Sunday, 11 October 2015

thermodynamics - Is there a quasistatic process that is not reversible?


I have seen several questions and good answers on the link between reversible and quasistatic processes, such as here or here. However, these questions only adress one side of the problem : a reversible process is necessarily quasistatic.


I am interested in the other side of the equivalence : is there a process that is quasistatic, yet not reversible ? It looks to me that an irreversible process cannot be made perfectly quasistatic.


The wikipedia article about quasistatic processes takes as an example the very slow compression of a gas with friction. As the compression occurs very slowly, the transformation is quasistatic, and the friction makes it irreversible. I am not convinced by this example : if you press on the piston with a vanishingly small force you will have to reach the threshold of the Coulomb law for solid friction before moving the piston anyway. It makes the process non-quasi-static, however small the Coulomb threshold might be.



Another example I've heard of is the reaction between a strong acid and a strong base. It is always an irreversible process, and you could make it quasistatic by adding very small drops of base into acid at a time. But by trying to do that, you would inevitably reach a limit to the size of the drop imposed by surface tension.


Even if "reversible" and "quasistatic" mean very different things, is it true to consider that in practice, a reversible process and a quasistatic process is essentially the same thing ?



Answer



Most quasi-static processes are irreversible. The issue comes down to the following: the term quasi-static applies to the description of a single system undergoing a process, whereas the term irreversible applies to the description of the process as a whole, which often involves multiple interacting systems.




  • In order to use the term quasi-static, one has to have a certain system in mind. A system undergoes a quasi-static process when it is made to go through a sequence of equilibrium states.




  • A process is irreversible if either (a) the system undergoes a non-quasi-static process, (b) the system undergoes a quasi-static process but is exchanging energy with another system that is undergoing a non-quasi-static process, or (c) two systems are exchanging energy irreversibly, usually via heat flow across a finite temperature difference.





One can imagine a (admittedly idealized, as most of basic thermodynamics in physics) process in which two systems undergo quasi-static processes while exchanging energy via heat due to a finite temperature difference between them. The irreversibility comes about due heating due to the temperature difference between them rather than due to irreversibilities inside each system.


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