Work Storage in States of Apparent Negative Thermodynamic Temperature

Inverted quantum states provide a challenge to classical thermodynamics, since they appear to contradict the classical formulation of the second law of thermodynamics. Ramsey interpreted these states as stable equilibrium states of negative thermodynamic temperature, and added a provision to allow these states to the Kelvin-Planck statement of the second law [N. F. Ramsey, Phys. Rev. 103, 20 (1956)]. Since then, Ramsey’s interpretation has prevailed in the literature. Here, we present an alternative option to accommodate inverted states within thermodynamics, which strictly enforces the original Kelvin-Planck statement of the second law, and reconciles inverted states and the second law by interpreting the former as unstable states, for which no temperature—positive or negative—can be defined. Specifically, we recognize inverted quantum states as temperature-unstable states, for which all processes are in agreement with the original Kelvin-Planck statement of the second law, and positive thermodynamic temperatures in stable equilibrium states. These temperature-unstable states can only be created by work done to the system, which is stored as energy in the unstable states, and can be released as work again, just as in a battery or a spring.

Figure 1

Processes on and across the entropy-energy relation $S(E)$. States on the ascending part of the curve are stable equilibrium states (black), states on the descending part are temperature-unstable states (red dashes). Processes $a\to b\to c$ and $a\to b\to d\to e\to a$ are permitted irreversible processes; see discussion in the text.