22

In statistical explanations of entropy, we can often read about a (thought) experiment of the following sort.

We have a bunch of particles in box, packed densely in one of the corners. We assume some temperature, and with it some random initial velocities of the particles. We don't exactly know the positions and the velocities, so these can be modeled as random variables in a mathematical sense. The random variables expressing the initial conditions have a certain joint probability distribution where the configurations expressing "particles in a bunch in the corner" have high probability. Now, we simulate physics (apply deterministic and reversible equations of motion) on this arrangement and we can mathematically prove that the random variables corresponding to the new positions and velocities of the particles have a joint distribution that makes it very likely that draws from it will fit the description "particles all over the place in a nothing-special arrangement".

This is very informal, but I know that all of this can be formalized by introducing the concept of a macrostate and then we have a mathematically provable theorem that the information theoretical conditional entropy of the full state given the macrostate will increase as time passes. This is basically the second law.

Now I don't see anything preventing me from applying the same logic backwards in time. Based on these mathematical results, I'd assume the following holds:

When I see a (moderately) clustered configuration of particles in the box, if someone asks me what I believe the particles looked like 10 seconds ago, my answer should be that 'they were probably more all over the place than now, with no particular arrangement or clustering'.

Or formulated otherwise, looking backwards in time, we should expect to see an increased thermodynamic entropy. The paradoxical thing to me is that we seem to assume that in the past entropy was even smaller than today!

Practical example: You arrive late to chemistry class and the teacher is demonstrating how some purple material diffuses in water. Common sense tells me to assume that the purple material was more concentrated in the water 10 seconds ago than it is now. But the above argument should make me believe that I look at the lowest entropy right now and the material was/will be more diffused in either direction of time. There is nothing time-asymmetric in the above statistical reasoning.

How can this paradox be resolved?

isarandi
  • 915
  • 2
  • 8
  • 14

2 Answers2

12

The reasoning in the question is correct. If you have a box with gas particles placed in half of a box but otherwise uniformly random and with random velocities then it is overwhelmingly likely that it entropy will increase with time, but if reverse the velocities, you will still have randomly distributed velocities and the same argument will apply. By time symmetry reversing the velocities and going forward in time is equivalent to going backward in time. So system prepared as described above would almost certainly be in local entropy minimum wrt to time.

If the whole universe only consisted of some water with unevenly distributed dye in it, and we knew nothing about its origin, then inferring that the dye was more evenly distributed in the past would be rational. The water and dye being in a beaker near a teacher in a far from equilibrium universe makes other explanations much more likely though. However, your line of reasoning has some bite at the cosmological level. This is the Boltzmann Brain Problem. It is still not satisfactorily resolved, as you can see on ArXiv.

The second law of thermodynamics works (and is a law) because the universe is far from equilibrium (ie low entropy) and is believed to have started much farther from equilibrium that than it is now. Of course a big part of the reason for believing that is the second law. ;)

Here is a more detailed explanation from my answer to Where does deleted information go?:


The apparent conflict between macroscopic irreversibility and microscopic reversibilty is known as Loschmidt's paradox, though it is not actually a paradox.

In my understanding sensitivity to initial conditions, the butterfly effect, reconciles macroscopic irreversibility with microscopic reversibility. Suppose time reverses while you are scrambling an egg. The egg should then just unscramble like in a film running backwards. However, the slightest perturbation, say by hitting a single molecule with a photon, will start a chain reaction as that molecule will collide with different molecules than it otherwise would have. Those will in turn have different interactions then they otherwise would have and so on. The trajectory of the perturbed system will diverge exponentially from the original time reversed trajectory. At the macroscopic level the unscrambing will initially continue, but a region of rescrambling will start to grow from where the photon struck and swallow the whole system leaving a completely scrambled egg.

This shows that time reversed states of non-equilibrium systems are statistically very special, their trajectories are extremely unstable and impossible to prepare in practice. The slightest perturbation of a time reversed non-equilibrium system causes the second law of thermodynamics to kick back in.

The above thought experiment also illustrates the Boltzmann brain paradox in that it makes it seem that a partially scrambled egg is more likely to arise form the spontaneous unscrambling of a completely scrambled egg than by breaking an intact one, since if trajectories leading to an intact egg in the future are extremely unstable, then by reversibility, so must trajectories originating from one in the past. Therefore the vast majority of possible past histories leading to a partially scrambled state must do so via spontaneous unscrambling. This problem is not yet satisfactorily resolved, particularly its cosmological implications, as can be seen by searching Arxiv and Google Scholar.

