18 2-todobutane can be readily converted into 2-aminobutane using ethanolic ammonia. " CHACHICH:CHs + 2NHs ++ CHCH(NH)CH,CHs + NH&E |i order to determine the rate equation for this reaction, an investigation was carried out at a Constant temperature. Equal volume of 0.20 mol dm“? 2-iodobutane and 4.00 mol dm? ethanolic ammonia were mixed. At sultable time intervals, 10 cm? of the reaction mixture was pipetted into a conical flask and quenched. Chlorine gas was bubbled into the aliquot and excess chlorine gas was subsequently removed. lodine Is liberated by the following reaction, Ch + 2r > 2Cr +1 The iodine was then titrated with 0.020 mol dm”? sodium thiosulfate in the presence of an indicator. 1+ 28,07 + 2r + S02 Fig. 5.1 shows the volume of sodium thiosulfate used a 40 35 30 25 20 Volume of S,0;?'/ cm 15 10 time/s Fig. 5.4 ‘ASRJC JC2 PRELIMS 2021 sTasmoamiaom tte mest 09 mirewerite main bend oe © Cranston nha anos on m (i) eee, we Fg. 51 acetic ed evenion wn apc dean, () Manta deondnonauihetndsneiee opener supe rca a ch pb wl charg ea snap ke he one ns Mans. es "0 (tore, ces beret er barasonbetveen ohne nd are ” guyana ance emer eat se tacos2a () odide ions, 1", can react with peroxodisulfate, S:0.". S:0 + 21 > 280.7 + A student wanted to investigate the effect of changes in volume used on the rate of this reaction. Table 5.2 shows the results obtained when a series of experiments was carried out using different volumes of the two reagents, each solution being made up to the same total volume with water, where necessary. Table 5.2 volume of KI | volume of NazS:0s | volume of water | initial rate / experiment | fom? Tem? Jom? mol dri? s~* 1 10 20 10 0.0200 2 5 20 15 0.0100 3 30 10 0 0.0303 Given that the order of reaction with respect to I” is 1, determine the order of reaction with respect to S:Ox*. order = m {Total: 11] ASRUC JC2 PRELIMS 2021 srzamoam2 [Turn over4° (a) © DHS 2021 won GS TS 1" Sodium boron tydtde, NaBH, is commonly used in the pharmaceutical indushie® sectactve rodusing apen. Aqueous NaBH fs used fo reduce bulana fo butan-1-2l ‘The reaction kinetics betweon butanal using excoss of NaBH is studied. The wee ceection ‘of butanal was. determined at regular intervals as the reaction progressed. ‘Two separate experiments wore carta out using ila (butanal] = 0.100 mol dv wae “giterent. NaBHs ‘concentrations. Tho results of Experiment 1 using [NaBH.] = 1.0 mol dm? are shown in Fig 4.1. 0.100 0.090 0.080 0.070 0.060 0,050 0.040 0.030 0.020 0.010 0.000 [butanal] / mol dir? 0 20 40 60 80 100 Time! min Fig 44 @ Using Fig 4.1, show that the reaction is first order with respect to (butanal]. 10} (i, Experiment 2 was carried out using [NaBH] = 1.5 mol dam, It was found that the reaction is first order with respect to [NaBH.). initial [butanal] | initial [NaBH] | Experiment | j mol dm? 1 mol dev? 1 0.100 40 | 2 0.100 1s | Plot on the same axes given in Fig 41, the graph you would expect 0 oPi2t? or Evperiment 2, showing the time taken for [outanal to decrease (0 125% ofits initial concentration. 2 9720102 {Turn over12 (wy Using Fig. 41, determine the Initia rate of Experiment 1. a Experiment 3 vos carried out using 0.060 mol dm? putanal and 1.0 mol der? NaBH. Predict and explain how ‘the halflife of butanal in Experiment 3 ‘« the inital rate of Experiment 3 ‘would compare with Experiment 1. used in the reduction of aldehydes to ism to reduce butanal to butan-t-ol. (v)_ NaBH. produces hydride fons, aleohols. The following shows the me 4.2. Show relevant partial charges and draw ‘ent of electron pairs in both steps. ‘Complete the mechanism in Fig. ‘curly arrows to show the moveme : 7 i { . s“™ ow Step 1: CHyCH,e H + —— chcH.cH, ul [ r Step 2: + 0. + otha He Sa Zé OH” oHycH, oxo Wi Fig. 4.2 1 _ © DHS 20216 ©] Nox can be formed from NO, as shown in equation 1. equation 1 2NO(g) + Ox{g) -> 2NO2(a) ‘Three experiments were carried out to determine order of reaction with respect to NO and O2, and hence the rate constant for this reaction. Experiment 1 was carried out with initial concentrations of NO and Oz at 0.10 mol dm and 0.0050 mol dm’* respectively. Fig. 2.2 shows the concentration of O2 recorded against time for this experiment. [02] / mol dm? 0.006 0.005 0.004 0.003 0.002 0 5 10 15 20 25 30 time /min Fig. 2.2 ‘The experiment was repeated to find the initial rate of reaction at different initial concentrations of NO and O2. The results of these experiments are shown in Table 2.2. Table 2.2 Experiment | Initial (NOJ/ | Initial [02] / | Initial rate of formation of mol dm? | _mol dm NOz/ mol dav?s* 0.001 0.002 5.55 x 10°? 