THERMODYNAMIC EQUILIBRIUM BASIC AND TUTORIALS


Classical thermodynamics places primary emphasis on equilibrium states and changes from one equilibrium state to another. Thus, the concept of equilibrium is fundamental. In mechanics, equilibrium means a condition of balance maintained by an equality of opposing forces.

In thermodynamics, the concept is more far-reaching, including not only a balance of forces but also a balance of other influences. Each kind of influence refers to a particular aspect of thermodynamic, or complete, equilibrium.

Accordingly, several types of equilibrium must exist individually to fulfill the condition of complete equilibrium; among these are mechanical, thermal, phase, and chemical equilibrium.

Criteria for these four types of equilibrium are considered in subsequent discussions. For the present, we may think of testing to see if a system is in thermodynamic equilibrium by the following procedure: Isolate the system from its surroundings and watch for changes in its observable properties.

If there are no changes, we conclude that the system was in equilibrium at the moment it was isolated. The system can be said to be at an equilibrium state.

When a system is isolated, it does not interact with its surroundings; however, its state can change as a consequence of spontaneous events occurring internally as its intensive properties, such as temperature and pressure, tend toward uniform values.  When all such changes cease, the system is in equilibrium.

Hence, for a system to be in equilibrium it must be a single phase or consist of a number of phases that have no tendency to change their conditions when the overall system is isolated from its surroundings. At equilibrium, temperature is uniform throughout the system.

Also, pressure can be regarded as uniform throughout as long as the effect of gravity is not significant; otherwise a pressure variation can exist, as in a vertical column of liquid.

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