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The oscillations of the piston assembly are damped out because the viscous nature of the gas gradually converts gross directed motion of the molecules into chaotic molecular motion This dissipative process transforms some of the work initially done by the gas in accelerating the piston back into internal energy of the gas Once the process is initiated, no injinitesimal change in external conditions can reverse its direction; the process is irreversible All processes carried out in finite time with real substances are accompanied in some degree by dissipative effects of one kind or another, and all are therefore irreversible However, one can imagine processes that are free of dissipative effects For the expansion process of Fig 22, such effects have their origin in the sudden removal of a finite mass from the piston The resulting imbalance of forces acting on the piston causes its acceleration, and leads to its subsequent oscillation The sudden removal of smaller mass increments reduces but does not eliminate this dissipative effect Even the removal of an infinitesimal mass leads to piston

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oscillations of infinitesimal amplitude and a consequent dissipative effect However, one may imagine a process wherein small mass increments are removed one after another at a rate such that the piston's rise is continuous, with minute oscillation only at the end of the process The limiting case of removal of a succession of infinitesimal masses from the piston is approximated when the masses m in Fig 22 are replaced by a pile of powder, blown in a very fine stream from the piston During this process, the piston rises at a uniform but very slow rate, and the powder collects in storage at ever higher levels The system is never more than differentially displaced from internal equilibrium or from equilibrium with its surroundings If the removal of powder from the piston is stopped and the direction of transfer of powder is reversed, the process reverses direction and proceeds backwards along its original path Both the system and its surroundings are ultimately restored to their initial conditions The original process is reversible Without the assumption of a frictionless piston, we cannot imagine a reversible process If the piston sticks because of friction, a finite mass must be removed before the piston breaks free Thus the equilibrium condition necessary to reversibility is not maintained Moreover, friction between two sliding parts is a mechanism for the dissipation of mechanical energy into internal energy This discussion has centered on a single closed-system process, the expansion of a gas in a cylinder The opposite process, compression of a gas in a cylinder, is described in exactly the same way There are, however, many processes which are driven by the imbalance of forces other than mechanical forces For example, heat flow occurs when a temperature difference exists, electricity flows under the influence of an electromotive force, and chemical reactions occur because a chemical potential exists In general, a process is reversible when the net force driving it is only differential in size Thus heat is transferred reversibly when it flows from a finite object at temperature T to another such object at temperature T - d T.

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