Gibbs free energy and equilibrium constant at a high T

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SUMMARY

The discussion centers on the relationship between Gibbs free energy (ΔG) and the equilibrium constant (Keq) at high temperatures. It is established that when ΔG is negative and ΔS is positive, ΔG becomes increasingly negative as temperature (T) rises, favoring product formation. However, the equilibrium constant equation, Keq = e^(-ΔG/TR), suggests that at very high temperatures, Keq approaches 1, indicating equal concentrations of products and reactants. This apparent contradiction is clarified by recognizing that the change in Keq with temperature is influenced by the sign of ΔH, as detailed in the Van 't Hoff equation.

PREREQUISITES
  • Understanding of Gibbs free energy and its equation (ΔG = ΔH - TΔS)
  • Familiarity with the concept of entropy (ΔS) and its role in thermodynamics
  • Knowledge of the equilibrium constant (Keq) and its mathematical representation
  • Basic grasp of the Van 't Hoff equation and its implications in chemical equilibria
NEXT STEPS
  • Study the Van 't Hoff equation in detail to understand temperature dependence of equilibrium constants
  • Explore the implications of ΔH and ΔS on chemical reactions at varying temperatures
  • Investigate the relationship between Gibbs free energy and spontaneity of reactions
  • Examine case studies of reactions with varying ΔH and ΔS to see practical applications of these concepts
USEFUL FOR

Chemistry students, researchers in thermodynamics, and professionals in chemical engineering who seek to deepen their understanding of reaction equilibria and thermodynamic principles.

gmianosi
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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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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.
 

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