复合反应动力学

1、123baBAkrhgHGkrhegebeaeHGkBAkbeaehegecBAHGkkKaA+bBgG+hHk+k-4则则 eexaxkkaxkkkeexakkkork+k-AB5dtdxxkxakrrr)(xkkakdtdx)(即txdtxkkakdx00)(tkkxkkakak)()(ln tkkxxxee)(ln 6tkkeeexxx)(tkkxxxee)(lnexatkxxxatxkeeelnxxxatxakeeelntkkeeexxaxa)()(70ktaexaAetkkeexaexxaxaA)()(BAkaaeaxBktetkkeexexxxB)(k+k-AB82lnRTUdTK

2、dmrc r T 9k+k-AB10 xxxatxkeeelneexxakk)( 11tkkxxxee)(ln12)()(2211xakdtdzrxakdtdyr 13dtdzdtdydtdxr)()(21xakxaktkkxaa)(ln21积分tkkaexaA)(21)(21xakk14tkkaekxakdtdy)(1121)(dteakdyttkky0)(10211 )(21121tkkekkakyB1 )(21221tkkekkakzC15tkkaexaA)(2116RTEAkRTEAk222111lnlnlnln121217ROHOHRXRRXXROHOHRXkk1221OHRXkRX

3、kdtRXd21OHkkdtRXRXdln21OHkkdtRXdlnOHdtRXd以18RTEAk111lnlnRTEAk222lnln19RTEARTEA2211lnlnRTERTEAA2121lnlnRT8012010ln10ln111320CBAkk2122BkdtCdrr11AkdtAdrr21) 1 (1AkdtAd)2(21BkAkdtBd)3(2BkdtCdtkaexaA12212AkBkdtBd)(21121tktkeekkakBtkaek110112 tkaekBkdtBd)(211121tktktkeekkakaeaCtktkekkkekkkaC211211221230)(

4、2121121tktkekekkkakdtBdmax12)(12tkkekk) 3(ln1212maxkkkkt24RTEAk111lnln1212RTEAk222lnln25k+k-A(g)B(g)+C(g)26PakkKppp79,100 . 4100 . 520. 0211211)()(lnTTRETkTka395/)(pKpKKpvp272lnRTHdTKdmrdTKdpln,pppkkK2lnRTEdTkd22,lnlnlnRTERTEdTkddTkddTKdppp2820)(pkppkppkpkdtdpCBAppkkpk)(029ppkkpkdtdp)(0)(0ppkdtdpspp

5、pkt47. 310)510(100 . 1ln20. 01ln14500t dkppdp03031CBAkk21即：即： 021BkAkdtBdtkssaekkAkkB1212132)1 ()(121121tkktkeaekkkBtkaekkB121332CBkdtPdr02CBkCkAkdtCd2BkkAkC22BkkBAkkk2k+k-AC, B+CP34Akkc22BAkBAkkkBCkdtpdr)(222很小条件其中：kBkkkkkkk2k+k-AC, B+CP353Ekdtpdr3637dTkdRTEaln2222123RTURTURTE213UUEEadTKddTKddTkd21

6、3lnlnln38212211kkEkEkEa证：证：dTdkkdTkdRTEa1ln2dTkkdkk)()(1212139dTeAeAdkkRTERTERTEa)()(1/2/121221 22/21/12121)(1RTEeAEeAkkRTERTE 2221121)()(1RTEkEkkk 212211kkEkEkEa 40414243442/122ClHkdtHCld 21121ClkrClClClk 22222HClkrHHClHClk 23323ClHkrClHClClHk 244224 ClkrMClMClk4532rrdtHCld2322HClkClHk032rrdtHd32rr

7、 4143210rrrrrrdtCld462/ 122ClHk) 0(212121412412EEEEEEEa2/ 12412421ClkkClClkClk22222ClHkrdtHCld2/ 1222/ 14122ClHkkk41rr 2/ 14122kkkk474849WkRgkRRAk1RPARk20)(221RkkARkARkAkdtRdgWgWkkAkAkR)1(2150gWkkAkAkkARkdtPdr)1(22212gWkkAkkr2215152222ONOkdtNOd 53推测：推测：54 2 NO22232OONkdtNOd N2O2 ， H0 2NO2N2O2 + O2Kk

