What prevents infinite potential with Nernst Equation

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Discussion Overview

The discussion revolves around the implications of the Nernst equation in electrochemistry, particularly regarding the potential for infinite electromotive force (EMF) due to concentration gradients. Participants explore the theoretical limits of the equation, its applicability at low ion concentrations, and the physical realities that may prevent infinite potential in practical scenarios.

Discussion Character

  • Exploratory, Technical explanation, Debate/contested

Main Points Raised

  • Some participants note that the Nernst equation includes a log Q term, which could theoretically approach infinity if the denominator is very close to zero, raising questions about the maximum achievable EMF in real-world scenarios.
  • Others argue that as ion concentration decreases towards zero, the driving force for diffusion increases, suggesting that the log function's sublinear nature complicates the interpretation of the equation's implications.
  • A participant expresses skepticism about the practical application of the Nernst equation, suggesting that other factors, such as half reactions or ion diffusion, may limit the voltage that can be obtained from concentration gradients.
  • Another participant proposes that the Nernst equation may lose accuracy at low ion concentrations, as the predicted potential could become physically meaningless due to low exchange current density and other dominating effects.
  • A question is raised regarding the observation of a 0.1V current in a galvanic cell with 0M copper ions, prompting discussion about the role of copper ions in attracting electrons and whether this understanding is correct.

Areas of Agreement / Disagreement

Participants express differing views on the implications of the Nernst equation, particularly at low concentrations, and there is no consensus on the practical limits of EMF or the behavior of the system under these conditions.

Contextual Notes

Limitations include the potential inaccuracy of the Nernst equation at low ion concentrations and the dependence on specific electrochemical conditions that may not be fully addressed in the discussion.

Gama
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The nernst equation has a log Q term. The denominator of that could be very close to zero. That would make Q close to infinity and log Q close to infinity. How high can the EMF be due to concentration in the real world and why?
 
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The Nernst equation is E = \frac{R T}{z F} \ln\frac{[\text{ion outside cell}]}{[\text{ion inside cell}]}.

As the concentration of ions on one side of the membrane goes down (towards zero), the driving force on ions on the other side of the membrane goes up- that's simple diffusion. Since the log function is sublinear, I'ts not clear what you are having problems with.
 
I wasn't thinking of membranes in particular. The log of infinity is infinity. My guess is the limiting factor is some other half reaction or diffusion of ions from one side of a battery to the other. Even if this is the case the Nernst equation makes it appear that a much higher voltage can be obtained from a concentration gradient than I think can occur.
 
I would imagine the Nernst equation loses accuracy at low ion concentrations. The physics would change and the equation would no longer be correct.

Wiki (not the most authoritative source, I realize) seems to agree:


At very low concentrations of the potential determining ions, the potential predicted by Nernst equation tends to ±infinity. This is physically meaningless because, under such conditions, the exchange current density becomes very low, and then other effects tend to take control of the electrochemical behavior of the system.
 
How would you explain a 0.1V current when the concentration of copper ions in solution is 0M ?

This is in a zinc || copper galvanic cell (with salt bridge) and the [Zn2+] is 1M?

I thought that the copper ions attract the electrons? Am I mistaken?
 

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