第二章化学反应动力学习题解答(2012-3-26)化09-1、2、31、补充题:本章子电子教案布置的习题的第5题:某气相反应在400K时的速率为hMPapdtdpAA/371.02。试问:(1)反应速率常的单位是什么?(2)若速率式写成hmkmolkcVdtdnrAAA./32,则此反应速率常数是多少?解:(1)单位:122//MPaMPahMPakhMPakpA(2)设气相符合理想气体规律,则:hmkmolcVdtdnhmmolcVdtdnhmmolcRTVdtdnhPaVRTnVdtdnRTdtVRTnddtdprVRTnpAAAAAAAAAAAAA./10234.1./10400314.8371.0./10371.0/10371.032632632662故速率常数131610234.1hmkmolk2、补充题:本章子电子教案布置的习题在间歇反应器中进行等温二级反应AB,反应速率为sLmolcrAA./01.02,当CA0分别为1,5,10mol/L时,求反应至CA=0.01mol/L所需反应时间。解:由题可知:速率常数1101.0Lsmolk不同初始浓度反应达到同一终了浓度所需反应时间:0111AAcckt分别将不同的初始浓度及终了浓度代入上式求解得:999010101.0101.0111199805101.0101.0111199001101.0101.01111030201AAAAAAccktccktcckt3、补充题:本章子电子教案布置的习题Acertainreactionhasarategivenby:132min..005.0cmmolcrAAiftheconcentrationistobeexpressedinmol/Literandtimeinhours,whatwouldbethevalueandunitoftherateconstant.解:11132132132300.300601.1.0.005.0min..005.0hLmolkhdmmolchdmmolccmmolcrAAAA4、陈甘棠第三版教材P29第4题解:12211224222229.4230273082.0/1065.2satmKmolKatmLsmolLRTkkppRTkdtdprRTpRTpkRTdtdprRTpCRTpCCCkdtdCrcpBAcAABAcAABBAABAcAA5、陈甘棠第三版教材P29第5题解:恒T、V下有:RTpnRTnVpkndtdnVnkdtdnVrAAAAAAAAA1AAkpdtdp由化学反应计量式可知:A3ppA3(pA0-pA)则总压:23300pppppppAAAAA,将此式代入上式得:23ppkdtdpAo5、陈甘棠第三版教材P29第6题解:反应式:2421042HHCHC(a)乙烯分压:1242104104424242104104..8.424.2scmkgfrrrrHCHCHCHCHCHCHCHC(b)氢的物质的量:smolskmolpnRTVrrRTVdtdpRTVdtdnscmkgfdtdpTHCHHCHCHC/3200/2.3344.24.24.24.2..4.2104210410412104(c)丁烷的摩尔分数:11041041041048.04.24.2spdtdydtdypdtdpydtdpHCHCHCHC6、陈甘棠第三版教材P29第7题解:设乙酸为关键组分A(1)经过120min后,乙酸的转化率:t=0时各物料的初始浓度:CA0=90.8/(60×0.3785)=4.0kmol/m3CB0=181.6/(46×0.3785)=10.43kmol/m3CR0=0kmol/m3CS0=[0.3785×1043-(90.8+181.6)]/(18×0.3785)=18.0kmol/m3设t=t时,A的转化率为xA,则各物料的浓度分别为:CA=CA0(1-xA)=4-4xACB=CB0-CA0xA)=10.43-4xACR=CR0+CA0xA=4xACS=CS0+CA0xA=18+4xA代入速率方程式得:AxAAAAAAAxxxxxxr0AAA02244)(-rdxCt)063.049.0248.0(108)418(41063.1)443.10)(1(41076.4)(AxAAAAxxxx02A291.007.007.0126.097.0126.0ln42.050)063.049.0248.0(dx1084tt=120min时,xA=0.35,即有35%的乙酸转化为乙酸乙酯。(2)如忽略逆反应,经过120min后,乙酸的转化率:AxAAAxxr0AAA04)(-rdxCt)443.10)(1(41076.4)(32.0x367.043.104x-10.43ln4111lnmin12043.104x-10.43ln4111ln1076.443.6143.104x-10.43ln4111ln1076.443.61)443.10()4x-d(10.4341)1()x-d(11076.443.61dx)443.10(4)1(143.611076.41)443.10)(1(4dx1076.44tAAA4A40A0A4A040A4AAAxAxAxAAxAAxxxxxxxxxAAAA(3)平衡转化率:平衡时正逆反应速率相等,即:545.041841063.1443.10441076.44421AAAAASPBAxxxxxcckcck