Gibbs free energy and equilibrium constant at a high T

In summary, the conversation discusses how the definitions of ΔG and Keq seem to contradict each other when considering the effects of temperature. While ΔG becomes more negative as temperature increases, Keq seems to approach a smaller value. However, the Van 't Hoff equation shows that the change of Keq with T depends on the sign of ΔH, providing a possible explanation for the apparent contradiction.
  • #1
gmianosi
9
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 :)
 
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  • #2
Without getting into any other arguments - Keq doesn't go to 1.

[tex]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}}[/tex]
 
  • #3
Borek said:
Without getting into any other arguments - Keq doesn't go to 1.

[tex]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}}[/tex]
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.
 
  • #6
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.
 

FAQ: Gibbs free energy and equilibrium constant at a high T

What is Gibbs free energy?

Gibbs free energy, also known as Gibbs function, is a thermodynamic quantity that measures the amount of energy available to do useful work in a system at a constant temperature and pressure. It takes into account both the enthalpy (heat content) and entropy (measure of disorder) of a system.

How is Gibbs free energy related to equilibrium constant?

The relationship between Gibbs free energy and equilibrium constant is given by the equation: ΔG = -RTlnK, where ΔG is the change in Gibbs free energy, R is the gas constant, T is the temperature, and K is the equilibrium constant. This equation shows that as the equilibrium constant increases, the change in Gibbs free energy becomes more negative, indicating a more favorable reaction.

What is the significance of a high temperature in relation to Gibbs free energy and equilibrium constant?

At a high temperature, the term -RTlnK becomes smaller, meaning that the change in Gibbs free energy becomes less negative. This indicates that the reaction is less favorable and the equilibrium constant is closer to 1. In other words, the higher the temperature, the less stable the system is and the more likely it is to shift towards equilibrium.

How does Gibbs free energy and equilibrium constant affect the spontaneity of a reaction?

A negative change in Gibbs free energy indicates that a reaction is spontaneous, meaning it will occur without any external intervention. Similarly, a high equilibrium constant also indicates a spontaneous reaction. Therefore, the relationship between these two quantities can determine the spontaneity of a reaction at a given temperature.

Can Gibbs free energy and equilibrium constant be used to predict the direction of a reaction?

Yes, Gibbs free energy and equilibrium constant can be used to predict the direction of a reaction. A negative ΔG and a high K value indicate a forward reaction, while a positive ΔG and a low K value indicate a reverse reaction. At equilibrium, ΔG = 0 and K = 1, indicating that the forward and reverse reactions occur at equal rates.

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