Steady thermodynamic fundamental relation for the interacting system in a heat flow

Abstract: There is a long-standing question of whether it is possible to extend the formalism of equilibrium thermodynamics to the case of non-equilibrium systems in steady states. We have made such an extension for an ideal gas in a heat flow [Ho\l{}yst \emph{et al.}, J. Chem. Phys. 157, 194108 (2022)]. Here we investigate whether such a description exists for the system with interactions: the Van der Waals gas in a heat flow. We introduce the parameters of state, each associated with a single way of changing energy. The first law of non-equilibrium thermodynamics follows from these parameters. The internal energy $U$ for the non-equilibrium states has the same form as in equilibrium thermodynamics. For the Van der Waals gas, $U(S^*, V, N, a^,b^ )$ is a function of only 5 parameters of state (irrespective of the number of parameters characterizing the boundary conditions): the entropy $S^*$, volume $V$, number of particles $N$, and the rescaled Van der Waals parameters $a^*$, $b^*$. The state parameters, $a^*$, $b^*$, together with $S^*$, determine the net heat exchange with the environment.