First Law of Thermodynamics - Spatially Inhomogeneous Systems

Spatially Inhomogeneous Systems

Classical thermodynamics is initially focused on closed homogeneous systems (e.g. Planck 1897/1903), which might be regarded as 'zero-dimensional' in the sense that they have no spatial variation. But it is desired to study also systems with distinct internal motion and spatial inhomogeneity. For such systems, the principle of conservation of energy is expressed in terms not only of internal energy as defined for homogeneous systems, but also in terms of kinetic energy and potential energies of parts of the inhomogeneous system with respect to each other and with respect to long-range external forces. How the total energy of a system is allocated between these three more specific kinds of energy varies according to the purposes of different writers; this is because these components of energy are to some extent mathematical artefacts rather than actually measured physical quantities. For any closed homogeneous component of an inhomogeneous closed system, if denotes the total energy of that component system, one may write

where and denote respectively the total kinetic energy and the total potential energy of the component closed homogeneous system, and denotes its internal energy.

Potential energy can be exchanged with the surroundings of the system when the surroundings impose a force field, such as gravitational or electromagnetic, on the system.

A compound system consisting of two interacting closed homogeneous component subsystems has a potential energy of interaction between the subsystems. Thus, in an obvious notation, one may write

The distinction between internal and kinetic energy is hard to make in the presence of turbulent motion within the system, as friction gradually dissipates macroscopic kinetic energy of localised bulk flow into molecular random motion of molecules that is classified as internal energy. The rate of dissipation by friction of kinetic energy of localised bulk flow into internal energy, whether in turbulent or in streamlined flow, is an important quantity in non-equilibrium thermodynamics. This is a serious difficulty for attempts to define entropy for time-varying spatially inhomogeneous systems.

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