Equilibrium Constant and Gibbs Energy

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Discussion Overview

The discussion revolves around the relationship between the equilibrium constant (K) and Gibbs free energy (ΔG), specifically addressing whether K refers to Kc or Kp. Participants explore the implications of this relationship in the context of thermodynamics and chemical equilibria.

Discussion Character

  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant states that ΔG = -RT ln K, but questions whether K should be Kc or Kp, noting the relationship Kp = Kc(RT)Δn.
  • Another participant argues that the initial equation should include ΔG° and that K should specifically refer to Kp, not Kc.
  • A later reply reiterates the need for ΔG° and emphasizes that Kp should involve only partial pressures, challenging the initial claim.
  • One participant acknowledges the relationship between Kp and Kc but questions the derivation and definitions involved.
  • Another participant mentions that K in the ΔG equation involves activities rather than concentrations or partial pressures, referencing ideal systems.

Areas of Agreement / Disagreement

Participants express differing views on the definitions and relationships between Kc and Kp, with no consensus reached on the correct interpretation of the equations involved.

Contextual Notes

There are unresolved assumptions regarding the definitions of standard states and the derivation of the relationships between ΔG and the equilibrium constants. The discussion also highlights potential confusion over the roles of activities versus concentrations in the context of ideal systems.

laser1
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We have that ##\Delta G = -RT\ln K##. This is in my lecture notes. However, it does not specify whether ##K## is ##K_c## or ##K_p##. Fair enough, I assumed that it could be both. However, when writing out the definitions of ##K_p## and ##K_c##, and using the fact that ##P=CRT##, where ##C## is the concentration, defined as ##n/V##, I noted the fact that ##K_p=K_c(RT)^{\Delta n}##.

So let's say $$\Delta G = -RT\ln K_p = -RT\ln K_c$$ It is clear that this equation cannot be true, right? As you get an extra factor of ##-RT\Delta n \ln(RT)## on one side. Where am I going wrong?
 
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You are going wrong in a number of places. First of all, in your initial equation, you should have ##\Delta G^0##, the free energy change between the standard states of reactants and products. Secondly, in your equation, you should have ##K_P##, nor ##K_C##. Third, the expression for ##K_P## should involve only partial pressures (in bars) and not ##\Delta n##.
 
Chestermiller said:
You are going wrong in a number of places. First of all, in your initial equation, you should have ##\Delta G^0##, the free energy change between the standard states of reactants and products. Secondly, in your equation, you should have ##K_P##, nor ##K_C##. Third, the expression for ##K_P## should involve only partial pressures (in bars) and not ##\Delta n##.
Thanks for the reply.

1. Fair enough.
2. Okay, so the ##K## in the formula refers to ##K_p##, NOT ##K_c##. Can you provide some insight on this? Or is it just by definition.
3. Are you sure? book states that ##K_p=K_c(RT)^{\Delta n}##.
 
laser1 said:
Thanks for the reply.

1. Fair enough.
2. Okay, so the ##K## in the formula refers to ##K_p##, NOT ##K_c##. Can you provide some insight on this? Or is it just by definition.
You need to review the derivation of the relationship between ##\Delta G^0## and ##K_P##
laser1 said:
3. Are you sure? book states that ##K_p=K_c(RT)^{\Delta n}##.
Your relationship between Kp and Kc is correct, if R is expressed in Joules/mole-K.
 
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Note that K in the Delta G equation involves the activities, not the concentrations or partial pressures. In ideal systems #c/c^o=p/p^o#
 

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