Equilibrium Constant and Gibbs Energy

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SUMMARY

The discussion centers on the relationship between Gibbs free energy change (ΔG) and equilibrium constants (K) in chemical reactions, specifically addressing the distinction between Kp and Kc. It is established that the correct form of the equation is ΔG° = -RT ln Kp, where K refers specifically to Kp, not Kc. The relationship Kp = Kc(RT)Δn is confirmed, emphasizing that Kp should involve partial pressures and not concentrations. Misunderstandings in the application of these concepts are clarified, particularly the importance of using ΔG° for standard states.

PREREQUISITES
  • Understanding of Gibbs free energy and its significance in thermodynamics.
  • Familiarity with equilibrium constants, specifically Kp and Kc.
  • Knowledge of the ideal gas law and its application in chemical reactions.
  • Basic grasp of standard states in thermodynamic equations.
NEXT STEPS
  • Review the derivation of the relationship between ΔG° and Kp.
  • Study the definitions and applications of Kp and Kc in chemical equilibria.
  • Explore the implications of using activities versus concentrations in thermodynamic equations.
  • Investigate the ideal gas law and its relevance to calculating Kp from Kc.
USEFUL FOR

Chemistry students, educators, and professionals involved in thermodynamics and chemical equilibria, particularly those focusing on the application of Gibbs free energy in reaction mechanisms.

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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