Thermoelectric Cycle and the Second Law of Thermodynamics

Entropy (Basel). 2023 Jan 12;25(1):155. doi: 10.3390/e25010155.

Abstract

In 2019, Schilling et al. claimed that they achieved the supercooling of a body without external intervention in their thermoelectric experiments, thus arguing that the second law of thermodynamics was bent. Kostic suggested that their claim lacked full comprehension of the second law of thermodynamics. A review of history shows that what Clausius referred to as the second law of thermodynamics is the theorem of the equivalence of transformations (unfairly ignored historically) in a reversible heat-work cycle, rather than "heat can never pass from a cold to a hot body without some other change" that was only viewed by Clausius as a natural phenomenon. Here, we propose the theorem of the equivalence of transformations for reversible thermoelectric cycles. The analysis shows that the supercooling phenomenon Schilling et al. observed is achieved by a reversible combined power-refrigeration cycle. According to the theorem of equivalence of transformations in reversible thermoelectric cycles, the reduction in body temperature to below the ambient temperature requires the body itself to have a higher initial temperature than ambient as compensation. Not only does the supercooling phenomenon not bend the second law, but it provides strong evidence of the second law.

Keywords: combined power–refrigeration cycle; reversible thermoelectric cycle; the second law of thermodynamics; theorem of the equivalence of transformations.