《化学反应工程》第十一章习题

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1、1.乙块与氯化氢在HgC—活性炭催化剂上合成氯乙烯的反应:C2H2+HC/<>C2//3C/(A)(B)(C)其动力学方程可有如下形式：⑴r=UPaPb一Pc/K)/(l+KaPa+KBpB+Kcpc)2(2)r=kKAKBpApB/(I+KbPb+KcPc)(l+KApA)(3)r=kKApApB/(I+KApA+KbPb)(4)r=kKBpApB/(I+KBpB+Kcpc)试说明各式所代表的反应机理和控制步骤。2.P10-4at-Butylalcohol(TBA)isanimportantoctaneenhancerthatisusedt

2、oreplaceleadadditivesingasoline[Ind.Eng.Chem.Res.,27,2224(1988)].t-Butylalcoholwasproducedbytheliquid-phasehydration(W)ofisobutene(I)overanAmberlyst-15catalyst.Thesystemisnormallyamultiphasemixtureofhydrocarbon,water,andsolidcatalysts.However,theuseofcosolventsorexcessTBAca

3、nachievereasonablemiscibility.ThereactionmechanismisbelievedtobeI+Se-—»ISW+SW・SW・S+I・S~~TBA・S+STBA-S»Derivearatelawassuming:(a)Thesurfacereactionisrale・limiting.(b)Theadsorptionofisobuteneislimiting・(c)ThereactionfollowsElcy-RidealkineticsTBA+S(P1041)(Pl0-4.2)(Pl0-4.3)(Pl0-

4、4.4)(d)IS+W(P1045)andthatthesurfacereactionislim让ing.Isobutene(I)andwater(W)areadsorbedondifferentsitesw+s、W・s,(PI0-4(P10-4TBAisnoton(hesurface,andthesurfacereactionisrate-limiting«(I♦人w)(I+)3.P10-8bIn1981theU.S.governmentputforththefollowingplanforautomobilemanufacturersto

5、reduceemissionsfromautomobilesoverthenextfewyearsYear198119932004Hydrocarbons0.410.250.125co3.43.41.7NO1.00.40.2Allvaluesareingramspermile.Anautomobileemitting3.74lbofCOand037lbofNOonajourneyof1000mileswouldmeetlhecurrentgovcmmenirequirements.Toremoveoxidesofnitrogen(assume

6、dtobeNO)fromautomobileexhaust,aschemehasbeenproposedthatusesunbumedcarbonmonoxide(CO)inIheexhausttoreducetheNOoverasolidcatalyst.accordingtothereactionCO+NO►Products(N2.CO2)Experimentaldataforaparticularsolidcatalystindicatethatthereactionratecanbewellrepresentedoveralarge

7、rangeoftemperaturesby%PcwhereP”=gas-phasepartialpressureofNOPc=gas-phasepartialpressureofCOk.K2=coefficientsdependingonlyontemperature(8)Basedonyourexperiencewithothersuchsystems,youareaskedtoproposeanadsorption-surfacercaction-desorpiionmechanismthatwillexplaintheexperimen

8、tallyobsersedkinetics.P10-14aTitaniumdioxideisawide-bandgapsemiconductorthatisshow