Gibbs free energy of activation and activation energy

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Discussion Overview

The discussion revolves around the concepts of Gibbs free energy of activation and Arrhenius activation energy in the context of chemical reactions. Participants explore the relationship between these energies, their definitions, and their implications for reaction kinetics and thermodynamics.

Discussion Character

  • Debate/contested
  • Conceptual clarification
  • Technical explanation

Main Points Raised

  • One participant suggests that the activation energy (Ea) required for a reaction to proceed is represented by the Gibbs free energy of activation (ΔG‡) rather than the Arrhenius activation energy.
  • Another participant notes that the Arrhenius activation energy is an empirical construct derived from the relationship between reaction speed and temperature, emphasizing that ΔG is temperature-dependent.
  • A participant questions the necessity of distinguishing between Ea and ΔG‡, seeking clarity on which energy value is required to initiate a reaction.
  • It is mentioned that the Gibbs free energy change indicates whether a reaction is spontaneous, while kinetics relates to the speed of the reaction without addressing the final state.

Areas of Agreement / Disagreement

Participants express differing views on whether the activation energy required for a reaction is best represented by ΔG‡ or Ea. There is no consensus on which energy value is more relevant for initiating reactions, indicating ongoing debate.

Contextual Notes

Participants reference the temperature dependence of both ΔG and the pre-factor in the Eyring equation, which may complicate the comparison between ΔG‡ and Ea. The discussion highlights the interplay between thermodynamics and kinetics without resolving the distinctions between the two concepts.

Govind
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Let's consider a reaction A (reactant) -> B(product) and activated complex is denoted by C.

DPB_PHY_CHM_IX_C08_E01_295_Q01.png


This graph ( potential energy vs reaction coordinate ) tells us that reactant need some amount of activation energy (Ea) to convert in product, which has low potential energy which is shown here in terms of enthalpy ∆H. We can assume from this graph that activation represent same kind of potential energy between A (reactant) and C (activated complex ) that Enthalpy ∆H represent between A and B (product).

Now look at another graph of reaction (Gibbs free energy vs extent of reaction)

images.jpeg


This graph represents that activation energy is difference between Gibbs free energy of reactant and activated complex or there is also possibility that the activation energy shown here is not arrhenius activation energy Ea but it is Gibbs energy of activation ΔG‡ according to transition state theory.

Q. But to perform a reaction what amount of energy we need to supply to reactants arrhenius activation energy Ea or gibbs free energy of activation ΔG‡ ? I think it's ΔG‡ as defination of Gibbs free energy states - minimum amount of work needed to supply for a non spontaneous reaction (here A -> C ) to be happened but then why arrhenius theory states that - for reactants to transform into products, they must first acquire a minimum amount of energy, called the activation energy Ea ?

And also what these two energies represent physically in terms of bonds , interatomic interactions etc ?

Mathematical equations -

ΔG‡ = ∆H‡ - T∆S‡

ΔG‡ = Ea - RT - T∆S‡ ( ∆H‡ = Ea - RT )
 
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Arrhenius activation energy is an empirical construct from regression of reaction speed vs inverse Temperature. The point is that Delta G is itself a function of T, so that changing the temperature will not only have an explicit effect via change of 1/T but also an effect due to the temperature dependence. Also the pre-factor in the Eyring equation is temperature dependent. All this dependence on temperature makes up for the difference between Delta G in the Eyring equation and E_A in the Arrhenius equation. A similar dependence of the equilibrium constant on inverse temperature is known as van't Hoff equation.
 
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@Lord Jestocost I was actually asking that to perform a reaction what amount of energy we need to supply to reactants arrhenius activation energy Ea or gibbs free energy of activation ΔG‡
 
DrDu said:
Arrhenius activation energy is an empirical construct from regression of reaction speed vs inverse Temperature. The point is that Delta G is itself a function of T, so that changing the temperature will not only have an explicit effect via change of 1/T but also an effect due to the temperature dependence. Also the pre-factor in the Eyring equation is temperature dependent. All this dependence on temperature makes up for the difference between Delta G in the Eyring equation and E_A in the Arrhenius equation. A similar dependence of the equilibrium constant on inverse temperature is known as van't Hoff equation.
I was actually asking that to perform a reaction what amount of energy we need to supply to reactants arrhenius activation energy Ea or gibbs free energy of activation ΔG‡

Reference: https://www.physicsforums.com/threa...n-and-activation-energy.1054511/#post-6921068
 
Thermodynamics tells us that a reaction should go if the products are more stable (have a lower free energy) than the reactants – the reaction has a negative free energy change. Kinetics, on the other hand, tells us how fast the reaction will go, though doesn't tell us anything about the final state of things once it gets there.

Have a look at “Kinetics vs. Thermodynamics” from the University of Utah:

Lecture 1: Kinetics vs. Thermodynamics: different but related
 

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