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Reaction Mechanisms.docx

Reaction Mechanisms.docx

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Published by: Mousumi Patnaik on Oct 28, 2013
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Reaction Mechanisms
 
Elementary Reaction Steps - Molecularity
 We have made a big deal out of the fact that you cannot predict the rate law for a chemicalreaction from the balanced equation for that reaction. We now introduce a new class of simple reactions, called
elementary reaction steps
, for which the rate law IS determined bythe balanced reaction equation. We also introduce a new term,
molecularity
, which tells usthe number of molecules involved in an elementary reaction step.We emphasize that the reaction velocity for each elementary reaction step IS determined bythe reaction step and, later on, we will string a sequence of elementary reaction steps together to form what is called a
mechanism
. A reaction mechanism is a detailed (theoretical)description of how we think the chemical reaction proceeds. That is, it describes our thoughtabout which molecule collides with which other molecule to form an intermediate product,which my go on to react with some other species, and so on, to produce the overall reaction.The elementary reaction steps must be balanced (as do all chemical reactions). We canusually tell the difference between an elementary reaction step and a balanced reaction by thefact that the elementary reaction step will have one or more rate constants associated with it,as we will see below.It is probably easiest to describe the elementary reaction steps and their associated rate laws by just telling you what they are. As we proceed you will become aware of the fact that therate law is completely determined by the elementary reaction step you write down. (Theconverse is not true. We will see in the examples below that several different elementarysteps may give rise to the same rate law.)
Unimolecular Reaction Steps
 The elementary reaction step,, (1)is unimolecular because there is only one molecule reacting, that is, molecule "A" is reacting.This unimolecular reaction step implies the rate law,, (2)or, equivalently,. (3)In words, these elementary reaction steps say that the molecule, A, spontaneously transformsinto B at some rate
1
. The algebraic sign in front of 
1
tells whether you are gaining productor losing reactant depending on whether the concentration in the derivative is increasing or decreasing. For example, in Equation 2, [B] is increasing, and in Equation 3, [A] isdecreasing. (All of the usual rules of stoichiometry still hold in elementary reaction steps. If you use up some reactant you must gain an equivalent amount of product.)
 
An elementary reaction step may be reversible or irreversible. Equation 1 is an irreversibleunimolecular step. Equation 4 below is a reversible unimolecular step:. (4)This reversible unimolecular step implies the following rate laws,(5)and/or . (6)(Either one of these may be used, depending on whether we are trying to account for thedisappearance of reactant, A, or the appearance of product, B, in our mechanism for a particular reaction.)A unimolecular reaction step can have more than one product, for example,. (7)The unmimolecular process given by Equation 7 implies the same rate law as the reaction inEquation 1, namely, either Equation 2 or Equation 3.
Bimolecular Reaction Steps
 There are several varieties of bimolecular steps. For example,(8)implies the rate law,, (9)or , (10)and so on. In Equations 8, 9, and 10 we have given only one product, "C." We would get thesame rate laws if there had been two or more products, for example as in,. (11)
Reversible Bimolecular Steps
 The bimolecular reaction(12)

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