Q value with species in different states

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Discussion Overview

The discussion centers around the setup of the reaction quotient (Q) for a specific half-reaction involving water and oxygen, particularly addressing the treatment of species in different states (liquid, gas, and aqueous). Participants explore how to express Q, the implications of using different units for pressure, and the relationship between Q and the equilibrium constant (K).

Discussion Character

  • Technical explanation
  • Debate/contested
  • Conceptual clarification

Main Points Raised

  • One participant asks how to set up the Q equation for the half-reaction, questioning whether to include the partial pressure of oxygen gas and how to handle different states.
  • Another participant suggests that it is acceptable to express the partial pressure of oxygen in bars and concentrations in M, noting that mixing states is a common approximation of activity.
  • A participant expresses confusion about using bars instead of atm for pressure in the Q equation, seeking clarification on the reasoning behind this convention.
  • There is a mention that Q is the reaction quotient and K is the equilibrium constant, with a participant noting the convenience of treating them separately.
  • One participant highlights that the Nernst equation is derived under the assumption of electrochemical equilibrium, implying that Q should equal K in that context.
  • Another participant points out that in slowly reacting systems, Q does not equal K initially, suggesting that introducing Q helps clarify the dynamics of the reaction.

Areas of Agreement / Disagreement

Participants express differing views on the appropriate units for pressure in the Q equation and the relationship between Q and K. There is no consensus on the best approach to setting up the Q equation or the implications of using different units.

Contextual Notes

Some participants mention limitations in their understanding of fugacity and the conventions used in expressing pressures, indicating that there may be unresolved assumptions regarding the treatment of gaseous species in the reaction quotient.

Who May Find This Useful

This discussion may be useful for students and practitioners in chemistry and related fields who are exploring the concepts of reaction quotients, equilibrium constants, and the implications of different units in chemical equations.

MathewsMD
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Given the half reaction:

2H2O(l) → O2(g) + 4H+(aq) + 4e-

How would you set up the Q equation for this reactions?

Would it be Q = [H+]4 only or do we assume the partial pressure of oxygen gas is 1 atm? Is there a general way to write the Q value for species in different states?
 
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Typically we will just express the partial pressure of the oxygen in bars and concentration in M. No problem with mixing states, as technically these are just approximations of the activity.
 
Borek said:
Typically we will just express the partial pressure of the oxygen in bars and concentration in M. No problem with mixing states, as technically these are just approximations of the activity.

Oh really? My class didn't delve too deeply into fugacity, but I was told when assigning partial pressure values in the Q equation, to ensure units were always in atm. I wasn't told exactly why, but why do you say to use bars? Do you mind referring me to a derivation or reasoning perhaps?

Also, in my class, the professor completed an example where he solved for Q but omitted the gaseous species involved since it was a half-reaction in a voltaic cell. It was not at standard conditions, though. Is it reasonable to assume the partial pressure was 1atm, though?
 
What is Q? I only see people talking about Q recently in this forum? Is there a new book which decided to use Q instead of K?
 
Q is the reaction quotient, K is the equilibrium constant. I found it is convenient to treat them separately, as they are not always identical.
 
MathewsMD said:
Oh really? My class didn't delve too deeply into fugacity, but I was told when assigning partial pressure values in the Q equation, to ensure units were always in atm. I wasn't told exactly why, but why do you say to use bars?

This is just a convention. Pressure should be in bar, since 1982. atm was an earlier standard.

Sorry, there are some problems with IUPAC servers and I can't trace it right now to any acceptable source, have it just on disk in a private discussion with people I trust.
 
Borek said:
Q is the reaction quotient, K is the equilibrium constant. I found it is convenient to treat them separately, as they are not always identical.
Ok, reaction quotient was new to me as a concept. I still don't see what it is good for. What I want to say is that the Nernst equation is derived for an electrochemical equilibrium situation, so Q=K.
 
When you mix some slowly reacting reagents Q doesn't equal K - it gets there, but slowly. Without introducing Q it is difficult to explain how come we have a solution in which... K doesn't equal K? But you can easily say Q doesn't equal K and the situation is clear.
 
Borek said:
This is just a convention. Pressure should be in bar, since 1982. atm was an earlier standard.

Sorry, there are some problems with IUPAC servers and I can't trace it right now to any acceptable source, have it just on disk in a private discussion with people I trust.

Okay, thanks for the help. If you ever do find the source you could link me to, that would be great!
 

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