By Badger R.M.
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Extra resources for Absolute Intensities in the Hydrogen-Chloride Rotation Spectrum
Sample text
Fortunately, in many eases the network is such that the steady state assumptions can be invoked. When this is possible, the kinetic rate expressions for the elementary processes of the reaction mechanism can often be solved analytically, as in the example above, to yield a simpler rate expression for the overall process. The identification of such a mechanistic rate expression, using experimental rate data from a kinetic study, can serve to identify the likely mechanism of that reaction. Unfortunately, several mechanisms may produce the same overall kinetic rate expression, in which case we have to be satisfied with using kinetics to reduce the number of likely mechanisms that can possibly apply to those whose rate expressions are of the form found to apply.
However, the experimental rate constant of this rate expression consists of a square root of a quotient of products of elementary rate constants. This fact notwithstanding, the experimental rate constant is usually subject to limits in A and E, similar to those described above for elementary rate constants. For example, an analysis of the experimental frequency factor shows why it should be in the expected range of magnitudes. 24) Assuming that the individual elementary reaction frequency factors composing A~, are limited in their magnitude to that theoretically possible, we see that the experimental frequency factor can be expected to be about the size of an average elementary frequency factor.
To illustrate the simplest changes in kinetics that can be observed as reaction conditions are changed, consider the simple chain mechanism for the pyrolysis of ethane. The initiation reaction must produce active species by breaking a bond in the ethane Using Kinetic Data in Reaction Studies 51 molecule. On examining the bond strengths of the C-C bond and the C-H bonds present in the molecule we find the C-C bond to be significantly weaker than the C-H bond. In line with previous discussion, this suggests that at reaction temperatures this will be the bond to break and initiate the chain reaction.
Absolute Intensities in the Hydrogen-Chloride Rotation Spectrum by Badger R.M.
by Thomas
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