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Could someone provide me with a mathematical proof of why, a system with an absolute negative Kelvin temperature (such that of a spin system) is hotter than any system with a positive temperature (in the sense that if a negative-temperature system and a positive-temperature system come in contact, heat will flow from the negative- to the positive-temperature system).

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up vote 21 down vote accepted

From a fundamental (i.e., statistical mechanics) point of view, the physically relevant parameter is coldness = inverse temperature $\beta=1/k_BT$. This changes continuously. If it passes from a positive value through zero to a negative value, the temperature changes from very large positive to infinite (with indefinite sign) to very large negative. Therefore systems with negative temperature have a smaller coldness and hence are hotter than systems with positive temperature.

Some references:

D. Montgomery and G. Joyce. Statistical mechanics of “negative temperature” states. Phys. Fluids, 17:1139–1145, 1974.

E.M. Purcell and R.V. Pound. A nuclear spin system at negative temperature. Phys. Rev., 81:279–280, 1951.

Section 73 of Landau and E.M. Lifshits. Statistical Physics: Part 1,

Example 9.2.5 in my online book Classical and Quantum Mechanics via Lie algebras.

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Arnold Neumaier's comment about statistical mechanics is correct, but here's how you can prove it using just thermodynamics. Let's imagine two bodies at different temperatures in contact with one another. Let's say that body 1 transfers a small amount of heat $Q$ to body 2. Body 1's entropy changes by $-Q/T_1$, and body 2's entropy changes by $Q/T_2$, so the total entropy change is $$ Q\left(\frac{1}{T_2}-\frac{1}{T_1}\right). $$ This total entropy change must be positive (according to the second law), so if $1/T_1>1/T_2$ then $Q$ has to be negative, meaning that body 2 can transfer heat to body 1 rather than the other way around. It's the sign of $\frac{1}{T_2}-\frac{1}{T_1}$ that determines the direction that heat can flow.

Now let's say that $T_1<0$ and $T_2>0$. Now it's clear that $\frac{1}{T_2}-\frac{1}{T_1}>0$ since both $1/T_2$ and $-1/T_1$ are positive. This means that body 1 (with a negative temperature) can transfer heat to body 2 (with a positive temperature), but not the other way around. In this sense body 1 is "hotter" than body 2.

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Take a hydrogen gas in a magnetic field. The nuclei can be aligned with the field, low energy, or against it, high energy. At low temperature most of the nuclei are aligned with the field and no matter how much I heat the gas I can never make the population of the higher energy state exceed the lower energy state. All I can do is make them almost equal, as described by the Boltzmann distribution.

Now I take another sample of hydrogen where I have created a population inversion, maybe by some method akin to that used in a laser, so there are more nuclei aligned against the field than with it. This is my negative temperature material.

What happens when I mix the samples. Well I would expect the population inverted gas to "cool" and the normal gas to "heat" so that my mixture ends up with the Boltzmann distribution of aligned and opposite nuclei.

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Ah, but who says that negative absolute temperatures exist at all? This is not without its controversies. There's a nature paper here which challenges the very existence of negative absolute temperatures, arguing that negative temperatures come about due to a poor method of defining the entropy, which in turn is used to calculate the temperature.

Other people insist that these negative temperatures are "real".

So, depending on which side of this debate you align yourself with, these systems can be described with positive temperatures (and behave accordingly), or negative temperatures which have very exotic properties.

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This does not answer the question (the proof that is asked for does not rely on whether such systems actually exist or not). – ACuriousMind Jun 30 '15 at 10:26
The one thing that everyone agrees on is that their behavior is a bit surprising, and that is to be expected as we don't encounter systems with temperature ceilings in day-to-day life. In any case, that paper is cited in the comments on most of our "negative absolute temperature" questions. I can assure you that most of the answer authors are aware of it. But the question presupposes the definition of temperature which generates 'negative' values and this post doesn't really address it. – dmckee Jul 1 '15 at 3:04
@ACuriousMind: What of E=-mcc? Matt Thompson's answer is to claim the negative temperatures are the similar beast of spurious mathematical solutions and have no meaning whatsoever. – Joshua May 22 at 16:20

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