浙江大学 普通化学 化学原理 英文课件Chapters 13 14化学动力学与平衡.pptVIP

ChemicalKineticsEquilibriumChapter1314Howfastorslowisthereaction?Whichoneistherate-determiningstep?Nosakaetal.2006.J.Phys.Chem.B.Kuboetal.2006.J.Am.Chem.Soc.

1.Reactionrate:rate=-D[A]Dtrate=D[C]DtaA+bBcC+dDrate=-D[A]Dt1a=-D[B]Dt1b=D[C]Dt1c=D[D]Dt1dCH4(g)+2O2(g)CO2(g)+2H2O(g)rate=-D[CH4]Dt=-D[O2]Dt12=D[H2O]Dt12=D[CO2]Dt

Br2(aq)+HCOOH(aq)2Br-(aq)+2H+(aq)+CO2(g)393nmlightDetector393nmBr2(aq)I0ItUV-visibleabsorptionspectroscopicspectrumA:absorbancee:molarcoefficient(cm-1.M-1)l:lightpathlength(cm)C:concentration(M)It=I0e-elCLambert-BeerLaw

averagerate=-D[Br2]Dt=-[Br2]final–[Br2]initialtfinal-tinitialslopeoftangentslopeoftangentslopeoftangentinstantaneousrate=arateforspecificinstanceintimeInitialrateistheratemeasuredintheinitialperiodoftime,soastoavoidpossibleinterferencefromreactionintermediatesorproducts.

rate=k[Br2]k=3.50x10-3s-1rateconstantSlope=3.50x10-3s-1Thisreactioniscalledasfirst-orderto[Br2].

ThisiscalledtheRatelaw.aA+bBcC+dDRate=k[A]x[B]yItmeansthatthereactionisthe(x+y)thorder,thexthinA,andtheythinB.Notethat:Theratelawsarealwaysdeterminedbyexperiment.Xorycanbeanyvalue,butitdoesnotnecessarilyequaltoaorb(x?a,y?b)Ingeneral,

F2(g)+2ClO2(g)2FClO2(g)As[F2]isconstant,quadruples[ClO2],therateisquadrupled.y=1Assume:rate=k[F2]x[ClO2]yAs[ClO2]isconstant,doubles[F2],therateisalsodoubled.y=1Therefore:rate=k[F2]x[ClO2]y

Determinetheratelawandcalculatetherateconstantforthefollowingreactionfromthefollowingdata:S2O82-(aq)+3I-(aq)2SO42-(aq)+I3-(aq)Experiment[S2O82-][I-]InitialRate(M/s)10.080.0342.2x10-420.080.0171.1x10-430.160.0172.2x10-4Assume:rate=k[S2O82-]x[I-]yWeseethatx=1