ࡱ> UWNOPQRST#` bjbjmm 43*R>R>R>R>n?,*5X.@L@@@@AAAWWWWWWW$cYh[RW9AAAAAW@@WJJJA>@@WJAWJJzMM@@ zL/R> G&MDOLX05XM\1I~\MM&\M|AAJAAAAAWWJ AAA5XAAAA***$'N,***N,*** How fast? Rates 4.3a Definition of terms (a) demonstrate an understanding of the terms rate of reaction, rate equation, order of reaction, rate constant, half-life, rate-determining step, activation energy, heterogeneous and homogenous catalyst rate of reaction This is the change of a quantity during a reaction with respect to time. E.g. rate = change of concentration/time units: moldm-3 s-1 For a reaction between A and B : A + B ------> Products If the rate of reaction depends upon the conc. of A and B. The relationship is: Reaction Rate proportional to [A]m[B]n Reaction Rate = k[A]m[B]n This known as a rate equation and k is the rate constant. The indices m and n are usually integers, often 0, 1 or 2, and are characteristic of the reaction. The rate constant and order of reaction are experimentally determined. Task 4.3a For the following reactions and rate equations state the order with respect to each reactant and the overall order. 2I-(aq) + S2O82-(aq) ---> I2(aq) + 2SO42-(aq) 2 mol iodide ions +1 mol of peroxodisulphate(VI) ions forms 1 mol iodine molecules + 2 mols sulfate ions Rate = k[I-][S2O82-] 2H2O2(aq) --> 2H2O + O2(g) Rate =k[H2O2] BrO3-(aq) + 5Br-(aq) + 6H+(aq) --> 3Br2(aq) +3H2O(l) Rate = k[BrO3-][Br-][H+]2 half-life, This is the time for half of a reactant in a reaction to disappear or for half of the theoretical maximum amount of a product to appear. rate-determining step This is the slow step in a reaction mechanism which determines the reaction rate. activation energy, The minimum amount of energy which colliding molecules must have before they can react together. This energy is measured in kJmol-1. homogenous catalyst These substances speed up chemical reactions and are present in the same phase as the reactants and products. E.g. conc sulphuric acid catalyses CH3CO2CH3+ H2O INCLUDEPICTURE "http://upload.wikimedia.org/math/e/9/d/e9d7d321f1402682958d3a88a1d13775.png" \* MERGEFORMATINET CH3CO2H + CH3OH the ester, water and acid are all in the liquid phase `heterogeneous catalyst These substances speed up chemical reactions and are present in a different phase from the reactants. E.g. solid manganese (IV) oxide catalyses the decomposition of liquid hydrogen peroxide. 4.3b Selecting suitable techniques for rate experiments (b) select and describe a suitable experimental technique to obtain rate data for a given reaction, eg colorimetry, mass change and volume of gas evolved Reactions can be followed by * sampling, quenching and titrating (suitable for acid base reactions) * measuring gas volumes (suitable for reactions involving a change in gas volume) * measuring mass changes * polarimetry (suitable for reactions involving optically active substances) * measuring conductivity (suitable for reactions producing or consuming ions) * colorimetry (suitable for reactions involving coloured substances) * dilatometry (suitable for reactions involving reactions in which liquids change volumes)  INCLUDEPICTURE "http://pic.srv104.wapedia.mobi/thumb/d1c914495/en/max/230/360/Dilatometer.jpg?format=jpg,png,gif" \* MERGEFORMATINET  4.3c Collecting data for concentration or volume against time graphs (c) investigate reactions which produce data that can be used to calculate the rate of the reaction, its half-life from concentration or volume against time graphs, eg a clock reaction Volume against time CaCO3(s) + 2HCl(aq) ( CaCl2(aq) + H2O(l)+CO2(g)  INCLUDEPICTURE "C:\\Documents and Settings\\David Bateman\\My Documents\\Dave\\My Webs\\school science uk web\\gcse2003\\gcsesums\\chemsums\\rates\\prac5.1.jpg" \* MERGEFORMATINET  concentration against time CH3CO2CH2CH3 + NaOH CH3COONa + C2H5OH 1. Start with a mixture of 0.1M concentrations of each reactant. 2. Remove 10cm3 samples every 5 minutes for 30 mins and place into separate 5cm3 samples of 0.1M HCl to quench the reaction. 