> 2B+C ‘A graph showing the change in concentration of A against time as the reaction proceeds at a particular temperature is shown below. 0.10 0.09 0.08 0.07 0.06 LAI! mol dav? 0.05 0.04 0.03 0.02 0.01 oO 1000 2000 3000 4000 5000 Time/s. (@) Define the term half life of reaction. wy (>) Use the graph to measure values of half-life of reaction, starting from 2} time = zero time = 2000s (© Deduce the order of the reaction with respect to A. giving a reason for your choice, and write the rate expression for the reaction. B @)_ Fora different reaction, between compounds D and E, the rate expression is, rate =k{DP TE] Calculate the value of & including units, for the reaction when the concentrations of both D and E are 135x107 mol dm™ and the reaction rate is 3.75*10~ mol dm min £3] HL SECTION A 05s Page 12 of 75, PB3. When a small quantity of a strongly smelling gas such as ammonia is released into the air, it ean be detected several metres away in a short time. (a) Use the kinetic molecular theory to explain why this happens. Py (©) State and explain how the time taken to detect the gas changes when the temperature is increased, PI HL SECTION A 05s Page 13 of 75 PB4. The following reaction 0, (2) + 4NO, (2) +0, (2) is described as first order with respect to NO; (@) Write the rate expression for the reaction ty (b) One possible mechanism for this reaction is given below. N,O,(2) — NO, (g)+NO, (2) Step 1 N,0,(2)+ NO, (g) > 2NO, (g}+ 0, (g) Step 2 Describe the rate expression that would result if the rate determining step in the mechanism is @ Step 1 fl Gi) Step2. PI Outline your reasonsing. (©) _ Fxplain what is meant by the term half-life for this reaction my @ State what is characteristic about the half-life of a first order reaction. ly HLSECTION A 04s Page 14 of 75 PB1, Nitrogen(II) oxide reacts with hydrogen as shown by the following equation 2NO(Q) + 2H, (g) +N, (@) + 2H,0(@) The table below shows how the rate of reaction varies as the reactant concentrations vary. Experiment | Initial [NO] / | Initial [,] / Initial rate / mol din mol din mol N, din” s™ 1 0.100 0.100 2.5310 2 0.100 0.200 5.05x10" 3 0.200 0.100 10.1010" 4 0.300 0.100 22.80x107 (a) Determine the order of reaction with respect to NO and with respect to H,.. Explain how you determined the order for NO. BI NO (b) Write the rate expression for the reaction, iy (©) Calculate the value for the rate constant, inchnding its units. Py Page 15 of 75 PB(@ A suggested mechanism for this reaction is as follows. H,+NO=X fast step X+NO+Y+H,O slow step Y+H, +N, +H,0 fist step State and explain whether this mechanism agrees with the experimental rate expression in (). [4] (©) Explain why a single step mechanism is unlikely for a reaction of this kind. PI (8 Dednce how the initial rate of formation of H,O(g) compares with that of Nz(g) in ‘experiment 1, Explain your answer. Py HL SECTION A 04s Page 16 of 75, PB6, Deseribe in molecular terms the processes that occur when (a) aminture of ice and water is maintained at the melting point PT (b) _asample of a very volatile liquid (such as ethoxyethane) is placed on a person’s skin. Ly HLSECTION A 035 3 (b) The following graph represents the change of concentration of reactant and product during a reaction, 07 06 0s T O4 SEONG epee [reactant] or ee product] / 0.3, mol dmv? 0.1 7 Wt T cco “ESE et 0 10 20 30 40 50 60 Time /s (i Calculate the average rate of reaction over the first 15 s, stating the units. BI) Page 17 of 75, PBHL SECTION Ao2w 3. A balloon, which can hold a maximum of 1100 cm? of air before bursting, contains 955 em! of air ats °C (a) Determine whether the balloon will burst if the temperature is increased to 25 °C. Assume that the pressure of the gas in the balloon remains constant a (0) Use the kinetic theory to explain what happens to the air particles inside the balloon as the temperature is increased to 25 °C P] HL SECTION A 