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Elementary rate law

  1. Dec 10, 2014 #1

    Maylis

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    Hello, I am having some confusion over elementary rate laws. This is a hydrodealkylation reaction.

    testb.13.gif

    The specific reaction rates k1 and k4 are defined w.r.t. H2.

    If I want to write the rate law for the hydrogen radical for the termination step, would the elementary rate law be ##r_{H \bullet} = -2k_{4}C_{H \bullet}^2## or ##r_{H \bullet} = -k_{4}C_{H \bullet}^2##. I think it is the former because of the part of k4 being with respect to hydrogen. If it was with respect to the hydrogen radical, then it would be the latter? Thanks
     
    Last edited: Dec 10, 2014
  2. jcsd
  3. Dec 10, 2014 #2

    Bystander

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    Is one hydrogen radical distinguishable from another?
     
  4. Dec 10, 2014 #3

    Maylis

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    No, but I don't see how it relates to the rate law
     
  5. Dec 10, 2014 #4

    Bystander

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    Not only are you being confused, so am I --- I took off the wrong direction with how you came up with "-2k4CH⋅2, and thought you were making distinctions among hydrogen radicals.
    And rereading the problem statement for the twentieth time, I'll agree, because ...

    , and this is the source of the confusion, I don't recall ever seeing a rate constant referred to the product. I'm a bit of a dinosaur, and conventions in kinetics may have evolved since I last had any use or interest for the field.
     
  6. Dec 11, 2014 #5

    epenguin

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    I wouldn't worry about it. I would just write
    myself, so as not to have to remember about the 2, and just get on with the problem.
    It would be quite reasonable to have an equilibrium constant defined as K = [H.]2/[H2].
    If it turns out later the other definition would have been more convenient, I can always change definition.
     
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