Thermodynamic Equations - Introduction

Introduction

One of the fundamental thermodynamic equations is the description of thermodynamic work in analogy to mechanical work, or weight lifted through an elevation against gravity, as defined in 1824 by French physicist Sadi Carnot. Carnot used the phrase motive power for work. In the footnotes to his famous On the Motive Power of Fire, he states: “We use here the expression motive power to express the useful effect that a motor is capable of producing. This effect can always be likened to the elevation of a weight to a certain height. It has, as we know, as a measure, the product of the weight multiplied by the height to which it is raised.” With the inclusion of a unit of time in Carnot's definition, one arrives at the modern definition for power:

During the latter half of the 19th century, physicists such as Rudolf Clausius, Peter Guthrie Tait, and Willard Gibbs worked to develop the concept of a thermodynamic system and the correlative energetic laws which govern its associated processes. The equilibrium state of a thermodynamic system is described by specifying its "state". The state of a thermodynamic system is specified by a number of extensive quantities, the most familiar of which are volume, internal energy, and the amount of each constituent particle (particle numbers). Extensive parameters are properties of the entire system, as contrasted with intensive parameters which can be defined at a single point, such as temperature and pressure. The extensive parameters (except entropy) are generally conserved in some way as long as the system is "insulated" to changes to that parameter from the outside. The truth of this statement for volume is trivial, for particles one might say that the total particle number of each atomic element is conserved. In the case of energy, the statement of the conservation of energy is known as the first law of thermodynamics.

A thermodynamic system is in equilibrium when it is no longer changing in time. This may happen in a very short time, or it may happen with glacial slowness. A thermodynamic system may be composed of many subsystems which may or may not be "insulated" from each other with respect to the various extensive quantities. If we have a thermodynamic system in equilibrium in which we relax some of its constraints, it will move to a new equilibrium state. The thermodynamic parameters may now be thought of as variables and the state may be thought of as a particular point in a space of thermodynamic parameters. The change in the state of the system can be seen as a path in this state space. This change is called a thermodynamic process. Thermodynamic equations are now used to express the relationships between the state parameters at these different equilibrium state.

The concept which governs the path that a thermodynamic system traces in state space as it goes from one equilibrium state to another is that of entropy. The entropy is first viewed as an extensive function of all of the extensive thermodynamic parameters. If we have a thermodynamic system in equilibrium, and we release some of the extensive constraints on the system, there are many equilibrium states that it could move to consistent with the conservation of energy, volume, etc. The second law of thermodynamics specifies that the equilibrium state that it moves to is in fact the one with the greatest entropy. Once we know the entropy as a function of the extensive variables of the system, we will be able to predict the final equilibrium state. (Callen 1985)