02s Page 18 of 75, PB1, The following data were obtained for the reaction between gases A and B: @ 0) ©) @ © Initial concentration of | . Experiment | veactants / mol din? ee a B 1 1.010% | 2.0x107 3.0107 2 2.0x10° | 2.0107 3.0x10~ 3 10x10? | 4.0x107 1.2x10% Define the term overall order of reaction. Deduce the order of reaction with respect to A and the order of reaction with respect to B. ‘Write the rate expression for the reaction between A and B. Use the data from Experiment 1 to caleulate the value of the sate constant for the reaction and state its units. The reaotion between gases A and B is repeated at a pressure double that of the original Determine how many times faster the reaction will be when the pressure is doubled Page 19 of 75, PB Al 2 ay 2 Wy(8 Some solids act as heterogeneous catalysts in this reaction. State what is meant by the term heterogeneous and outline how such catalysts work, BI (g) State and explain how the following changes affect the rate of reaction between A and B: G) Using a catalyst 2] (i) Decreasing the temperature 2] HLSECTION A o1w 1 (b) The reaction between methanol and oxygen is spontaneous at all temperatues. Explain why methanol vapour is stable in air, but the mixture reacts quickly when ignited, Py HL SECTION AO1w 3a (b) Asa volatile liquid in an isolated container evaporates. its temperature drops. Account for this observation in terms of the behaviour of the molecules. PI Page 20 of 75, PBHL SECTION A Ow 3. _Dinitrogen oxide decomposes to give nitrogen and oxygen according to the following equation: 2N,0(g) > 2N, (g) +0, (2) AH® =-82 kT mol (@) 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 162x10* s (i) Calculate the rate constant (velocity constant), & for the reaction at this temperature and give the units of & Gi) Calculate the activation energy of the reaction at this temperature, given the Arrhenius constant, A - 2567 Gii) The decomposition of dinitrogen oxide without a catalyst is bimolecular. Suggest a possible mechanism for the reaction indicating the equation for each step: Slow step: Fast step: (b) Daw a labelled diagram showing the potential energy changes dusing the catalysed and uneatalysed reaction given above. HL SECTION A 00s1 Page 21 of 75, PB uy Py Py} 2}() The depletion of ozone, O,, in the upper atmosphere can be caused by the reaction of automobile exhaust gases, such as NO, with the ozone, The reaction between O;(g) and NO(g) has been studied and the following data were obtained at 25 °C Experiment |[NO(@)]/auuldur’ | [0,()]/ uel dur? | Rate / molds? L 100x 10% 3.00 10° 0.660 x10 2 100 10* 6.00x 10° 132x10+ 3 300x104 9.0010" 594x107 4 450x10* 720x104 (@ Give the rate equation for the seaction between NO(g) and O,(g). showing your reasoning, 2] (Gi) Calculate the value of the rate constant, k, stating its units re ii) Calculate the rate of the reaction for Experiment 4. ly HL SECTION A.99wO3 (f) Explain why iron ix used in the Haber process to manufacture ammonia and why is it added in finely jed form rathcr than in large pieces. 12] HL SECTION A995 Page 22 of 75 PB4. The following data were obtained for the reaction between A and B: A(aq) + 2B(aq) + 3C(aq) + Dag) Thitial concentration Initial Rate Experiment | of Reactants (moldm™)| of Reaction A B (mol dm br} L 0.200 0.200 0.50 2 0.400 0.200 2.00 a 0.400 0.800 8.00 (@) Give the order with respect to A. (b) Give the order with respect to B. {©) Write the rate expression for this reaction. HL SECTION A .99s Page 23 of 75 PB my al up ay8. Evidence suggests that reaction between the gases nitrogen dioxide and fluorine is a two-step process: 2NO, (g) + Fig) > 2NO; Fie) Step 1 NO, +E, 9 NO,F+F Glow) Step 2 F+NO, > NO,F (fast) (2) State and explain which step 1s the rate determining step. mw (©) State and explain which of the two steps is expected to have the higher activation energy. 