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I know in an isolated system entropy always tends to increase, but what about the speed of that increase (e.g. the acceleration of entropy-the derivative of its speed)? Is there any law or relation giving the rate of that increase? Can it be decreased? (I am not asking here about a way to decrease entropy itself but its rate of increase-is it always increasing, too, is it constant, or can it be decreased?) Also, is there any difference in the answer of the question if it is asked for isolated and for non-isolated (both closed and open) systems?

Can anybody show me any links to work done on the subject? Or if there isn't any such work explain me what are the reasons why nobody has tackled the issue up until now (e.g. impossibility of experimental verification, lack of theoretical framework to put the question in, difficulty to make a sound mathematical model and so on)?

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  • $\begingroup$ I believe your first statement should say "isolated system". A closed system can exchange heat with its surroundings, so it can be cooled and experience a decrease in entropy (although this might just be different definitions). $\endgroup$
    – John
    Commented Mar 3, 2017 at 21:11
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    $\begingroup$ In addition, the entropy will not increase indefinitely. It will reach a maximum eventually, so I guess a quick answer to your question is that yes, the rate of increase will eventually decrease to zero. $\endgroup$
    – John
    Commented Mar 3, 2017 at 21:12
  • $\begingroup$ Thank you for the remark, I will correct it in a minute. Just wait a little bit. The mistake is on my side. $\endgroup$ Commented Mar 3, 2017 at 21:15
  • $\begingroup$ Is it better now? $\endgroup$ Commented Mar 3, 2017 at 21:20
  • $\begingroup$ Entropy is only always increasing for isolated systems. There is no such restrictions on entropy if your system is either open or closed. Also, I have just said that the rate of increase will decrease to zero eventually. $\endgroup$
    – John
    Commented Mar 3, 2017 at 21:26

4 Answers 4

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From a thermodynamical point of view, you may consider the following: 1) Entropy is only defined for a system in the state of equilibrium. 2) An isolated system in equilibrium cannot depart from it spontaneously. Therefore, the entropy of an isolated system is constant.

From a quantum mechanical point of view: the Von Neumann entropy is invariant under unitary transformations, and since time evolution for isolated systems is unitary, the entropy remains constant.

However, I understand your question. Imagine a bottle with some gas trapped inside that you might prepare as an isolated system in equilibrium with an entropy $S_1$. Then, if the gas is released to let fill the entire room, after some time, it will reach again the equilibrium with an entropy $S_2>S_1$. As I said before, you can only have entropy at the initial and the final states, because there is no equilibrium intermediate state, therefore there's no rate of change in the entropy. In addition, that system had changed its entropy because it wasn't isolated, there had to be some external agent to open the bottle. Right?

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  • $\begingroup$ Actually I am trying to ask (I seem to have problem editing my question), if there is a system where entropy is increasing (due to the flow of energy and/or matter) can there be a model where the rate of this entropy increase is decreasing while the flow is continuing with the same rate-can there be some mechanism able to in a way "counter" the increase of entropy and allow the system to accumulate more Gibbs free energy in itself? Or is the Gibbs free energy always destined to decrease in time? $\endgroup$ Commented Mar 3, 2017 at 21:45
  • $\begingroup$ Gibbs free energy is enthalpy minus unavailable energy due to entropy and which is due to volume. So it can achieved by helmholtz free energy, by doing mechanical work which reverse the system, also by extracting heat which further lowers internal energy. So gibbs energy after all this is adding more particles, by introducing more fuel for enthalphy. So mechanism is mechanical work that makes system reversible. $\endgroup$ Commented Nov 17, 2022 at 2:54
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    $\begingroup$ There is a large class of non-equilibrium states in which the entropy is well-defined from thermodynamics. This is the class where the system can be regarded as a set of regions each in internal equilibrium but not necessarily in equilibrium with each other. It is well known that the entropy of an isolated system (not already in internal equilibrium) need not be constant and usually is not. $\endgroup$ Commented Dec 28, 2023 at 16:38
  • $\begingroup$ "Entropy is only defined for a system in the state of equilibrium." -- this is completely wrong. $\endgroup$
    – Paul
    Commented Aug 27 at 12:12
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In the absence of mass transfer, the local rate of generation of entropy in a system is proportional to the square of the velocity gradient (actually, the double dot product of the rate of deformation tensor with itself) and to the square of the temperature gradient. See Transport Phenomena by Bird, Stewart, and Lightfoot, John Wiley, NY, 2nd Edition, 2002, p372, problem 11D.1 for the exact relationship for the local rate of entropy generation. Since this relationship involves squares of the gradients, the terms involved make positive definite contributions to the entropy generation rate.

