Sunday, October 1, 2017

kinetics - Why are equilibrium constants unitless?


I haven’t quite reached the point where I can read a full-fledged text on chemical kinetics and thermodynamics yet, so bear with me, please.


I’m wondering why a value like $K_\text{eq} = \frac{[\ce{NO}]^2[\ce{O2}]}{[\ce{NO2}]^2}$ wouldn't have units of M?



Answer



I goofed up the first time I tried to answer this question, erroneously applying dimensional analysis to your equilibrium expression.



It turns out that Silberberg[1] gives a good explanation of why $K_\text{eq}$ is dimensionless, which is often glossed over as the terms of the equilibrium expression are generally taught as concentrations. In actual fact, the terms are ratios of the concentration or activity of each species with a reference concentration (1 $\mathrm{mol\cdot{L^{-1}}}$ for solutions.) For example, a concentration of 2 $\mathrm{mol\cdot{L^{-1}}}$ divided by a reference of 1 $\mathrm{mol\cdot{L^{-1}}}$ yields a ratio of 2, with no units. As each term has no units, so too does $K_\text{eq}$.


[1] Silberberg, M.E.; Chemistry – The Molecular Nature of Matter and Change 3e; 2003, p. 719


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