3. Titrate each quenched sample with 0.1M NaOH. Clock reaction  INCLUDEPICTURE "C:\\Documents and Settings\\David Bateman\\My Documents\\Dave\\My Webs\\school science uk web\\gcse2003\\gcsesums\\chemsums\\rates\\pracC51.jpg" \* MERGEFORMATINET  Task 4.3c Draw results tables for the data available from the above experiments to investigate rate and surface area, concentration and temperature respectively. 4.3d Drawing and interpreting conc-time and rate-conc graphs Volumes of hydrogen are collected at different times for a reaction where different concentrations of HCl react with magnesium ribbon. Initial concentration = 0.1M 1.5cm3min-1 1.7, 2.0, 1.66, 2.0, 2.0, Time/min01234567Vol/cm30246781011Initial concentration = 0.25M 10.0, 10.0, 10.0, 10.0 8.5 cm3min-1 Time/min01234567Vol/cm3010172429344044intial concentration = 0.5M 20.0, cm3min-1 Time/min01234567Vol/cm3020344454626976Initial concentration = 1.0M Time/min01234567Vol/cm3040566877838993Initial concentration = 2.0M Time/min01234567Vol/cm308092969899100100Task 4.3d Plot volume against time for each concentration on the same graph. Calculate the gradient to find the rate and plot rate against initial concentration. Complete the rate equation by finding k and x in rate = k[HCl]x 4.3(e) The reaction of iodine with propanone investigate the reaction of iodine with propanone in acid to obtain data for the order with respect to the reactants and the hydrogen ion and make predictions about molecules/ions involved in the rate-determining step and possible mechanism (details of the actual mechanism can be discussed at a later stage in this topic) I2(aq) + CH3COCH3(aq) ( CH3COCH2I(aq) + H+(aq) + I-(aq) The rate equation for this is of the form: rate = k[CH3COCH3(aq)]p[I2(aq)]q[H+(aq)]r The rate is found by experiment with different starting concentrations of reactant. Experiment numberInitial conc. I2(aq) /moldm-3Initial conc. CH3COCH3(aq) /moldm-3Initial conc. H+(aq) /moldm-3Initial rate /moldm-3min-110.0040.40.42.0*10-420.0040.80.43.7*10-430.0041.20.46.3*10-440.0080.40.42.2*10-450.0020.40.41.8*10-460.0040.40.83.5*10-470.0040.41.26.0*10-4This data shows that the rate equation is: rate = k[CH3COCH3(aq)][H+(aq)] For example in exp 1,2 and 3 the conc. of propanone changes but the other reactant concentrations remain constant. In exp 1 and 2 if we double the conc. We double the rate or if we triple the conc. we triple the rate. This shows that the rate is directly proportional to the conc. of propanone and the index p =1. Task 4.3e which exp allow the indices q and r to be found and what is there value. Explain your reasoning. The rate determining (slow) step must therefore contain two chemical species. These are CH3COCH3(aq) and H+(aq). The mechanism will contain a step with these two species forming a new species. E.g. CH3COCH3 + H+ ( CH3COH+CH3 4.3(f)(i)Half life (f) deduce from experimental data for reactions with zero, first and second order kinetics: i half-life (the relationship between half-life and rate constant will be given if required) ii order of reaction iii rate equation iv rate-determining step related to reaction mechanisms v activation energy (by graphical methods only; the Arrhenius equation will be given if needed) The half life of a reaction can be determined from the graph showing the change of a quantity in a reaction against time. It is the time for the quantity the halve (or double. First order reaction For a first order reaction a simple formula can also be used. This is: t1/2 = 0.6932/k where t1/2 is the half life and k is the rate constant. Second order reactions These also have a mathematical expression for half life: t1/2 = 1/ka where t1/2 is half life, k is the rate constant and a is the concentration of both reactants at the start of the reaction. 