Gibbs free energy and equilibrium constant at a high T

Click For Summary

Discussion Overview

The discussion revolves around the relationship between Gibbs free energy (ΔG), entropy (ΔS), and the equilibrium constant (Keq) at high temperatures. Participants explore how these concepts interact and the apparent contradictions that arise when considering their definitions and implications.

Discussion Character

  • Debate/contested
  • Technical explanation
  • Conceptual clarification

Main Points Raised

  • One participant notes that with ΔG<0 and ΔS>0, ΔG becomes increasingly negative as temperature rises, suggesting a stronger favoring of products over reactants.
  • Another participant challenges the claim that Keq approaches 1 at high temperatures, providing a mathematical expression for Keq that indicates it does not necessarily equal 1.
  • A later reply acknowledges the correction but expresses confusion about how Keq decreases while ΔG becomes more negative, indicating a lack of clarity on the relationship between these variables.
  • Links to the Van 't Hoff equation are shared, suggesting it may provide insight into the temperature dependence of Keq.
  • One participant asserts that the change of K with T is dependent on the sign of ΔH, aligning with earlier arguments made in the thread.

Areas of Agreement / Disagreement

Participants do not reach a consensus, as there are competing views on the behavior of Keq and its relationship with ΔG at high temperatures. The discussion remains unresolved regarding the apparent contradictions between the two concepts.

Contextual Notes

There are limitations in the discussion, including assumptions about the behavior of ΔG and Keq at high temperatures, and the dependence on the sign of ΔH, which are not fully explored or clarified.

gmianosi
Messages
9
Reaction score
0
I posted this earlier, but I just realized it might have been in the wrong section. Sorry

Okay, so consider you have system in which ΔG<0 and ΔS>0. Using Gibbs free energy (ΔG=ΔH-TΔS), you'll know that it will always be negative. As the temperature increases, it will actually become more and more negative. This means that as the temperature increases to a higher T, ΔG will become even more negative. making the system favor products much more than reactants.

Now consider the equation for the equilibrium constant, Keq=e^-ΔG/TR. Using this definition, as T gets very high, Keq seems to be going to 1, meaning that there will be an equal amount of product and reactants at a very high temperature.

These two definitions are both correct, yet they seem to contradict one another. Why is that? I feel like I'm missing something very definition based.

Thanks in advance to anyone who helps :)
 
Chemistry news on Phys.org
Without getting into any other arguments - Keq doesn't go to 1.

K_{eq} = e^{\frac {-\Delta G}{TR}} = e^{\frac {-(\Delta H - T\Delta S)}{TR}} = e^{\frac {-\Delta H}{TR}}e^{\frac {\Delta S}{R}}
 
Borek said:
Without getting into any other arguments - Keq doesn't go to 1.

K_{eq} = e^{\frac {-\Delta G}{TR}} = e^{\frac {-(\Delta H - T\Delta S)}{TR}} = e^{\frac {-\Delta H}{TR}}e^{\frac {\Delta S}{R}}
Oh wow, I can't believe I did that. Thank you.
But still, Keq seems to be going to a smaller value, while ΔG is becoming more negative, which doesn't make sense.
 
It shows that the change of K with T depends on the sign of ##\Delta H##. This is in line with the argument of Borek.
 

Similar threads

  • · Replies 4 ·
Replies
4
Views
4K
  • · Replies 3 ·
Replies
3
Views
3K
  • · Replies 15 ·
Replies
15
Views
12K
  • · Replies 9 ·
Replies
9
Views
2K
  • · Replies 1 ·
Replies
1
Views
2K
  • · Replies 4 ·
Replies
4
Views
2K
  • · Replies 3 ·
Replies
3
Views
3K
  • · Replies 11 ·
Replies
11
Views
3K
  • · Replies 8 ·
Replies
8
Views
3K
  • · Replies 13 ·
Replies
13
Views
3K