$$\Delta G = -nFE$$

My textbook says that we can measure that this $\Delta G$ is measured when the work is done reversibly. But my confusion is how will we work reversibly when we have an electrochemical cell? And what guarantee do we have that while measuring $\Delta G$, E will remain constant? Isn't it possible that after 0.25 moles of electrons have reacted, E would change because it depends on concentration.

  • $\begingroup$ As the reaction progresses toward completion, it becomes less spontaneous, so that is exactly correct. $\endgroup$ – Zhe Oct 5 '18 at 13:39

What that means is that $\Delta G$ is the maximum work available and therefore is only a thermodynamic limit. That's why $E$ is measured with a voltmeter where no current is flowing (actually extremely low current, i.e. the voltmeter has very high impedance). An analogy would be measuring gas pressure in a pressurized vessel, only in e-chem this is "electron pressure". Once you do work with an e-chem cell, the current will encounter many resistances which translate into voltage drop and in turn are energy losses and E will change.

  • $\begingroup$ The limited current will also ensure that the concentrations of reactant and product species don't change noticeably so that $E$ is constant during the time it takes to measure the voltage. $\endgroup$ – Karsten Theis Apr 17 at 5:18

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