04_part1b - 1.B: The Second Law of Thermodynamics [IAW...

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1.B: The Second Law of Thermodynamics [IAW 42-50; VN Chapter 5; VWB&S-6.3, 6.4, Chapter 7] 1.B.1 Concept and Statements of the Second Law (Why do we need a second law? ) The unrestrained expansion, or the temperature equilibration of the two bricks, are familiar processes. Suppose you are asked whether you have ever seen the reverse of these processes take place? Do two bricks at a medium temperature ever go to a state where one is hot and one is cold? Will the gas in the unrestrained expansion ever spontaneously return to occupying only the left side of the volume? Experience hints that the answer is no. However, both these processes, unfamiliar though they may be, are compatible with the first law. In other words the first law does not prohibit their occurrence. There thus must be some other “great principle” that describes the direction of natural processes, that tells us which first law compatible processes will not be observed. This is contained in the second law. Like the first law, it is a generalization from an enormous amount of observation. There are several ways in which the second law of thermodynamics can be stated. Listed below are three that are often encountered. As described in class (and as derived in almost every thermodynamics textbook), although the three may not appear to have much connection with each other, they are equivalent . 1) No process is possible whose sole result is the absorption of heat from a reservoir and the conversion of this heat into work. [Kelvin-Planck statement of the second law] Q System T 2 W This is not possible T 1 2) No process is possible whose sole result is the transfer of heat from a cooler to a hotter body. [Clausius statement of the second law] Q T 2 T 1 For T 1 < T 2 , this is n ot possible Q 1B-1
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3) There exists a property called entropy , S , which is a thermodynamic property of a system. For a reversible process, changes in this property are given by dS = (dQ reversible )/T The entropy change of any system and its surroundings, considered together, is positive and approaches zero for any process which approaches reversibility. S total > 0 For an isolated system , i.e., a system that has no interaction with the surroundings, changes in the system have no effect on the surroundings. In this case, we need to consider the system only, and the first and second laws become: E system = 0 S system > 0 For an isolated system the total energy ( E = U + Kinetic Energy + Potential Energy + . ...) is constant. The entropy can only increase or, in the limit of a reversible process, remain constant. All of these statements are equivalent, but (3) gives a direct, quantitative measure of the departure from reversibility. Entropy is not a familiar concept and it may be helpful to provide some additional rationale for its appearance. If we look at the first law, dU = dQ dW the term on the left is a function of state, while the two terms on the right are not. For a simple compressible substance, however, we can write the work done in a reversible process as dW = PdV , so that dU = dQ PdV ; First law for a simple compressible substance, reversible process.
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This note was uploaded on 12/22/2011 for the course AERO 16.050 taught by Professor Zoltanspakovszky during the Fall '02 term at MIT.

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04_part1b - 1.B: The Second Law of Thermodynamics [IAW...

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