21 (© Give the rate expression of the reaction based on your answer to (a). mW HLB 135, Page 24 of 75 PB(©) Thetime taken to produce certain amount of product using different initial eoneentrations of CH,Br and NaOH is measured. The results are shown in the following table Reaction | [C,H,Br] /107 moldm™ | [NaOH] /10°moldm™ [7/s A 1.0 20 46 B 2.0 23 é 2.0 40 23 (i) Deduce the order of reaction with respect to C,H,Br and NaOH, using the data above By CAB: NaOH: (i) Deduce the rate expression i )) Based on the rate expression obtained in (e) (i) state the units of the rate constant, k ft) HLB 12w Page 25 of 75, PB6. — Chemical kinetics involves an understanding of how the molecular world changes with time. (a) (®) Define the term rate of reaction. ay )) Temperature and the addition of a catalyst are two factors that can affect the rate of a reaction, State two other factors PJ (ii) In the reaction represented below. state one method that can be used to measure the rate of the reaction. C10, (aq) + SCT" (aq) + 6H" (aq) + 3Cl,(aq) + 3,0 () on Page 26 of 75, PB(6) A catalyst provides an altemative pathway for a reaction, lowering the activation energy. @ Define the term activation energy. E, Ly () Sketch the two Maxwell-Boltzmana energy distribution curves for a fixed amount of gas at two different temperatures, Z, and T; (T, > T,). Label both axes BI Page 27 of 75, PB(c) Sketch graphical representations of the following reactions, for X > products. @ Concentration of reactant X against time for a zero-order reaction. 7] [x] t (ii) Rate of reaction against concentration of reactant X fora zero-order reaction. [I] Rate [x] (iii) Rate of reaction against concentration of reactant X for a first-order reaction. iy Rate I Page 28 of 75 PB(@) For the reaction below. consider the following experimental data. 2C10, (aq) + 20H (aq) C10, (aq) + C10, (aq) + H,0(1) ae ee 1 1.00x107 1.00107 230x107 2 5.00% 107 100x107 5.75x107 3 $.00%107 3.00107 173x107 @_ Deduce the rate expression. PJ] Gi) Determine the rate constant, k and state its units, using the data from Experiment 2. 2] [OH-@aq)]= (ii) Calculate the rate, in moldm™ s*, when [ClO,(aq)]=1.50x107moldm™ and 35x107moldar* al Page 29 of 75, PB(e) (ii) Describe qualitatively the relationship between the rate constant, & and temperature, T. iy Page 30 of 75 PB(iii) The rate of this reaction was measured at different temperatures and the following data were recorded. Ink 3.00 3.10 3.20 3.30 3.40 Using data fiom the graph, determine the activation energy, E,, correct to three significant figures and state its units. 4 Page 31 of 75 PB(6 Atwo-step mechanism has been propased for the following reaction. Step 1: C1O™(aq) + C10“ (aq) > C10," (aq) + CI" (ag) Step 2: C1Oz (aq) + C1O-(aq) + C1, (aq) + CY (aa) (@ — Deduce the overall equation for the reaetion, ay (ii) Deduce the rate expression for each step, Pi Step 1: Step 2: HUB 1tw Page 32 of 75, PB& (a) Define the tenn activation energy. E,. iW (b) Nitrogen monoxide, NO, is involved in the decomposition of ozone according to the following mechansm. 0; 90) +0+ 0; +NO+ NO; +0, NO; + 0+ NO +0; Overall: 20, +30, State and explain whether or not NO is acting os a catalyst. PI (©) @ Define the term endotitermic reaction. w Page 33 of 75 PBGi) Sketch the Maxwell-Boltzmann energy distribution curve for a reaction with and without 2 catalyst, and label both axes, 3) (@) Nitrogen reacts with hydrogen to form ammonia in the Haber process, according to the following equilibrium. Ny(g)+3Hy(g) = 2NH(@) AH? =-92.61 @ Define the term rate of reaction. iy HLB 11w Page 34 of 75, PB(@) _BE,(g) resets with NH, (g) to form F,BNH, (g) according to the equation below. BE, (g) + NH, (2) > FBNH, (g) (Identify the type of bond present between BF, and NH, in F,BNH,(g) and state another example of a compound with this type of bondi P] (a) The table below shows initial rates of reaction for different concentrations of each