0.002 0.003 3.33x 10% . (Define the terms order of reaction and rate constant. [2] #2 Chemistry 9729/02 NYJC J2/2021 PRELIM.7 (i) Explain why NO Is used in large excess in experiment 1- ction with respect to each of the the data given, determine the order of rea ting its units. (iu) Using id hence, calculate the rate constant, reactants ant 3) (iv) Determine the intial rate of depletion of Os when [NO] = 0.002 mal dmv and [02] = 0.002 mol driv. ie) 790m? NYC 422021 PRELIM. {Tum Over(aj) The removal of NO: is important because of is significant environmental Impact. The ae orto this problem is to enforce the installation of catalylic converter onto the th the aid of a Maxwell Boltzmann distribution curve, exhaust pipes of vehicles. Wit eXpiain how catalytic converters help to reduce the release of NOP inio the environment.@o qi) Based on the results obtained, show that the reaction is first order with respect to the ester and first order with respect to H’ ions. eee eee _ State the units of the rate constant, k. (4) (1){c) )With the ald of a sketch of the Boltzmann distribution, explain how an increase in perature changes the rate of ester hydrolysis. 1B temy (Total: 9 marks}(D0 NOT WRITE THIS MARGIN 2: Do NOT WATE IN THis MARGIN SECTION'A ‘Answer all the questions in this section, ‘The Contact Process is an industrial process for manufacturing sulfuric acid. The key stage in this process is the reaction between Sulfur dioxide and oxygen. 2804q) + O.(9) = 250.(9) SH = 197 kJ mot? Vanadium(V) oxide, V2Os, is used as a:tiéterogeneous catalyst for this process. With the aid of an energy profile diagram; explain using collision theory why the addition of the catalyst speeds up the reaction. BI 9728 / TJC PRELIM / 2021 100 NOT WAITE IN THIS MARGIN = rowyw SIL m1 34N¥M LON 3Section A ‘Answer all the questions from this section. -The rate of reaction between an unknown bromoalkane, RBr, and aqueous sodium hydroxide, NaOH, undergoing hydrolysis to form an alcohol can be investigated experimentally using phenolphthalein as an indicator. ‘Afew drops of phenolphihalein were added to @ ‘sample of hot aqueous sodium hydroxide. An excess of bromoalkane was added to the mixture, shaken, and the relative rate was measured when the end of the reaction was observed. . The experiment was then repeated with various initial concentrations of the bromoalkane and aqueous sodium hydroxide. All experiments were carried out at the same temperature. (2) Explain what you understand by the term ‘rate of reaction’. i (il) Describe how the end of the ‘experiment would be determined. ia) Table 1.1 below shows the results for the series of hydrolysis experiments. Table 1.1 experiment [RB] / mol dm= [NaOH]/ mol dm | _ relative rate 1 0.120 0.0400 0.0238 2 0.040 0.0400 0.00794 3 0.048; 10,0800 0.00952 4 0.180 0.0200 x ©) 0 Dedvce the order of reaction for both RBr and NaOH. ra) (ii) Hence write the overall rate equation for the reaction. 1) (iii) Predict the relative rate, x, for the reaction in experiment 4. i (iv) It was determined that 20% of the RBr in experiment 1 was reacted in 46's. Predict the time taken for the same percentage of RBr to be reacted i) ‘experiment 3, giving your reasoning. a 2024 JC2 Prolim H2 Chemistry2(@))0 w n aqueous solution of permanganate( Vil) ions, MnO«", ‘The reaction between ai ‘can be represented by the following equation: ‘and ethanedioate ions, C20.", 5C20,?{aq) + 2MnO«{aq) + 16H*(aq) + 10COAg) + 2Mn**(aq) + 8H20(/) ‘The presence of Nn’, which are produced in the reaction between MnO and C0, is thought to catalyse this reaction. ‘An experiment was performed to measure the volume of COz gas produced at regular time intervals until the reaction goes to completion. ‘The graph of volume of CO2 gas produced against time has three distinct regions. ‘Sketch on Figure 2.1, the graph of volume of CO2 gas produced against time you would expect to obtain. volume of COz time Figure 2.1 10} Explain why there are three distinct regions of the graph you have drawn in (ai). 3)(iii) _ Using your answer in (a)(ii), sketch on Figure 2.2, the graph of rate against time ‘you would expect to obtain for the same reaction in (ai). rate time Figure 2.2 (1) (iv) The reaction mechanism for the second region of the graph you have drawn in ™ (wi) © We 2021 (a)() can be described as follows. step 1: MnO. reacts with Mn**, producing Mn as one of the products. step 2: C,0.?-is then oxidised to form CO; gas as one of the products. Using the information given above, write down the balanced equations for both steps of the mechanism. You may find the half-equation given below useful. 2002 +2e" = C20 = =-0.49V (2) Use of the Data Booklet is relevant to this question. Calculate E*.# for each step you have written in (a)(iv). Explain how your calculated values support or contradict the proposed mechanism in (a)(iv). 13) State the step in (a)(iv) you would expect to be the rate determining step. Explain your answer. ] 9729/0/PRELM21 [Tum over