Statistical Mechanics: Does Entropy Increase Backwards in Time Too?

arrow-of-timeentropystatistical mechanics

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?

Best Answer

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.

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