化学动力学综述

17.5120019()k2AA2rxn(1)UNrate=-d[U]/dt=d[N]/dt=k[U]rxn(2)ABA+Brate=-d[AB]/dt=d[A]/dt=k[AB]rxn(3)A+BABrate=-d[A]/dt=-d[B]/dt=k[A][B]rxn(4)2AA2rate=-d[A]/dt=2d[A2]/dt=k[A]2rxn(5)2A+BA2Brate=-d[A]/dt=-2d[B]/dt=2d[A2B]/dt=k[A]2[B]rxn(6)A+B+CAB+Crate=-d[A]/dt=-[B]/dt=k[A][B]rxn(3)CC/M•sec-1M•min-1nM•sec-1sec-1min-1min2k[A][B]M-1•time-1M•time-1[A]m[B]nm+n[A]m[B]nrxn(1)rxn(2)rxn(3)[A][B]rxn(4)[A]rxn(5)[A][B]rxn(6)[A][B][C]rxn1rxn2time1rxn3rxn4M1time11012sec1106sec11091109M1sec1A+BAB109M1sec1[A][B]∆Gu‡∆Gu‡3ABA+BABA+Bd[AB]/dt=kon[A][B]-koff[AB]konandkoffkon[A][B]ABAB-koff[AB]AB[AB][A][B]d[AB]/dt=kon[A][B]-koff[AB]=0[A][B]/[AB]=koff/kon=KdNUd[N]/dt=kf[U]-ku[N]=0[U]/[N]=ku/kf=KuHPLCABABABABABpHpH74AB-d[A]/dt=k[A]d[A]/[A]=-kdtln[A]=-kt+ln[Ao][A]=[Ao]e–ktAB[A0]=10-3Mk=0.1sec-1ln[]k5ln[]t1/2t1/2t1/2=-ln(0.5)/k=0.693/k6.9seck=0.01sec-170seck=10sec-1,0.07sec70milliseconds20sec20sec-2AA2-d[A]/dt=k[A]2d[A]/[A]2=-kdt1/[A]=-k(t)+1/[A0][A]=A0/(A0kt+1)[A0]=10-6Mk=2x105M-1sec-1[A][A]61/[A]k1/[A2]t1/2=1/(k[A0])5sect1/2A5sec10secA2AA+BAB-d[A]/dt=-d[B]/dt=k[A][B]31ABt0[A]=[A0][B]=[B0]k=()/([A0][B0])2[A0][B0]1/[A]1/[B]3[A0][B0]ABA7-d[B]/dt=k[A0][B]=kapparent[B]kapparent=k[A0]ln[B]k[A0][A0]kkapparen20bpDNADDNARDNA[R]R+DRDd[R]/dt=-k[R][D][R]22R+DR2Dd[R]/dt=-k[R]2[D]DNAR+DRDR2+DR2DR4+DR4D2R+DR2D2R2+DR4D2R4+DR8D2R+DRDR2+DR2DR4+DR4D2R+DR2D32DNAR2D2R+DR2+DR2D/2R+DRD+RR2D8DNARDR2RDDNAR2RDR2RDR2RDR2DR29R2DR2D2RDR2DBCABBCAABBCBCtimesecBCC0.7sec1sec1ABBCB10timesecBCBCC0.7sec1sec1pre-equilibriumBACBABC10CBA10ABKab=[A]/[B]=(200s-1)/(1s-1)=200ABC20s-1[B][B]d[C]/dt=(20s-1)/(200)[A]=0.1s-1[A]C7secBAC0.7secBAC11k1k2BABCC3d[C]/dt=(k1k2)/(k-1)[A]3.1k2k1BCBABAk1k2BBBd[B]/dt=k1[A]-k-1[B]-k2[B]=k1[A]-(k-1+k2)[B]=0(k-1+k2)[B]=k1[A][B]=(k1)/(k-1+k2)[A]d[C]/dt=k2[B]d[C]/dt=(k1k2)/(k-1+k2)[A]k-1k2d[C]/dt=(k1k2)/(k-1)[A]3.1k2k-1d[C]/dt=(k1k2)/(k2)[A]=k1[A]3.23.2k1BB9BCA1sec1k2k-13.2d[B]/dt012AB10ACA+BAB10AC[AB]d[AC]/dt=(k1k2)/(k-1+k2)[A][B](k1k2)/(k-1)[A][B]k2k-1ABAB13rxnABBCBCBBrxnBA14rxnABABBACBCBC100rxnBCABBCAC