mechanism 1 overall reaction is 2NO + Cl2 --> 2NOCl NO + Cl2 = NOCl2     fast equilibrium NOCl2 + NO--->  2NOCl     slow rate law for mechanism 1 is rate=k[no2]^2[cl2] mechanism 2 Cl2 --> 2Cl     slow Cl + NO --> NOCl     fast rate law for this mechansim 2 is rate=k[cl2] i noticed that when the mechanism has a fast reaction at equilibrium, the rate law includes reactants form both fast and slow, whereas when the reaction has fast reactions not at equilibrium, the rate law is only the reactants from the slow step (rate determining step) why is the rate law different when the fast reaction is at equilibrium vs when the mechansim has a fast reaction not at equilibrium?

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Chapter12: Chemical Kinetics
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Problem 75AE: One mechanism for the destruction of ozone in the upper atmosphere is a. Which species is a...
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mechanism 1

overall reaction is 2NO + Cl2 --> 2NOCl

NO + Cl2 = NOCl2     fast equilibrium
NOCl2 + NO--->  2NOCl     slow

rate law for mechanism 1 is rate=k[no2]^2[cl2]

mechanism 2

Cl2 --> 2Cl     slow
Cl + NO --> NOCl     fast

rate law for this mechansim 2 is rate=k[cl2]

i noticed that when the mechanism has a fast reaction at equilibrium, the rate law includes reactants form both fast and slow, whereas when the reaction has fast reactions not at equilibrium, the rate law is only the reactants from the slow step (rate determining step)

why is the rate law different when the fast reaction is at equilibrium vs when the mechansim has a fast reaction not at equilibrium? 

 

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