第九章 化学动力学基本原理

1、积分法微分法半衰期法对峙反应连续反应一级反应 molnnniiiiidef/0, iidefdndor dtdndtdJiidef 1dtdnhdtdngdtdnbdtdnaJHGBA1111 VdtdnVdtdVJrii 1dtiddtdciii11 dtNOBrddtBrddtNOdr21212 ctRTpVnciii dtdpRTdtdcr酯酯1dtdpRTdtdcr光光2121dtdpRT总1dtdpRT总1dtdccfriii 1)( 22IHkr /122/122BrHBrkBrHkr 2/122ClHkr /122/122BrHBrkBrHkr dtAddtBddtCddtDdn

2、ndmmolBAsdmmolrsdmmolk)/(/)/(313113 ckdtdcr1dtkcdc1tkcc10lntkecc10cctk01lncckt01ln1 xaa ln12lnk 2/ln10012/1cckt x11lnRTpVnc ckdtdcc pkdtdpp RTpkdtdpRTc 1pckk cctk0ln1 VVVt ln1tVVVln 以以22ckdtdcr dtkcdc 22Btkc 21tkcc2011 tccdtkcdc0220)(111102xaaxaxacctk akckcckt2020022/11112/11 2ckdtdcc 2pRTkdtdpc 22)

3、(1RTpkdtdpRTc RTkkcp 2pkdtdpp 2pkp 1)( ncpRTkk00121ppp 总总2pkdtdpp tkppp 011 2kcdtdcr dtdxdtdcdtdcrBA )(xbxak )(xbxakdtdx )(1102xaaxcctk kdtxbxadx )()(1)()()()(1abxbxaxaxbxbxa txkdtdxxbxaab00111ktxbaxabba )()(ln1 xbxaab11)(1txbaxab)()(lntxbaxabba)()(ln1txbxalnktxbaxabba)()(ln1200 400 600 800 t/s-1.0-

4、1.3-1.2-1.1ktxbaxabba )()(ln1)2/(2/ln)(12abaabbakt 0kdtdc /mol.dm-3.s-1 tccdtkdc000txtcck 00002/12kct 3CBAkdtdx 23BAkdtdx 33Akdtdx 33)(xakdtdx tkaxa32221)(1 txdtkxadx0303)( 20222311211)(121cctaxatk232/123akt cctk01ln102111cctk)(100cctk20231121cctkpptk0ln10143. 065.8025.84ln05. 31k010. 027.4225.84ln0

5、5.681k0129. 045.6125.84ln55.241k41074. 125.84165.80105. 31pk0111pptkp41073. 125.84127.42105.681pk002kc12lnk021ck20323ckln)1(ln002/12/1ccntt ) /ln() /ln(1002/12/1ccttn 3999.2)10.1/5 .0ln()885/4280ln(1 n30008.3)48.2/10.1ln()174/885ln(1 n202/123ctk 12232/1040. 1)10. 1(88523 sLmolk12232/1040. 1)50. 0(42

6、8023 sLmolk12232/1040. 1)48. 2(17423 sLmolknkcdtdcr21212121lnlnlnln)/ln()/ln(ccrrccrrncnkrlnlnlnctctBAkr 若若 ab )()()(22xbkxbakxbxakdtdxtkatkxbb2ln AkkBkr299. 1)041. 0/064. 0ln()0 .14/00. 9ln(1 n00. 2)041. 0/025. 0ln()0 .14/00.23ln(1 n08. 112. 2)/ln()/ln(2121 ccrrn297. 1 Tdkd1lndTkdRTEadefln2 REa lnk

7、1/T2lnRTEadTkdBRTEaklnRTEaAek/k+keeeeCBADCKkk2lnRTHdTKdmr22lnRTRTHTRTHdTKdmrmrC 2lnRTUdTKdmrC dTKdplnTdTKdCln2lnRTEdTkd dTkddTkddTkkddTKdC lnln)/ln(ln22RTERTE 2RTUmr BRTEka ln 212111)()(lnTTRETkTka450. 8650/ln)650(ln REAKka615. 6/ln)(ln RTEATkadtdcZqr 双分子的互碰频率和速率常数的推导 两个分子在相互的作用力下，先是互相接近，接近到一定距离，分子间

8、的斥力随着距离的减小而很快增大，分子就改变原来的方向而相互远离，完成了一次碰撞过程。 粒子在质心系统中的碰撞轨线可用示意图表示为：两个分子的一次碰撞过程obvv有效碰撞直径和碰撞截面 运动着的A分子和B分子，两者质心的投影落在直径为 的圆截面之内，都有可能发生碰撞。ABd 称为有效碰撞直径，数值上等于A分子和B分子的半径之和。ABdABABd分子间的碰撞和有效直径 虚线圆的面积称为碰撞截面(collision cross section),数值上等于 。2ABdVNVNmmmmkTddzBABABABAAB2/1282 0BAABccz VNVNurrzBAABBAAB2 VNVNMMMMRT

9、dBABABAAB2/128 2/18 kTuAB22/122 VNMRTdzAAAAA22/122cMRTdAA 解：解：32523.1005. 1700314. 81013251002. 6 mmolecRTLpVN22/122 VNMRTdZHIHI1331.1002. 1 smkTQNkTiQNiiieegn/ 0/dedeeeNnqkTkTkTkTiiciiciici)(/cCRTEkTLEeeCc RTECZeZqr/ RTEBABACeCCZCCrk/ 113/0./ molecsmeZRTEcAB131./ sdmmolCCrkBA2/12/120118TZMMRTdZBAABAB RTERTECCeTZeZk/2/1/0 RTETZkC/lnlnln21 dTkdRTEaln2 2221RTETRTCRTEECa21 RTEcePZk/0 O2NO2NBrOH +Br-+OH-A+BC RTGccccccccccKBCABCAexp)/)(/(/RTHRSee/ KcccckBCA1)(BCAckccr RTHRSBeehcTk KchTkB1)(21lnRTUTdTkd Kck1)(RTnHU)1 ( 2)1 (1lnRTRTnHTdTkd22HnRTEaRTRTEaHnRT