4.3(f)(ii) Deducing order of reaction and (iii) rate equation experimentInitial conc. of NO /moldm-3Initial conc. of H2 /moldm-3Initial rate of formation of N2 / moldm-3s-116.0*10-31.0*10-32.88*10-326.0*10-32.0*10-35.77*10-336.0*10-33.0*10-38.62*10-341.0*10-36.0*10-30.48*10-352.0*10-36.0*10-31.92*10-363.0*10-36.0*10-34.30*10-32H2(g) + 2NO(g) ( 2H2O(g) + N(g) Rate = [H2(g)]x[NO(g)]y X=1 and y=2 so rate equation is: Rate = [H2(g)][NO(g)]2 The reaction is first order wrt hydrogen, second order wrt NO and third order overall. Task 4.3e(ii) State which experiments give the above results and explain how. Iodide and iodate(V) ions react as follows: IO3-(aq) + 5I-(aq) +6H+(aq) ( 3I2(aq) + 3H2O(l) The rate equation must be of the form rate = k[IO3-(aq)]x[I-(aq)]y[H+(aq)]z This reaction can be followed by colorimetry or by sampling, quenching (in NaHCO3) and titration (of I2 against thiosulfate). Data might be as follows: experimentInitial[IO3-(aq)] /moldm-3Initial[I-(aq)] /moldm-3Initial[H+(aq)] /moldm-3Initial rate /moldm-3s-110.100.100.101.2*10-320.200.100.102.4*10-330.100.200.102.4*10-340.100.100.204.8*10-3Task4.3e(iii) explain how the rate equation is rate = k[IO3-(aq)][I-(aq)][H+(aq)]2 4.3eiv rate-determining step related to reaction mechanisms From a rate equation you can decide on one step in the mechanism. This will be the slow, rate determining step and must contain all species in the rate equation. For Rate = [H2(g)][NO(g)]2 H2(g) + 2 NO(g) ( products is the rate determining step. Any sensible species can be chosen as possible products, only further experiment can show if they really are present in the reaction. E.g. H2(g) + 2 NO(g) ( 2NOH or H2O2 + N2 (g) This must match the overall equation 2H2(g) + 2NO(g) ( 2H2O(g) + N2 (g) Task 4.3eiv Suggest suitable rate determining steps for reactions given the following reactions and rate equations: A(g) + 3B(g) ( AB3(g) rate = k[A][B]2 H2O2 +2H+ + 2I- ( 2H2O + I2 rate = k[H2O2][I-][H+]0 2NOCl ( 2NO + Cl2 rate = k[NOCl]2 2ICl + H2 ( 2HCl +I2 rate = k[ICl][ H2] 4.3f(v) activation energy The Arrhenius equation is k = A10-E/2.3RT where k= rate constant, A = constant, E= activation energy, R = gas constant, T = temperature in Kelvin. This can be rewritten as log k = log A E/2.3RT A graph of log k against 1/T gives a straight line with a gradient = -E/2.3R and intercept = log A. Task 4.3f(v) Calculate the activation energy for the decomposition of HI given the data below: Temperature(T)/KRate constant(k)/dm3mol-1s-1663 666 697 715 7811.78*10-5 1.07*10-4 5.01*10-4 1.05*10-3 1.51*10-2 4.3(g) investigating the activation energy of a reaction Iodide and iodate(V) ions react as follows: IO3-(aq) + 5I-(aq) +6H+(aq) ( 3I2(aq) + 3H2O(l) The rate equation must be of the form rate = k[IO3-(aq)][I-(aq)][H+(aq)]2 Iodine can react with a fixed amount of thiosulfate after which it turns starch blue-black. This clock reaction allows the rate at different temperatures to be determined. Example data is shown below: Temp/oC3036394551Temp(T)/KTime(t)/s2041381157555Ln(1/t)1/T /K-1Task 4.3(g) Complete the table and plot ln(1/t) against 1/T. Assuming that 1/t represents the rate and is proportional to k at a particular temperature calculate activation energy (Eact) using slope = -Eact/R where R = 8.31JK-1mol-1 4.3(h) Rate equations and mechanisms Nucleophilic substitution reactions are common for halogenoalkanes. E.g. the hydrolysis reaction shown below. C(CH3)3I +NaOH ( C(CH3)3OH+NaI 2-methyl-2-iodopropane 2-methylpropan-2-ol The rate equation for this reaction is: rate = k[C(CH3)3I] It is first order wrt 2-methyl-2-iodopropane, a tertiary halogenoalkane. It is first order overall. It is unimolecular. It has an SN1 mechanism. The rate determining step must involve only this compound. E.g. C(CH3)3I ( C+(CH3)3 + I- slow A likely further step is: C+(CH3)3 + OH- ( C(CH3)3OH fast CH3CH2CH2Br +NaOH ( CH3CH2CH2OH + NaBr Bromopropane is a primary halogenoalkane. The rate equation for this reaction is rate =k[CH3CH2CH2Br][ OH-1] This is second order overall and has an SN2 mechanism. The rate determine g step must involve both species: CH3CH2CH2Br + OH-1 ( [ CH3CH2C(OH)H2Br ] -1 slow step [ CH3CH2C(OH)H2Br ] -1 ( CH3CH2CH2OH + Br- fast step Task 4.3h(i).1 Draw mechanisms above showing curly arrows. mechanism for the reaction between propanone and iodine I2(aq) + CH3COCH3(aq) ( CH3COCH2I(aq) + H+(aq) + I-(aq) rate = k[CH3COCH3(aq)][H+(aq)]  Task 4.3h(i).2 Explain how this mechanism matches the rate equation, the stochiometric equation and the fact the reaction is catalysed by hydrogen ion. 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