Consider a system not undergoing any change. At this point, all the properties can be measured or calculated throughout the entire system, which gives us a set of properties that completely describes the condition, or the state, of the system. At a given state, all the properties of a system have fixed values. If the value of even one property changes, the state will change to a different one. In Fig. 1–23 a system is shown at two different states.
Thermodynamics deals with equilibrium states. The word equilibrium implies a state of balance. In an equilibrium state there are no unbalanced potentials (or driving forces) within the system. A system in equilibrium experiences no changes when it is isolated from its surroundings.
There are many types of equilibrium, and a system is not in thermodynamic equilibrium unless the conditions of all the relevant types of equilibrium are satisfied. For example, a system is in thermal equilibrium if the temperature is the same throughout the entire system, as shown in Fig. 1–24. That is, the system involves no temperature differential, which is the driving force for heat flow. Mechanical equilibrium is related to pressure, and a system is in mechanical equilibrium if there is no change in pressure at any point of the system with time. However, the pressure may vary within the system with elevation as a result of gravitational effects. For example, the higher pressure at a bottom layer is balanced by the extra weight it must carry, and, therefore, there is no imbalance of forces. The variation of pressure as a result of gravity in most thermodynamic systems is relatively small and usually disregarded. If a system involves two phases, it is in phase equilibrium when the mass of each phase reaches an equilibrium level and stays there. Finally, a system is in chemical equilibrium if its chemical composition does not change with time, that is, no chemical reactions occur.
A system will not be in equilibrium unless all the relevant equilibrium criteria are satisfied.
Reference: Thermodynamics – An Engineering Approach 5th Edition by: Yunus A. Cengel and Michale A. Boles