Wednesday, 30 November 2016

kinetics - Unit consistency in rate equations


I suppose that my problem is not one of great profundity, but it is an annoying one. The problem is related to the measurement units involved in rate equations of different order. Not being a chemist myself, I have in my work encountered equations of the type: $$\frac{-\mathrm{d}[A]}{\mathrm{d}t} = k [B]^b [A]^a$$ representing the decay of some species $A$. The brackets denote concentration and $k$ is the rate constant. $B$ is some other chemical species (cooking chemical) and then there are the exponents $a$, $b$. For a first order reaction with $b = 0$ and $a = 1$ everything is still under some kind of control; if time is measured in minutes the unit of the rate constant is $\mathrm{min^{-1}}$.



However, if we have a pseudo first order reaction where the species $B$ is present albeit constant during an experimental run, problems arise. In my line of work the species $B$ is typically hydroxide ions and their concentration is traditionally given in molar, $\mathrm{mol/L}$. Even if the concentration of $B$ does not change, the initial concentration plays a role, hence the power of $[B]$ usually appears as a separate factor in the rate equation. Unfortunately, this complicates the unit balance in the equation as frequently the exponent $b$ is a non-integer number. One workaround would be to rescale the concentration to a dimensionless number, but the choice of scaling parameter would be rather arbitrary. Another, perhaps more elegant solution would be to work with molar fractions, but this would be discordant with most of the literature in the field, where the question of unit consistency mostly is disregarded.


A second order rate equation ($b = 0$, $a = 2$, or $b = 1$, $a = 1$) leads to the unit $\mathrm{L\,mol^{-1}\,min^{-1}}$ for the rate constant. I suppose this is still somehow acceptable, even if I would prefer to work with scaled concentrations (divided by the initial concentrations) with unit $\mathrm{min^{-1}}$ for the rate constant, but for fractional order rate equations there is the same problem as in the earlier described pseudo first order case.


Is there any prescribed remedy to this dilemma?




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