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There's been a lot of study on trying to reduce entropy production in things like turbines and compressors. The efficiency of turbines and compressors is based on the an isenthalpic prosses (where entropy does not increase). So an ideal turbine or compressor with 100% efficiency would not increase entropy at all. Typical real world efficiencies rarely get into the 90% range.

As Chet Miller noted in their answer: where and how the entropy increases in fluid dynamics has been thoroughly studied analytically. In simple terms shearing of the fluid and temperature gradients both increase entropy, so trying to limit those should result in more efficient processes.

This is just one small area of fluid dynamics where people have spent time and effort trying to improve efficiency by reducing entropy. The general principle applies to many fields of engineering from electrical, to civil, to chemical.

One thing I wanted to highlight that might be a misunderstanding from you question is that a closed system that's already reached equilibrium will not increase in entropy. So the rate is already 0. It's only during a process that the entropy will change, and the rate of change always relates to the efficiency of the process so in general people designing processes will be trying to minimize entropy increase, even if they aren't thinking about it directly.

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One of the best definition of entropy is increase in volume, but wait without pressure there is no energy involve in expansion and the definition of entropy is unavailability of energy to do more work. We know pressure is rate of momentum change or increase in speed, that is some acceleration or force. If there is no pressure, then no force or acceleration but increase in volume possible. Now what this means, this means that when entropy is maximum, there is state of equilibirium that there is no further increase in work available from given energy and all the energy supplied is doing a maximum limit of work done for system.

This also applies for maximum speed can be gain by an object subjected to constant force for infinite time. Thus Newton's law of motion is as good for tansient state. Now to show how this can be expressed, let's take an example of isothermal process in which increase in work done is increase in volume and that is increase in entropy, or change in entropy is proportional to availibilty of work,$$\frac{W}{T}=S=Nk\ln V$$As we see that entropy has maximum value and if this change in entropy is divided by volume, then we have expression of entropy as,$$S_V=\frac{-Nk}{V}$$which shows that change in entropy decreases as volume further increases, it is somewhat similar to Wein's law. The better expression is given first by Planck, which shows both increase and decrease in entropy, contribution of higher modes are negligible or zero.

This shows that what called as instantaneous action in classical mechanics was not answered by relativity, but by quantum mechanics from Boltzmann as treating thermodynamics at particle level and significantly by Planck. The answer is approach of classical mechanics was on applying low rate of energy that is power, equated to instantaneous result im work done. That is possible if very high amount of energy is provided, as at very high temperature, entropy tends to minimum and result is instantaneous. An example is, if capacity of a capacitor is very low, then change in voltage appear at it instantaneously, any voltage can fulfill its capacity or higher voltage can also do so.

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  • $\begingroup$ Please if anyone downvote, then comment about error. Not just because author gave opinion which not match with indoctrination. If established or settled were never challenged then we don't have new theories. $\endgroup$ Commented Nov 17, 2022 at 2:59
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    $\begingroup$ Not my downvote, but your first paragraph makes no sense. $\endgroup$ Commented Nov 17, 2022 at 17:21
  • $\begingroup$ @JohnRennie Don't go on word that if there is no pressure means no force, it means if there is no pressure that means no force present. It is about that entropy limit maximum work obtained from energy or its gradient. This also means that increase in volume is only meaningful when new energy states available, and which is due to energy or pressure. Once entropy is maximum, all energy is utilizing to keep state of motion, no acceleration. If one says inertia keep in motion, then it took time to reach given speed and it take further time to come at zero in absence of force. $\endgroup$ Commented Nov 17, 2022 at 18:07
  • $\begingroup$ ESL AI post /10 $\endgroup$ Commented Apr 27 at 16:19

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