reactant for this resetion at temperature, T. Experiment | [BF,(g)] /moldm™ [NH, (g)] / moldm™ vate { moldm*s* 1 1.00 = 107 6.67 x 10 2.27 x 107 2 1.00 x 107 3.75 x 107 1.28 107 3 2.50 x 107 2.50 x 107 2.13 x 107 4 3.00 « 107 1.00 « 10" 1.02 « 10" Deduce the rate expression, the overall order of the reaction and determine the value of k, the rate constant. with its units, using the data from Experiment 4. B] Page 35 of 75 PB(© The following is a proposed mechanism for the reaction of NO (g) with H,(g) Step 1 2NO(g) > N,0,(g) Step 2. N,0,(g) + H,(g) > N,O(g)+H,0(g) (i) Identify the intermediate in the reaction. py (ii) The observed sate expression is sate = K[NOF[H,]. Assuming that the proposed mechanism is correct, comment on the relative speeds of the two steps. fll (g) The following two-step mechanism has been suggested for the recction of NO,(e) with CO(g), where Step 1: NO,(g)+NO,(g)—L + NOL) + NO,(e) Step2: NO, (g)+CO@)—B>NO,(g)+C0,(@) Overall: NO5(g) + CO(2)—» NO(2) + CO, (2) The experimental rate expression is rate=k,[NO,]. Explain why this mechanism produces a rate expression consistent with the experimentally observed one. 2 Page 36 of 75, PB(bh) HI(g) decomposes into H, (g) and I, (g) according to the reaction below: 2HI(g) > H,(g) +1,(2) The reaction was carried ont at different temperatures and a value of the rate constant. k. was obtained for each temperature, A graph of In k against : is shown below. Calculate the activation energy. £,. for the reaction using these data and Table 1 of the Data Booklet showing your working (4 HLB09w Page 37 of 75, PB6. (@)_ Consider the following reaction studied at 263 K. 2NO(g) + Cl,() = 2NOCI(g) Tt was found that the forward reaction is first order with respect to Cl, and second order ‘with respect to NO. The reverse reaction is second order with respect to NOC. @ State the rate expression for the forward reaction, ay (ii) Predict the effect on the rate of the forward reaction and on the rate constant if the concentration of NO is halved. 21 Gi) 1.0 wel of Cl, aud 1.0 mol of NO we iiacd in a closed coutaiuer at constant temperature. Sketch a graph to show how the concentration of NO and NOCI change with time until after equilibrium has been reached. Identify the point on the graph where equilibrium is established. 4 (>) Consider the following reaction. NO,(g) + CO(g) > NO) + CO,(e) Possible reaction mechanisms are: Above 715K: NO, +CO->NO+C0, slow Below 773K: 2NO, > NO+NO; stow NO, +CO- NO, +CO, fast Based on the mechanisms. deduce the rate expressions above and below 775 K. ey (©) State two situations whea the rate of a chemical reaction is equal to the rate constant [2] Page 38 of 75, PB@ Consider the fllowing graph of Ink against forthe fst order decomposition ofN,O, into NO,. Determine the activation energy in kJ mo!” for this reaction. BI 98 96 oa 92 0 Ink 8s 86 84 82 HL B 08s Page 39 of 75 PB(b) HLBO7w Page 40 of 75, The oxidation of nitrogen monoxide takes place as follows: 2NO (g) + 0, (g)—> 2NO,(g) The following experimental data was obtained at a constant temperature. Experiment | Initial [NO] / mol dav? | Initial [O,]/ mol dmv? | Initial cate / mol dav?s* 1 350x107 175x107 3.75x10% z 3.50x107 3.50x107 750x107 a 7.00x10* 7.00x10* 6.00107 (@ _ Deduce the order of reaction with respect to O, and with respect to NO. 2 (ii) _ State the sate expression for the reaction. 1 (iii) Caloulate the value of the rate constant and state the nits, 2} (iv) Calculate the expected rate of reaction if the reactants from experiment 2 were placed in a container of twice the original volume. Explain your answer. 22] (x) Suggest a possible two step mechanism that is consistent with the rate expression. Identify the rate-determining step. [3] The seaction in (2) is faster at 323K than at 298K. Explain the increase in sate in terms of collision theory and Maxwell-Boltzmann energy distribution curv: 0) PB