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A thermodynamic process may be defined as the energetic evolution of a thermodynamic system proceeding from an initial state to a final state. Paths through the space of thermodynamic variables are often specified by holding certain thermodynamic variables constant. It is useful to group these processes into pairs, in which each variable held constant is one member of a conjugate pair.
The pressure-volume conjugate pair is concerned with the transfer of mechanical or dynamic energy as the result of work.
- An isobaric process occurs at constant pressure. An example would be to have a movable piston in a cylinder, so that the pressure inside the cylinder is always at atmospheric pressure, although it is isolated from the atmosphere. In other words, the system is dynamically connected, by a movable boundary, to a constant-pressure reservoir.
- An isochoric process is one in which the volume is held constant, meaning that the work done by the system will be zero. It follows that, for the simple system of two dimensions, any heat energy transferred to the system externally will be absorbed as internal energy. An isochoric process is also known as an isometric process or an isovolumetric process. An example would be to place a closed tin can containing only air into a fire. To a first approximation, the can will not expand, and the only change will be that the gas gains internal energy, as evidenced by its increase in temperature and pressure. Mathematically, δQ = dU. We may say that the system is dynamically insulated, by a rigid boundary, from the environment.
The temperature-entropy conjugate pair is concerned with the transfer of thermal energy as the result of heating.
- An isothermal process occurs at a constant temperature. An example would be to have a system immersed in a large constant-temperature bath. Any work energy performed by the system will be lost to the bath, but its temperature will remain constant. In other words, the system is thermally connected, by a thermally conductive boundary to a constant-temperature reservoir.
- An adiabatic process is a process in which there is no energy added or subtracted from the system by heating or cooling. For a reversible process, this is identical to an isentropic process. We may say that the system is thermally insulated from its environment and that its boundary is a thermal insulator. If a system has an entropy which has not yet reached its maximum equilibrium value, the entropy will increase even though the system is thermally insulated.
- An isentropic process occurs at a constant entropy. For a reversible process this is identical to an adiabatic process. If a system has an entropy which has not yet reached its maximum equilibrium value, a process of cooling may be required to maintain that value of entropy.
Any of the thermodynamic potentials may be held constant during a process. For example:
The above have all implicitly assumed that the boundaries are also impermeable to particles. We may assume boundaries that are both rigid and thermally insulating, but are permeable to one or more types of particle. Similar considerations then hold for the (chemical potential)-(particle number) conjugate pairs.
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