The equilibrium constant and solids

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Discussion Overview

The discussion centers around the role of solids in equilibrium expressions, particularly why the concentrations of pure solids are not included. Participants explore the implications of solid concentration in reactions and the concept of activity in equilibrium calculations.

Discussion Character

  • Debate/contested
  • Conceptual clarification
  • Technical explanation

Main Points Raised

  • One participant questions the reasoning that the concentration of a pure solid is constant, suggesting that if a solid dissociates, its concentration should change.
  • Another participant introduces a scenario involving a nail dropped into a solution, questioning whether it reacts and what its concentration would be.
  • A follow-up post speculates that the size of the solid affects its concentration change, proposing that smaller amounts of solid might significantly impact the original mass.
  • Another participant counters that the size is not the critical factor, emphasizing that reactions occur only at the surface of the solid.
  • A further inquiry raises the issue of how a solid that dissolves significantly can still be considered to have a constant concentration when only a small fraction remains.
  • One participant notes that concentration is an approximation and explains that the reaction quotient is based on activities, stating that for solids, the activity is always 1.
  • It is mentioned that there are various approaches to this problem, which have been discussed previously.

Areas of Agreement / Disagreement

Participants express differing views on the significance of solid concentration in equilibrium expressions, with no consensus reached on the underlying principles or implications.

Contextual Notes

Limitations include the dependence on definitions of concentration and activity, as well as the unresolved nature of how significant changes in solid mass affect equilibrium considerations.

whsmt85
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Why are the concentrations of solids not incorporated into the equilibrium expression? All the books say it's because the "concentration of a pure solid is constant", but that doesn't make sense to me... If the solid is dissociating to produce a given product, why doesn't the concentration change?

Thanks for your help
 
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You drop a nail into the solution.

Does it react?

What is its "concentration"?
 
Borek said:
You drop a nail into the solution.

Does it react?

What is its "concentration"?


So I'm guessing that because the nail is so big, whatever ions it loses to the solution don't cause a significant change to its "concentration".

But aren't there any situations where you have a small enough amount of solid that the ions it produces does detract significantly from the solid's original mass?...

Thanks
 
It is not the size that matters, what is important is the fact that reaction takes place only of the surface.
 
Borek said:
It is not the size that matters, what is important is the fact that reaction takes place only of the surface.


Alright, but say you have a solid that dissolves 99% into solution, and you are left with only 1% of the original solid, how can one consider the solid's concentration to be constant if only 1% of it is left?..
 
Concentration is already an approximation. Reaction quotient is built using activities of all substances. For diluted solutions activity equals concentration, for solids activity is always 1.

There are several other ways of approaching the problem. They were discussed here on many occasions.
 

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