Fractional Calculus Extension of the Kinetic Theory of Fluids: Molecular Models of Transport within and between Phases

Abstract

The application of fractional calculus in the field of kinetic theory begins with questions raised by Bernoulli, Clausius, and Maxwell about the motion of molecules in gases and liquids. Causality, locality, and determinism underly the early work, which led to the development of statistical mechanics by Boltzmann, Gibbs, Enskog, and Chapman. However, memory and nonlocality influence the future course of molecular interactions (e.g., persistence of velocity and inelastic collisions); hence, modifications to the thermodynamic equations of state, the non-equilibrium transport equations, and the dynamics of phase transitions are needed to explain experimental measurements. In these situations, the inclusion of space- and time-fractional derivatives within the context of the continuous time random walk (CTRW) model of diffusion encodes particle jumps and trapping. Thus, we anticipate using fractional calculus to extend the classical equations of diffusion. The solutions obtained illuminate the structure and dynamics of the materials (gases and liquids) at the molecular, mesoscopic, and macroscopic time/length scales. The development of these models requires building connections between kinetic theory, physical chemistry, and applied mathematics. In this paper, we focus on the kinetic theory of gases and liquids, with particular emphasis on descriptions of phase transitions, inter-phase mixing, and the transport of mass, momentum, and energy. As an example, we combine the pressure–temperature phase diagrams of simple molecules with the corresponding anomalous diffusion phase diagram of fractional calculus. The overlap suggests links between sub- and super-diffusion and molecular motion in the liquid and the vapor phases.

Keywords

• fractional calculus
• statistical mechanics
• kinetic theory
• phase transitions
• anomalous diffusion
• critical point