W17-Chem-260-L35_rate_law_1.pdf - 3/31/17 Chemistry 260...

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3/31/171Chemistry 260Chemical PrinciplesLecture 35Mon Apr 3 201703.0(1,25)kJGmolatmCΔ=SpontaneousFastImmeasurably slow!DiamondGraphiteAre diamonds forever (?)
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3/31/172JThermodynamics = ThermostaEcsLThe name thermodynamics is somewhat misleading since thermodynamics completelyavoids dealing with dynamical processes in a direct manner (in fact – Eme is not arelevant variable)Hence,ThermostaEcswould probably have been a more appropriate name for it.Avoiding real dynamics, which is usually system-specific and far more complicated todescribe, is the source of both strength and weakness of thermodynamics.Jit gives rise to a very general and universal theory that can be applied to pracEcallyany macroscopic system.LThermodynamics cannot answer dynamical quesEons on the rates of processes. Inother words, it can tell us if a process will happen or not and what the finalequilibrium state will be, but it cannot tell us anything about how fast or how slow itwill happen!The incorporaEon of such dynamical aspects into the thermodynamics is the goal ofnonequilibrium thermodynamics, which is a current area of acEve research (andoutside of the scope of this course...).Thermo-dynamicsStaEsEcalmechanicsKineEcsMoleculardynamicsQuantumChemistryElectronicstructurePhysical Chemistry
3/31/173The rate of a reactionaA+bBcC+dDis given by:v t( )=1adAdt=1bdBdt=1cd Cdt=1ddDdtExamples:(1)NO2(g)+CO(g)NO(g)+CO2(g)v t( )=ddtNO=ddtCO2=ddtNO2=ddtCO(2)NO2(g)+F2(g)2NO2F(g)v t( )=12ddtNO2F=ddtNO2=ddtF2Comments:(1) No intermediate species (unless their concentration is constant).(2) The definition depends on the way of writing the chemicalreaction.The reac(on ratedNOdt=Δt0limΔNOΔt=Δt0limNO2NO1t2t1
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