When the concentration of NADH increases while the concentration of NAD+ decreases, the electrochemical potential will increase.
The electrochemical potential is a measure of the difference between the average energy of the outer most electrons of the molecule or element in its two valence states.
In the conversion from NaD to NADH there will be the formation of either oxidation or reduction potential.
The net cell potential is cathode - anode. So if it is reduction or oxidation there will be a subsequent change in the potential, and thus can be determined.
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