Gibbs free energy of activation and activation energy

In summary: 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 ?
  • #1
Govind
11
1
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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  • #2
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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  • #3
@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‡
 
  • #4
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
 
  • #5
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
 

What is Gibbs free energy of activation?

The Gibbs free energy of activation is a thermodynamic quantity that represents the difference in Gibbs free energy between the transition state and the reactants in a chemical reaction. It is a crucial factor in determining the rate of the reaction, as it reflects the energy barrier that must be overcome for reactants to convert into products.

How does Gibbs free energy of activation differ from activation energy?

While both Gibbs free energy of activation and activation energy refer to the energy required to initiate a reaction, they differ in their specific definitions and implications. Activation energy primarily refers to the minimum energy needed to break bonds in reactants to form the transition state, usually considered in terms of kinetic molecular theory. Gibbs free energy of activation, on the other hand, includes not only the enthalpic components (like activation energy) but also the entropic components, providing a more comprehensive understanding of the reaction's energy requirements under constant temperature and pressure.

How is Gibbs free energy of activation determined experimentally?

Gibbs free energy of activation can be determined experimentally by measuring the reaction rate at different temperatures and applying the Arrhenius equation or transition state theory. By plotting the natural logarithm of the reaction rate constant against the inverse of the temperature (in Kelvin), a straight line can be obtained. The slope of this line, when multiplied by the negative of the universal gas constant, gives the Gibbs free energy of activation.

What role does entropy play in Gibbs free energy of activation?

Entropy plays a significant role in the Gibbs free energy of activation as it accounts for the disorder or randomness associated with the reactants moving towards the transition state. A positive entropy change indicates an increase in disorder as the reaction progresses towards the transition state, which can lower the Gibbs free energy of activation and facilitate the reaction. Conversely, a negative entropy change suggests a more ordered system, potentially increasing the Gibbs free energy of activation and making the reaction less favorable.

How does the Gibbs free energy of activation affect the rate of a chemical reaction?

The Gibbs free energy of activation is inversely related to the rate of a chemical reaction. A lower Gibbs free energy of activation means that the energy barrier to reach the transition state is lower, leading to a faster reaction rate. Conversely, a higher Gibbs free energy of activation indicates a larger energy barrier, which slows down the reaction rate. This relationship is fundamental in understanding and controlling the kinetics of chemical reactions in various industrial and biological processes.

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