Next: Up: Previous:  6. 5 Irreversibility, Entropy Changes, and ``Lost Work'Consider a system in contact with a heat reservoir during areversible process. If there is heatabsorbed by thereservoir at temperature, the change in entropy of the reservoiris.

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If we use the definition of entropy S=−kB∑iPilnPi. Where Pi is the probability of the i'th microstate, then at 0K, we know the system is certainly in the ground state,. Zero entropy means perfect knowledge of a state; no motion, no temperature, no uncertainty. Occurs at absolute zero. It's when your knowledge of state is so complete that only one microstate is possible. So W (number of microstates) = 1. Therefore S = k ln (W) = k ln(1) = 0. It is the essence of the third law of thermodynamics.

In general, reversible processes areaccompanied by heat exchanges that occur at different temperatures.To analyze these, we can visualize a sequence of heat reservoirs atdifferent temperatures so that during any infinitesimal portion ofthe cycle there will not be any heat transferred over a finitetemperature difference.During any infinitesimal portion, heatwill betransferred between the system and one of the reservoirs which is at. Ifis absorbed by the system, the entropychange of the system is. 6)Either of Equation or can be interpreted to mean that theentropy of the system, is affected by two factors: the flow ofheatand the appearance of additional entropy, denoted by, due to irreversibility. This additional entropy is zero when theprocess is reversible and always positive when the process isirreversible. Thus, one can say that the system developssources which create entropy during an irreversible process.The second law asserts that sinks of entropy are impossiblein nature, which is a more graphic way of saying thatandare positive definite(always greater than zero), or zero in the special case ofreversible processes.The term. Which is associated with heat transfer to the system, can beinterpreted as a flux of entropy.

The boundary is crossed by heatand the ratio of this heat flux to temperature can be defined as aflux of entropy. There are no restrictions on the sign of thisquantity, and we can say that this flux either contributes towards,or drains away, the system's entropy. During a reversible process,only this flux can affect the entropy of the system. Thisterminology suggests that we interpret entropy as a kind ofweightless fluid, whose quantity is conserved (like that of matter)during a reversible process. During an irreversible process,however, this fluid is not conserved; it cannot disappear, butrather is created by sources throughout the system.

While thisinterpretation should not be taken too literally, it provides aneasy mode of expression and is in the same category of concepts suchas those associated with the phrases ``flux of energy' or ``sourcesof heat.' ' In fluid mechanics, for example, this graphic language isvery effective and there should be no objections to copying it inthermodynamics.Muddy PointsDo we ever see an absolute variable for entropy? So far, we haveworked with deltas only (MP )I am confused as toas opposed to.(MP )For irreversible processes, how can we calculateif not equalto?(MP ).