Thermodynamics – Understanding Quasi-Static Processes that Are Not Reversible

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I have just begun reading Huang's Statistical Mechanics textbook and am confused by his definition of a quasi-static process. In his definition, he states that a quasi-static process is one in which "the external condition changes so slowly that at any moment the system is approximately in equilibrium". In my mind, this brings to mind that such a process can be represented by a series of points on the state space, representing equilibrium states, thus defining a curve. I would imagine that this curve be continuous, else there may be a non-equilibrium state involved in the discontinuity.

However, there seems to be some conflict of this interpretation with his definition of a reversible process as he states that only those can be represented as a continuous path on the state space surface.

Is my interpretation of his definition of quasi-static too restrictive? If only reversible processes can be represented as a continuous curve on the state space surface, how, if they can be, are non-reversible quasi-static processes represented on the state space?

Best Answer

The problem with irreversible transformations, even if quasi-static, is that one needs to add some non-equilibrium quantities to the set of variables describing the system's state. In this sense, we cannot represent an irreversible process by using only state variables.

Indeed, if there is some internal entropy production, this gives an additional contribution to the change of entropy related to the heat fluxes. From a more mathematical point of view, entropy production would make a function of the thermodynamic state a multi-valued object. In this sense, it cannot be represented as a unique curve on the state space.