Maxwell and a Third 2nd Law of Thermodynamics

Abstract

It has long been recognized that there are two distinct laws that go by the name of the Second Law of Thermodynamics. The original says that there can be no process resulting in a net decrease in the total entropy of all bodies involved. A consequence of the kinetic theory of heat is that this law will not be strictly true; statistical fluctuations will result in small spontaneous transfers of heat from a cooler to a warmer body. The currently accepted version of the Second Law is probabilistic: tiny spontaneous transfers of heat from a cooler to a warmer body will be occurring all the time, while a larger transfer is not impossible, merely improbable. There can be no process whose expected result is a net decrease in total entropy. According to Maxwell, the Second Law has only statistical validity, and this statement is easily read as an endorsement of the probabilistic version. I argue that a close reading of Maxwell, with attention to his use of "statistical," shows that the version of the second law endorsed by Maxwell is strictly weaker than our probabilistic version. According to Maxwell, even the probable truth of the second law is limited to situations in which we deal with matter only in bulk and are unable to observe or manipulate individual molecules. Maxwell's version does not rule out a device that could, predictably and reliably, transfer heat from a cooler to a warmer body without a compensating increase in entropy. I will discuss the evidence we have for these two laws, Maxwell's and ours.