化学动力学第二章习题集和答案解析

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1、化学反应动力学第二章习题1、Thefirst-ordergasreactionSO2Cl2®SO2+Cl2hask=2.20´10-5s-1at593K,(1)WhatpercentofasampleofSO2Cl2wouldbedecomposedbyheatingat593Kfor1hour?(2)HowlongwillittakeforhalftheSO2Cl2todecompose?解：一级反应动力学方程为：(1)反应达1小时时：=0.924=92.4%已分解的百分数为：100%-92.4%=7.6%(2)当时，s=31500s=8.75hour

2、2、T-butylbromideisconvertedintot-butylalcoholinasolventcontaining90percentacetoneand10percentwater.Thereactionisgivenby(CH3)3CBr+H2O®(CH3)3COH+HBrThefollowingtablegivesthedatafortheconcentrationoft-utylbromideversustime:T(min)091824405472105(CH3)CBr(mol/L)0.10560.09610.08560.0767

3、0.06450.05360.04320.0270(1)Whatistheorderofthereaction?(2)Whatistherateconstantofthereaction?(3)Whatisthehalf-lifeofthereaction?解：(1)设反应级数为n，则若n=1，则t=9，t=18t=24，t=40t=54，t=72，t=105若n=2，则t：918244054k：0.10400.12290.14870.15090.1701若n=1.5t：91824k：0.01650.01890.0222若n=3t：91824k：2.067

4、2.603.46反应为一级。(2)k=0.0123min-1=2.05×10-4s-1(3)=56.3min=3378s3、已知复杂反应：的速率方程为，推导其动力学方程。要求写出详细的推导过程。解：设时，，，时，，，代入得：令α=，β=，γ=则，移项积分：令，得动力学方程：4、已知复杂反应由下列两个基元反应组成：求反应进行过程中，A1物种浓度与A3物种浓度间的关系。要求写出详细的推导过程。解：速率方程：（1）（2），得：设时，，，移项积分：考虑物料平衡：，代入上式，得[A1]~[A3]关系式为：即：若时，，，则：5、Considerthereaction

5、mechanismi.Writechemicalrateequationsfor[A]and[X].ii.Employingthesteady-stateapproximation,showthataneffectiverateequationfor[A]isd[A]/dt=-keff[A][B]iii.Giveanexpressionforkeffintermsofk1,k-1,k2,and[B].解：ⅰ.ⅱ.对X进行稳态近似，则即：即：ⅲ.6、(a)Thereaction2NO+O2®2NO2isthirdorder.Assumingthatasma

6、llamountofNO3existsinrapidreversibleequilibriumwithNOandO2andthattherate-determiningstepistheslowbimolecularreactionNO3+NO®2NO2,derivetherateequationforthisthemechanism.(b)Anotherpossiblemechanismforthereaction2NO+O2®2NO2is(1)NO+NO®N2O2k1(2)N2O2®2NOk2(3)N2O2+O2®2NO2k3Applythestea

7、dystateapproximationto[N2O2]toobtaintheratelawford[NO2]/dt.IfonlyaverysmallfractionoftheN2O2formedin(1)gosetoformproductsinreaction(3),whilemostoftheN2O2revertstoNOinreaction(2),andiftheactivationenergiesareE1=79.5kJ/mol,E2=205kJ/mol,andE3=84kJ/mol,whatistheoverallactivationenerg

8、y?(c)Howwouldyoudistinguishexperimentall