Wednesday 2 March 2016

reaction mechanism - Rate Constant Units and Eyring Equation


Rearranging the Eyring equation leads to the following:



$$\Delta^\ddagger S^\circ = R \ln{\frac{k \times h}{{k_\text{B}}{T}}}+\frac{\Delta^\ddagger H^\circ}{T}$$


where $k$ is the rate constant, $h$ is the Planck constant, $R$ is the universal gas constant, $k_\text{B}$ is the Boltzmann constant, $T$ is temperature, $H$ is enthalpy, and $S$ is entropy. The entropy term should ultimately be in units of $\mathrm{\frac{J}{mol\ K}}$. The right term of the equation will clearly yield the correct units. For the left term, the universal gas constant can be expressed in $\mathrm{\frac{J}{mol\ K}}$, which means that the log term should be dimensionless. For the bottom part of the fraction, the units evaluate to $\mathrm{J}$. For the top part, the Planck constant has units of $\mathrm{J\cdot s}$. To get the top part of the fraction to evaluate to $\mathrm{J}$, the rate constant would have to be in units of $\mathrm{s^{-1}}$. For first order reactions, this is indeed the case. For reactions of higher order, this will never work out to the correct units.


This makes me think that the Eyring equation is simply using the unitless values of these variables. This still leads to some ambiguity about which value of the rate constant to use. Take for instance a second-order reaction in which the rate constant is in units of $\mathrm{M^{-1}\ s^{-1}}$. If we rearrange the units to SI units ($\mathrm{m^3\ mol^{-1}\ s^{-1}}$), the value of the rate constant changes. So is the rate constant $k$ in the Eyring equation simply the value of the rate constant when that rate constant is expressed in certain units? And if so, are the concentration units always expressed in molarity? I kept missing a homework problem because I was converting $k$ from molarity to SI units, which makes me believe this is indeed the case.




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