Jason R. Green edited Introduction.tex  over 9 years ago

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An inequality between two important quantities known as the statistical length and Fisher divergence is able to quantitatively measure the amount of static and dynamic disorder of a rate coefficient over a period of time, and is able to determine when traditional kinetics is truly valid[insert citation]. When the inequality is minimized, the statistical description of rate coefficients is also minimized, which can help one determine the best data set to use during a kinetic analysis. This inequality measures the temporal and spatial variation in the rate coefficient. When there is no static or dynamic disorder, this inequality is reduced to an equality and it is the only time where traditional kinetics is truly valid. This inequality has been interpreted as a measure of how constant a rate coefficient can be. It captures the fluctuations associated with the rate coefficient for first order irreversible decay processes. In this work we expand on this idea providing more generality and utility to the theory by gernealizing to higher order kinetics.  We consider the irreversible elementary reaction types  \begin{eqnarray}  A \begin{equation}  A^i  &\to& \mathrm{products}\\  A^2 &\to& \mathrm{products}\\  \vdots\\  A^n &\to& \mathrm{products}\\  \end{eqnarray} \mathrm{products}\quad\quad\textrm{for}\quad i=1,2,3,\ldots,n  \end{equation}  The mass-action rate laws for these kinetic schemes are  \begin{equation}  \frac{dC_{A^i}(t)}{dt} = k_iC_{A^i}(t)\quad\quad\textrm{for}\quad i=1,2,3,\ldots,n  \end{equation}  Experimentalists deduce rate laws from data that is the integrated rate law. For the $i^{th}$-order reaction the integrated rate law is  \begin{equation}  \frac{1}{[C_A(t)]^{i-1}} = \frac{1}{[C_A(0)]^{i-1}}+(i-1)\omega t.  \end{equation}  Survival functions are the input to our theory  \begin{equation}  S(t) = \frac{C_A(t)}{C_A(0)},  \end{equation}  which come from the integrated rate law. The survival function for this class of reactions is  \begin{equation}  S(t) = \sqrt[i-1]{\frac{1}{1+(i-1)\omega tC_A(0)^{i-1}}}  \end{equation}