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My lecture notes state the following (albeit in a very hand-wavy way):

If we are gentle and careful however, we can change the state of the system slowly, making sure that while the state is changing (e.g. its P and V is changing with time), it remains in equilibrium. Hence the state travels around its state space, remaining in equilibrium at every point such a process is called reversible.

However, I also found information that says a system with internal temperature variations is not in equilibrium. Are these two pieces contradictory, or am I missing something obvious? What are the conditions for stable equilibrium in a reversible process?

Qmechanic
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3 Answers3

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Here's maybe a different answer with some equations. I don't think your two statements are contradictory, because they are too (as you say) ``hand-wavey'' to be definitive. I think establishing a bit of the thermodynamics (equilibrium statistical mechanics) and non-equilibrium statistical mechanics is necessary to give proper definitions which show there is no contradiction between "[we can] state of the system slowly, making sure that while the state is changing (e.g. its P and V is changing with time), it remains in equilibrium" and "a system with internal temperature variations is not in equilibrium".

Within thermodynamics, pressure P(n,T) is a function of the number density $n=N/V$ and the temperature $T$ (e.g. ideal gas law $P=nT$). this known as an equation of state. Further, there are many known relations between thermodynamic variables and such relations can be arrived at via Maxwell Relations for a given ensemble (e.g. cannonical ensemble). In short, changing one quantity may mean another quantity is changed.

Using statistical mechanics, we can define these thermodynamic variables in terms of a phase space distribution $f(x,v,t)$ cite. They are given $$n(x,t) = \int dv f(x,v,t),$$ $$u(x,t) = \frac{1}{n}\int dv \, v f(x,v,t),$$ $$T(x,t) = \frac{m}{3n} \int dv \, (v-u)^2 f(x,v,t),$$ $$\overset\leftrightarrow{P}(x,t) = m \int dv \, (\vec{v}-\vec{u}) \otimes (\vec{v}-\vec{u}) f(x,v,t).$$ Since every quantity explicitly depend on $f$, changes in density, $\partial_t n(x,t)$, temperature $\partial_t T(x,t)$, etc... are defined by $\partial_t f(x,v,t)$. The main take away is that.. we can talk about all of them at the same time, by speaking of $\partial_t f(x,v,t)$.

Okay now show there is now contradiction and hence answer your question... "What are the conditions for stable equilibrium in a reversible process?". The conditions are that entropy is not being generated. We know that Boltzmann entropy is $$S = \int dx dv \, f(x,v,t) \log (f(x,v,t))$$ and so entropy generation is defined as $$\partial_t S = \int dx dv \, \partial_t f(x,v,t) \left( \log (f(x,v,t)) + 1 \right) $$ So if we have $\partial_t f(x,v,t)$ such that $\partial_t S = 0$ then we can change the density, temperature, pressure, etc.. and keep the system in ``equilibrium''.

Having established a definition of equilibrium, I want to revisit the claim that 'a system with internal temperature variations is not in equilibrium'. This is a misleading heuristic because entropy generation can manifest changes in the temperature, but the temperature can also change without entropy being generated. To get a full picture of this, consider $\partial_t f$ in an ideal gas system, such that entropy is generated ($\partial_t S \geq 0$). Eventually entropy will maximize and the particles will have a Gaussian velocity distribution. (also discussed here). The temperature defines the width of that Gaussian (variance of particle velocity). So maybe temperature change occurs because of entropy generation that changes the variance of the velocity distribution, but this is not the only way that the velocity distribution variance can change (see Vlasov equation) and so changes in temperature need not imply that entropy is being generated.

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The two statements refer to very different situations and descriptions/approximations. A system in equilibrium is characterized by a temperature, pressure, and other parameters which do not vary - the system is assigned a specific scalar value for each of those. If the system is not in equilibrium, talking about its temperature simply doesn't make sense...

...however, one would often speak of a macroscopic volume of, a liquid or gas as a system that can be considered to be in equilibrium, but the parameters of the adjacent volumes are different, varying smoothly through space. In this case we speak of local equilibrium, but the whole system is not in equilibrium, because the adjacent volumes can exchange energy and will continue exchanging energy until their temperatures (as well as pressures, etc.) equilibrate.

Returning to the definition of a quasistatic process - here we speak about changing the parameters in time (not in space.) Of course, in practice changing parameter in time involves its spatial variation - e.g., if we heat a wall of a container, it takes time for the temperature gradient to propagate through the system. I.e., there is some degree of non-equilibrium. The point is that for very slow change, the the effects of this non-equilibrium (such as an increase of temperature) are negligible - so that we can retrace the change to its initial state, and return to the state very close to the initial one - the closer the slower is the process.

Roger V.
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However, I also found information that says a system with internal temperature variations is not in equilibrium. Are these two pieces contradictory, or am I missing something obvious?

They are referring to finite temperature variations. If the temperature variations are infinitesimal, there is no conflict with the quoted statement. Infinitesimal temperature variations (as well as infinitesimal pressure and volume variations, if applicable) will exist if the change in the system occurs "very slowly", as stated. (There should be the additional stipulation that there is no friction).

Hope this helps.

Bob D
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