8、kNOON 21222:平平衡衡浓浓度度法法k1k2k3k55222NOKON 222232ONOkONOKkdtNOd 5657/ 122/122BrHBrkBrHkdtHBrdr58) 1 (432rrrdtHBrdrBrBrk212HHBrHBrk22BrHBrBrHk3224HBrHBrHkMBrMBrk252验证：验证：59)2(0432rrrdtHd)3(02254321rrrrrdtBrd)4(2/1251BrkkBr6042322HBrHkBrHkHBrk 22233BrHkrdtHBrdr 42322HBrkBrkHBrkH )/(4232/1222/1512HBrkBrkB

9、rHkkk 2/1251 BrkkBr61)/(24232/3222/15132HBrkBrkBrHkkkkdtHBrd/)/(1)/(22342/1222/1512BrHBrkkBrHkkk/ 122/122BrHBrkBrHk62TiHgTiHg232222322HgTiHgkrKk263222HgHgKHg2322232HgTiHgKkTiHgkr2322HgTiHgk646566676869707172730211xkxkCAkdtxd211kkCAkx21212CAkkkCAkkxkdtPdk2k1k-1A+CXP+C7432222SOOSO222ONNO 22222NOOON322

10、SONOSONO750AkAOHkAHkAkrba0OHkHkkkba0HkOHkkabAkAHkra7677AAAbpkbpkr1AAAAAbpbppkkpk1k+k-k7822332HNNHW222IHHIAu22222ONONAu222IHHIPtAAAbpkbpkr17923HNHppkr 32332HNNHPtAAPPpbpb1若：PAPPAAppkpbpkbrPPAAAAApbpbpb180AABAABApbppkbpkr 1 k+k-k81BBAAAAApbpbpb 1 BBAABBBpbpbpb 1 k+k-82BBAAAAApbpbpb 1 BAkr BBAABBBpbpbp

11、b 1 BBAApbpbkr AABBpbpb 1若：k2)1 (BBAABABApbpbppbkb 8384嘌 呤糖糖85氢键HNCNCCCNRCHNH2NONHHOHOCH3860211EAkEAkEAkdtEAd1211EAKkkEAkEAm2EAKkrm121kkkKmk2k1k-1A+EEAE+P87)(110EAEAKEAKEAmmmKAEAEA0mKAEAkr0288一一级级02EAKkrm mmmKAArKAEAkr02mmKAArr8911ArKrrmmm11ArmmKAArr90 xxakdtdx)( 91(2)23)3/2(2323HNHkHNHkdtdx txdtkxa

12、xdx00)(xddxxaadxxaxaaxxx 000)(ktxxaaa ln)5 . 02(ln2/1 kat92 AkdtAd AkdtAdHkk93 )10(1093. 62ln532/1 ktk )10(1093. 6 2ln 422/1 ktk 10101010 54 kk94 95)()(xbkxakdtdxeecxaxbKkktkkxxxee)(ln22lnRTEERTUdTKdmrck+k-AB96zyxxakkdtdx其中)(21tkkxaa)(ln21)(2ln212/1kkt21kkzy212211kkEkEkEa97221)(xakkdtdxtkkaxa)(1121z

13、yx其中)(1212/1kkat21kkzy98CBAkk2121BkAkdtBd tktkeekkakB21121 2121max,)/ln(kkkktB tkaekB11 BAk1990dtdcX2CBkdtPdr22BkkBAkk02CBkCkAkdtCd22BAkBAkkkCBkrk2k+k-AC, B+CP100101kkkk2其中2lnRTEdTkd222lnlnlnRTEEEdTkddTkddTkdk+k-A+BABk2PAB+C102BAk2dtdp总202)2(ppkkpA总103212. 9/4606lnTk212. 9/4606lnTKck+k-104常数RTUKmrcl

14、n常数RTEkln212. 94606T212. 94606T105eeeecxaxbABKkktkkxxxee)(ln106107221)(xakkdtdxtkkaxa)(112121kkzy且6 . 025. 015. 021aazykk108tkkaxa)(1121109iiiakEkEnnixakxakdtdx)()(110dTkdRTEaln2dTkdilndTkdkii1dTRTEAdkiii/exp12/exp1RTERTEAkiiii2RTkEkiiiiiiakEkE111 AkdtAd AkdtAdHkk112 )10(1093. 62ln532/1 ktk )10(1093. 6 2ln 422/1 ktk 10101010 54 kk113114 1222/112/1)()(HHtt 201. 002. 0218003600 1152/12lntHk11212219 .52)()(ln)( molkJTkTkTTTRTEa116HIHIbpkbpkr 1 117HIHIHIHIpkkbpbpbpkr21141100 . 51sPakkbpkbprHIHIHIHIHIHIppbpkbpr3101501118k+k-k211903223OOkOOkOk