Trouble with Gibbs Free Energy & Equilibrium Constant Calc.

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Discussion Overview

The discussion revolves around the calculation of Gibbs Free Energy and its relationship to equilibrium constants, specifically in the context of chemical reactions. Participants explore the implications of altering the stoichiometry of a reaction on the Gibbs Free Energy and the corresponding equilibrium constant.

Discussion Character

  • Technical explanation
  • Debate/contested

Main Points Raised

  • One participant presents the equation ΔG° = -RT * ln(K) and discusses the calculation of equilibrium constants from Gibbs Free Energy of reactions.
  • There is confusion regarding which ΔG° to use when altering the stoichiometry of the reaction, specifically whether halving the coefficients affects the equilibrium constant.
  • Another participant asserts that changing the coefficients of the reaction does indeed change the equilibrium constant, providing an example with the Haber-Bosch equation and its K values.
  • A later reply corrects the previous claim, stating that dividing the coefficients increases the K-value significantly, suggesting a more complex relationship than initially presented.

Areas of Agreement / Disagreement

Participants express differing views on the impact of changing the stoichiometry of a reaction on the equilibrium constant. There is no consensus on whether the equilibrium constant remains unchanged or is affected by such alterations.

Contextual Notes

Participants mention the units of ΔG° and whether it should be expressed in KJ/mol, indicating a potential area of confusion regarding the interpretation of Gibbs Free Energy in relation to stoichiometric coefficients.

Electric to be
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Hello. A known equation that is useful for calculating equilbrium constants is:

ΔG° = -RT * ln(K)

This is all well and good. Given a standard gibbs free energy of reaction for some given reaction, the equilibrium constant for the reaction can be found.

My trouble is in which ΔG° to use. For example given the following reaction:

N2 + 3H2 ↔ 2NH3 ΔG° = -33.0 KJ

The ΔG° can be calculated by taking the difference of Gibbs Free Energy of formation of each reactant and product, multiplying by the respective stoichiometric constant, and taking the difference.

Then, when I plug in this value for ΔG° I can find a unique equilibrium constant to describe this reaction.My trouble is the following. What's to stop me from halving all constants of the equation and getting this? :

1/2N2 + 3/2H2 ↔ 1NH3 ΔG° = -16.5 KJ

Now, per "mole" of the equation (which is 1/2 N2, 3/2H2 and 1NH3), there is one half of the original Gibb's free energy release. However, this still represents a standard gibbs free energy, by following the same process as before of taking the difference between products and reactants. However, I will certainly get a different value of K. The equilibrium constant should remain the same though, should it not? It shouldn't matter what multiple of the equation have. This is my confusion.As a side question, should ΔG° describing this type of reaction have units of KJ/mol? I know in the Gibbs free energy of formation it is. However, generally when I've seen free energy of reaction written it has only had units of J or KJ, since the moles were multiplied through in the process of finding ΔG°. If it does have KJ/mol units, would 1 "mol" of reaction essentially be 1 mol * each stoichiometric constant of the products and reactants for a given equation?
 
Last edited:
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Electric to be said:
The equilibrium constant should remain the same though, should it not?

\frac{[NH_3]^2}{[N_2][H_2]^3} = \sqrt{ \frac{[NH_3]}{[N_2]^{\frac 1 2}[H_2]^{\frac 3 2}}}
 
Use the ΔGo for the reaction of interest. Changing the coefficients of the reaction does change the reaction kinetics and the equilibrium constant. By dividing the Haber-Bosch equation (N2(g) + 3H2(g) => 2NH3(g)) by 2 effectively doubles the equilibrium constant value of the reaction. The equation which yields 2 moles NH3(g) has a KSTD = 1.64 X 10-6, but dividing by 2 => KNON-STD = 1.28 X 10-3.

[K(2NH3)]½ = [([NH3]2/[N2][H2]3)]½ = [K(NH3)] = [NH3]½/[N2]½[H2]3/2]
 
Correction... Dividing by 2 => increases K-value by ~780x. SBT
 

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