IMG_0004_NEW_0028 - L" RaU = P"fflW Pre quilibrium...

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Pre-equilibrium In reactions with a fast initial equilibrium step: Fast Slow k' k, A+B -i- lntermediate-a> Products k_r Fast Determining ltc Rete Law O *, and *-, mrcl hster than /ct + Second st p b ratedetermining ** ='lT*l = a But. .. don't wut intermediate species in rate law! @ Equilibrinn corertrations of A, B and intermediate are reachcd vcry npidty = Forserd rlltc = rwerse rate t, IAltBl : t-, fintermediate] O Combine O ard e to rvrite rate law without concentrdim of intermediates. > Overall Rate: ot+^ - olU; Kr,ta- !ftr = k, [aJt7J b, ,041 = k -t L,t,ltQ * (oJ= l,rvwbl bt b^,t
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Unformatted text preview: L" RaU = P"fflW Pre+quilibrium Rate Law Step 1 kl q .- Oz * O kl and k -1both fast k_1 Step 2 k2 Or + O - 2Oz k2 slow (rate{etermining) Since tr and t-1 are fast + Reversible Step at equilibrium: ,qtorl=,t [Or][O] Substitute into rate expression: Example: Pre-Equilibrium . Decomposition of Ozone [email protected]) -+ 3oz(g) Experimentally determined Rate Law: Rate: k[o'l' '"[or][email protected] Proposed Mechanism: . Step 2 is rate-determining (or rate-limiting) 1l<rltz : T,rhT I<1 ' Ft t C0"1 K k,.!J h (04 Step 1 k1 o3 k -,1 Step 2 k2 oa+o , 2oz k2 LiZ L-'La I-tft J C0"1 a r:w...
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