Saturday 30 January 2016

electrochemistry - How to determine the value for n in the Gibbs free energy and redox potential equation?


I am having a problem with this equation for redox potentials



$$\Delta G = -nFE_\mathrm{cell}$$


In this equation I never am totally sure about what the value of $n$ should be, for example for the reaction shown below, would the $n$ be 2 electrons or 1 electron? Personally, I think it should be 2 electrons because that is the number of mol of electron under the simplest whole number ratio.


\begin{align} \ce{cyt $c$(Fe^3+) + e- &-> cyt $c$(Fe^2+)}\\ \ce{NADH &-> NAD+ + H+ + 2e- }\\ \end{align}


I think this is a different matter than in the already answered question "Does the relationship equation between standard cell potential and equilibrium constant violate potential's intensive properties?" Because in that Nernst equation the change in $n$ would be balanced by the change in the equilibrium constant. I assume that you are insinuating that there is one of the variables here which will correct for the increase in $n$. I don't see which would, as $E_\mathrm{cell}$ should be independent of quantity and $F$ is a constant.



Answer




Personally, I think it should be 2 electrons because that is the number of mol of electron under the simplest whole number ratio.



Yes, it is $\ce{2e-}$.


Assuming that the two reactions provided above are half-reactions, the $n$ has to be $2$.



$E_\mathrm{cell}$ is independent of quantity because it is an intensive property. It does not depend on the amount of matter present. The $n$ accounts for the number of moles of $\ce{e-}$, this is used to calculate $\Delta G$, which in turn depends on the amount of matter present.


Overall, one must understand that $E_\mathrm{cell}$ is just the difference in cell potentials of two half-reactions. Increasing or decreasing the amount of both does not matter.


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