Kinetic vs thermodynamics control

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Discussion Overview

The discussion revolves around the concepts of kinetic and thermodynamic control in chemical reactions, particularly in the context of organic chemistry. Participants explore the implications of these controls on reaction reversibility and the establishment of equilibrium, as well as the interpretations of statements made by an organic chemistry professor regarding these topics.

Discussion Character

  • Debate/contested
  • Conceptual clarification
  • Technical explanation

Main Points Raised

  • Some participants assert that thermodynamic control relates to Gibbs free energy and reversible reactions, while kinetic control pertains to activation energy and irreversible reactions.
  • Others challenge the professor's statements, suggesting that the relationship between kinetic/thermodynamic control and reaction reversibility may be oversimplified.
  • A participant proposes that under thermodynamic control, reactions can establish equilibrium due to sufficient energy to overcome activation barriers in both directions.
  • Another participant questions whether a reaction can be under kinetic control while also occurring under reversible conditions, raising the issue of how to reach thermodynamic products under irreversible conditions.
  • One participant discusses the distinction between controlling the rate of a reaction versus its direction, emphasizing that kinetics relates to speed while thermodynamics relates to the direction and equilibrium of reactions.
  • There is mention of specific examples, such as the H-O fuel cell and H-O explosion, to illustrate the concepts of reversible and irreversible reactions.
  • Some participants express skepticism about the professor's credibility based on his statements regarding microwave ovens and their safety in food preparation.

Areas of Agreement / Disagreement

Participants do not reach a consensus on the professor's statements or the relationship between kinetic and thermodynamic control. Multiple competing views remain regarding the definitions and implications of these concepts in chemical reactions.

Contextual Notes

Participants highlight the complexity of the relationship between kinetic and thermodynamic control, suggesting that the language used by organic chemists may oversimplify the underlying processes. There are also unresolved questions about the conditions under which reactions can be classified as kinetic or thermodynamic.

Delta what
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So I understand that thermodynamics of a chemical reaction is the change in Gibbs free energy and that kinetics mainly deal with the activation energy (or production of a high energy intermediate). My question comes from something that my organic chemistry professor stated in class. He said the thermodynamically controlled reactions were reversible and kinetic controlled reactions are irreversible. Would anyone have any insight on this statement or where I can look to find any info about it.
 
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He's "zero for two," given that you've not misquoted him.
 
He did say that he doesn't use microwave ovens because it's a type of radiation (not a misquote). I don't believe that I misquoted him because I talked to my study group about this (they were in the lecture as well) and they had no idea either.
One thing that I can think of is that when a reaction is under thermodynamic control it can establish an equilibrium because there is enough energy in the system to overcome the activation energy going both ways in the reaction(product to reactant and reactant to product).
Please correct me if I am not correct on that statement!
Also under kinetic control there isn't sufficient energy to overcome the activation energy going form product to reactants and therefore an equilibrium isn't established?
Maybe this is what he was meaning by reversible/ irreversible.
So have I interpreted these types of controls (thermodynamic/ kinetic) correctly?
 
"Microwave ovens?" Photolysis, yes; there're some reactions that can be induced to proceed in higher yields with specific wavelengths of higher energy radiation (well into/beyond visible) than just general thermal excitation (the microwave). But the "kinetic/thermodynamic" arguments are nonsense.
 
The explanation sounds okay to me. Here's another nice explanation of thermodynamic vs kinetic control of reactions: http://www.masterorganicchemistry.com/2012/02/09/can-opener-economics/

Bystander said:
He's "zero for two," given that you've not misquoted him.
Is it possible for a reaction to be under kinetic control if the reaction is occurring under reversible conditions? How can you reach the thermodynamic product if the reaction is occurring under irreversible conditions?
 
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Ygggdrasil said:
Is it possible for a reaction to be under kinetic control if the reaction is occurring under reversible conditions?
H-O fuel cell vs. H-O explosion.
Ygggdrasil said:
How can you reach the thermodynamic product if the reaction is occurring under irreversible conditions?
See last: first is reversible; second is not.
 
What does it mean for a reaction to be under irreversible conditions?When you change the temperature, you can change the direction of the reaction. Like ice and liquid water, though that's not a chemical reaction, the idea is the same. Think heat packs

With kinetic control, you only control the rate of a reaction, not the direction. Like adding an impurity to pure water just below 0 C to initiate nucleation.
A reaction that goes extremely slow to the point that it is approximately an equilibrium, though there is a thermodynamic driving force, you can speed up and make viable/happen at working day time scales.

Important to remember is that kinetics are about rate of reactions i.e. speed. Thermodynamics is about direction in time. Either A goes to B or B goes to A. Where is the equilibrium, where is the Gibbs energy of the reaction zero? At what ratio/concentrations?

You can have an extremely fast reaction that does not happen because it already went from B all the way to A, and the other direction is unfavoured/doesn't produce net entropy. It already found the concentrations of A and B where the Gibbs energy is minimized. Think acid-base reactions. Those proton shifts are fast, near diffusion speed. But they go one direction, not the other, even though the reaction going in either way would happen at diffusion speed rates. Change concentrations and it will be fast, in the reverse direction. Think acid-base solutions with ph indicators where you add acid or base, go through a pH gradient and see all colour changes instantly.

You can have an extremely slow reaction that produces tons of energy. Like a bunch of TNT just sitting there, not decomposing and delivering that sweet entropy. Or diamond turning into graphite.

So kinetics and thermodynamics are completely orthogonal.
See last: first is reversible; second is not.

But both are the same reaction. In one you do work on the system, in the other you waste all the work you could be doing by making it all go into heat.Every reaction is reversible. Some just mean you need to go to very extreme concentrations or temperatures/pressures.
 
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I have a sneaking suspicion that my prof sometimes spews b.s.. This is why I mentioned the microwave thing. However, I confused the statement. He was saying to not use microwave ovens on your food because it was unsafe to the consumer of that food. From what I understand and what the evidence backs up is that microwave ovens are safe to use on food and if made properly are safe to use.
 
Bystander said:
H-O fuel cell vs. H-O explosion.
See last: first is reversible; second is not.

Both give the same product, so the kinetic product and thermodynamic product are the same.

Anyway, talking about reactions being under kinetic/thermodynamic control and reactions being reversible/irreversible probably oversimplifies things, but this is the language organic chemists use to talk about competing reaction pathways such as the one discussed in the link I posted earlier.
 
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