Question involving REDOX REACTIONS and EQUILIBRIUM?

2016-10-18 7:02 pm
My main question is surrounded by triple asterisks below (and I care about its answer the most of all the questions I asked), but I ask other related questions throughout my post.

From link 2:
(i) At dynamic equilibrium, reactants are converted to products and products are converted to reactants at an equal and constant rate.
(ii) Static equilibrium occurs when all particles in the reaction are at rest and there is no motion between reactants and products. [What if the only particles in the reaction that move are electrons (as opposed to atoms)? That counts as "motion between reactants and products", right?]

From link 3:
Redox (short for reduction–oxidation reaction) is a chemical reaction in which the oxidation states of atoms are changed (which, if I'm correct, implies MANDATORY motion of electrons, by definition).

So, if a redox reaction requires electron motion and electron motion of a redox reaction does indeed count as motion between reactants and products, then redox reactions should ALWAYS have motion between reactants and products, right?

Someone has told me that a redox reaction with a potential of 0 means the system in question is in equilibrium, so, ***must redox reactions with a potential of 0 ALWAYS be in dynamic equilibrium (as opposed to static equilibrium), or can they also be in static equilibrium?***

If I'm wrong (anywhere in this post, but especially with my main question), please correct me.

Any input would be GREATLY appreciated!
更新1:

Links I found that I liked (but I still need help, despite having them): 1) http://www.ausetute.com.au/redoxspon.html 2) http://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Equilibria/Chemical_Equilibria/Principles_of_Chemical_Equilibria/Dynamic_equilibrium 3) https://en.wikipedia.org/wiki/Redox

回答 (2)

2016-10-18 7:07 pm
All chemical equilibria are dynamic equilibria. There are no static equilibria in chemical systems.
2016-10-18 7:49 pm
if there is no interaction between reactants and products, that is not equilibrium. Stasis is not equilibrium. Equilibrium is a dynamic condition. Static equilibrium, at least in terms of chemical reactions, is a false concept, an oxymoron. Even the example given on your link is incorrect: graphite to diamond will never actually and truly see every single carbon atom stuck in the diamond phase. There will always be an occasional atom that vibrates out of the diamond structure. Nothing is actually fixed in place permanently at 100% probability, because when we are discussing 10^25 atoms (which is a tiny amount), it is effectively impossible that not one of those will be in process of breaking its bonds with its near neighbors.

You cannot have "no movement" in a real system, except at absolute 0, and absolute 0 is not achievable.

The concept of "static" equilibrium is a mechanical one, not a physicochemical one. It does not apply to chemistry. Even rock has a vapor pressure, and if there is a vapor pressure that means that none of the liquid or solid phases is permanent, "static". You cannot shake an atom out of its structural surroundings and pretend that the system is unchanging, and there is ALWAYS some atom or another at the interface of the substance which will get kicked out into the "Not part of this substance".

The problem with the concept of "static" equilibrium is that it is a macro-scale term that ignores real processes on the micro-scale, and thus assumes, falsely, that lack of perceptible (measurable) change is not due to a failure to measure things at the appropriate scale, but is instead due to an absence of change. There is change, even if it is minuscule (both literally and metaphorically).

This brings me to the concept of motion and your questions about it. The issue here, based on the description of "static equilibrium" in your link, is that the idea of motion refers to atoms but you wish it to include electrons, which are not atoms. It may be that there is a trivial back-reaction when a condition so favors the formation of a product over the reactant that the reaction is what would typically be termed unidirectional (rather than "static" equilibrium), but this does not mean that the electrons ever stop moving. You need to ignore that very concept of "motion" and lack thereof, because, as I said previously, no motion (no kinetic energy) can only occur at absolute 0 and that is not ever going to happen.

A redox potential of 0 means that there is no electromotive force driving the preferential migration of electrons from one phase to another. It is not a definition of equilibrium, it is a sign of it. Redox potential is a voltage (a measurement of electromotive force or electrical potential).

I hope this helps, but I suspect that the idea of static equilibrium has been promoted via what you would consider a reasonably qualified or competent source and thus you will not accept that there is no such thing. But there is no such thing and no chemist that I have ever worked with would defend the term.


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