Is the Nernst equation limited to dilute ionic solutions?

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    Nernst equation
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Discussion Overview

The discussion centers on the applicability of the Nernst equation, particularly whether it is limited to dilute ionic solutions. Participants explore the relationship between concentration and activity in the context of thermodynamics and the conditions under which the Nernst equation remains valid.

Discussion Character

  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • One participant references a source stating that the Nernst equation is only accurate for dilute ionic solutions, questioning if this implies a concentration limit of under 10-3 M.
  • Another participant argues that while the Nernst equation is based on activity, concentration and activity can be approximately equal at low concentrations, suggesting that adjustments may be necessary when conditions deviate from ideality.
  • A participant expresses concern over the validity of approximations in calculations involving every particle, indicating a need for clarity on this issue.
  • One participant notes that activity can be used in the Nernst equation when concentration cannot, highlighting the need for experimental data to determine activity in certain cases.
  • Another participant claims that using activity and fugacity in the Nernst equation is exact, while using concentration and partial pressures is only approximate, mentioning the Robinson-Stokes equation for converting concentration to activity for ionic species.

Areas of Agreement / Disagreement

Participants express differing views on the limitations of the Nernst equation, with some supporting the idea that it is restricted to dilute solutions and others suggesting that activity can provide a more accurate framework under various conditions. The discussion remains unresolved regarding the extent of these limitations.

Contextual Notes

There are unresolved assumptions regarding the definitions of activity and concentration, as well as the conditions under which the Nernst equation is applied. The discussion also highlights the complexity of converting concentration to activity for different species.

somasimple
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As the link states the Nernst equation is for activity. Concentration and activity are approximately equal when small. Do you know any thermodynamics? It is common in thermodynamics to make some approximations. When the conditions are not met we need do adjust the variables. For example often (as here) we define a new variable that behaves in the idealized way, then we must calculate it. Often a variable has dependence that we cannot always ignore.

http://en.wikipedia.org/wiki/Thermodynamic_activity
 
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my chemistry teacher told me that we can't make approximations, when we are dealing with calculations consisting of each and every particle...
please help me on this...
 
Yes so in thermodynamics activity is defined. Activity can be used in the Nernst equation when concentration cannot. The trouble is experimental data is often needed for the activity in this case.
 
Nernst equation using concentration and partial pressures is approximate; Nernst equation using activity and fugacity is exact as far as I know.

Concentration can be converted exactly to activity for ionic species in solution by Robinson-Stokes equation. For cases besides ionic species in solution it is trickier, fugacity is trickier also.
 

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