Thermodynamics of irreversible processes

The thermodynamics of irreversible processes, formulated by Onsager and Prigogine, considers small deviations from equilibrium in open systems. Despite the fact that the name contains ‘‘thermodynamics,’’ this is a type of kinetic theory that describes the rates of irreversible processes. Since there are no currents of any type in thermodynamic equilibrium, the concept of a current is never used in classical thermodynamics. On the other hand, the thermodynamics of irreversible processes introduces currents as the rates at which processes proceed: the heat or energy current (measured in J/s), matter current (measured in mole/s or kg/s), charge or electrical current (measured in C/s or Amps). Since these currents have a direction and magnitude, they are vectors. The thermodynamics of irreversible processes also considers scalar currents (e.g. rates of chemical reactions) and tensor currents (e.g. momentum currents). In this text, we will focus on current densities or fluxes (that is the current per unit area) rather than currents themselves. The dimensions of the currents described above can be converted to the dimensions of fluxes by dividing through by area or m2. Associated with each flux is a driving force. These forces are known as thermodynamic forces. How can we determine these driving forces? What is the relation between fluxes and driving forces? The answers to these questions can be found in the thermodynamics of irreversible processes briefly described in this chapter. Onsager’s first postulate states that the flux of property i ( ji) is a linear function of all thermodynamic forces, Xk, acting in the system where Lik are called Onsager (or kinetic) coefficients. This postulate was formulated as a generalization of a wide body of experimental observations. In fact, long before Onsager’s work it was known that the heat fluxes are proportional to temperature gradients (Fourier’s law, 1824), charge fluxes are proportional to electric potential gradients (Ohm’s law, 1826), and matter fluxes are proportional to concentration gradients (Fick’s law, 1855). However, Onsager’s contribution was the inclusion of the word ‘‘all’’ in his first postulate.