Nothing in this depends on any non classical effects.

1

Or formulated otherwise, looking backwards in time, we should expect to see an increased thermodynamic entropy. The paradoxical thing to me is that we seem to assume that in the past entropy was even smaller than today!

The following assumes that the description of microscopic motion of the particles of the system is Hamiltonian (your system qualifies for this).

I will use the word thermodynamics in its restricted sense, i.e. the subject treating effects of heat and work exchange between bodies on their states of thermodynamic equilibrium. 2nd law of thermodynamics talks about changes between equilibrium states only.

The impression of a paradox and disagreement about its importance, resolution and whether resolution was found persists for more than a century now. No doubt this is partially due to the fact people teach many misconceptions at universities and their students later publish some of them in their papers.

Here is one solution that is known at least since 60's when Jaynes published it (see below). In contrast to resolutions based on various wild and misguided assumptions on the alleged entropy of the Universe and its value in the past, it is quite prosaic.

The short version of this prose is this: there is no paradox or contradiction between probabilistic reasoning and thermodynamics, because the theorems concluding the same trend for entropy for both the actual and the velocity-reversed specially prepared microstate talk about different kind of entropy than thermodynamics and 2nd law do. People got confused by two different concepts of entropy here.

The derivations actually talk about evolution of some coarse-grained information entropy $I_{CG}$ (or similarly, about minus Boltzmann H-function). This is typically defined for all microstates of the mechanical system, how different soever they are from its microstates compatible with equilibrium thermodynamic state of thermodynamic system modeled.

This is very different concept of entropy from thermodynamic entropy $S$ (Clausius' entropy), which makes sense only for microstates that are compatible with state of thermodynamic equilibrium. For general states of thermodynamic system (for example, its possible non-equilibrium states), the concept of thermodynamic entropy does not generally apply.

Also, any implication of the 2nd law for thermodynamic entropy is restricted to states of equilibrium. Trying to apply it to non-equilibrium states is a suspicious operation that may be useful in some cases, but has no general validity whatsoever.

This means 2nd law actually says nothing about the special microstate imagined or its reverse. Both correspond to highly non-equilibrium thermodynamic state and do not have thermodynamic entropy. The coarse-grained entropy increases, but there is no connection to thermodynamic entropy and thus no contradiction with 2nd law.

2nd law says only that when container with system in equilibrium with thermodynamic entropy $S_1$ is suddenly enlarged so that the system is no longer in equilibrium state, the final equilibrium state of the system will have thermodynamic entropy $S_2 \geq S_1$. There is no problem with thermodynamic entropy increase as time coordinate is decreased below the time of enlargement, because the entropy retains value $S_1$ since the system was in equilibrium state in the original volume.

This is one of the reasons why it makes no sense in thermodynamics to talk about thermodynamic entropy of systems such as living cell, fly, Earth or the Universe. These are not systems in thermodynamic equilibrium and are not eligible for thermodynamic description (in the above restricted sense).

Finally, this means that the above-mentioned derivations actually do not derive 2nd law of thermodynamics at all, but only a theorem about evolution of certain theoretical quantity - information entropy of coarse-grained description $I_{CG}$ - that is only similar in wording to the 2nd law of thermodynamics, but has completely different meaning.

The quantity $I_{CG}$ expresses ignorance about the actual microstate of the system when all we know is a cell in phase space. It is too general as far as allowed microstates go, and too specific as far as cell specification goes, to identify it with thermodynamic entropy in all cases.

Thermodynamic entropy of equilibrium state does correspond to information entropy, but in a very different way; its value is equal to maximum possible value of information entropy given mathematical constraints on the probability distribution implied by the thermodynamic state maintained by physical constraints (volume of the container). This is very different from coarse-graining.

If you got interested, you can read the original and more exhausting explanations in Jaynes' contributions to physics, mainly the papers

http://bayes.wustl.edu/etj/articles/gibbs.vs.boltzmann.pdf

http://bayes.wustl.edu/etj/articles/brandeis.pdf

http://bayes.wustl.edu/etj/articles/mobil.pdf - from page 141

http://bayes.wustl.edu/etj/articles/ccarnot.pdf - sec. 6 & Appendix C