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Y Y Shan

Chapter 4

Thermodynamic Entropy

Introduction:

In science, the term "entropy", which means “transformation” in Greek, has two

distinct interpretations: one is the thermodynamic entropy in the field of physics, the

other is information entropy in information theory. Thermodynamic entropy, being the

subject to be discussed in the following, is a fundamentally different concept from

information entropy in information theory

There are two viewpoints explaining the thermodynamic entropy.

Classical

**thermodynamics gives a macroscopic viewpoint, while statistical thermodynamics
**

gives a microscopic viewpoint. From the two different viewpoints, two equivalent

definitions of entropy had been developed in classical thermodynamics and statistical

thermodynamics, respectively.

The definition of entropy in classical thermodynamics was developed in the early

1850s by thermodynamicist Rudolf Clausius. It makes no reference to the microscopic

nature of matter.

The entropy is interpreted simply as a state function of a

**thermodynamic system: that is, a property depending only on the current state of the
**

system, independent of how that state came to be achieved.

The definition of entropy in statistical thermodynamics was developed by Ludwig

Boltzmann in the 1870s. This definition describes the entropy as a measure of the

number of possible microscopic configurations of the individual atoms and molecules

of the system (microstates)

1.

Macroscopic perspective of entropy in classical thermodynamics: a State

Function

In thermodynamics, if the balance of function Z remains unchanged during a

cyclic process, i.e.,

AP3290

50

1. if a function is defined as: S = its infinitesimal change: dS = Q . ∫U = 0 ..e. ∆Z fi = Z f − Z i Then function Z is called a state function. i. or the difference between the initial state and final state is independent of paths. such as the internal energy U. T What is the change of the function after a cycle A→B→C→D→A: ∆S ABCDA = ∫ dS = ∫ AP3290 dQ =? T 51 .1 An example to calculate Q/T: In the following thermodynamic cycle. so that T dQ .Thermodynamics Y Y Shan ∫ dZ = 0 .

that for a Carnot engine cycle.2. we get the even more useful relation: AP3290 52 . Clausius theorem: Entropy –a state function proved mathematically It has been obtained in chapter 2. the efficiency is : η Carnot = Q T W =1− C =1− C . the function S as defined is a state function 1. QC QH TH so that QC TC Q Q = → H = C QH TH TH TC From above.Thermodynamics Y Y Shan ∆S ABCDA = ∆S AB + ∆S BC + ∆S CD + ∆S DA B dQAB T A C dQ = ∫ BC T B D dQ = ∫ CD T C A dQ = ∫ DA T D ∆S AB = ∫ = ∆S BC = ∆S CD ∆S DA = = Therefore.

representing heat taken from the system. T2 = TC In principle. any loop(cycle) can be broken up into a grid of infinitesimal Carnot cycles. 4-3 can be written as: QH QC + = 0. T1 T2 where T1 = TH . we have AP3290 53 . For the far left Carnot cycle “abcd”. and take Q to be negative value. representing heat energy added to the system. The smooth closed curve(black) is a reversible cycle and the zigzag closed path is made up of alternating isothermal(red) and adiabatic(blue) processes from neighboring Carnot cycles. or TH TC Q1 Q2 + =0 . as shown in the following:.Thermodynamics Y Y Shan QH QC − =0 TH TC eqn4-3 If we take Q to be positive value.

. ef) become shorter. It can be integrated to calculate the change in entropy S during any part of a thermodynamic cycle.5 It is called the Clausius theorem. we may write Qj ∑T j =0 j where the summation is taken over the entire zigzag cycle consisting of Carnot cycles. then the result obtained is that Q1 Q2 Q3 Q4 Q5 + + + + + . Q3 Q4 + =0 T3 T4 Similar equations can be written for each Carnot cycle and if all the equations are added. j in number. This function S. in limit we obtain: Qj ∑T j =0 → j ∫ dQ =0 T 4. then a zigzag path can be made to approximate the original cycle as closely as we please. namely Entropy (in Greek. meaning "transformation").. = 0 T1 T2 T3 T4 T5 Since no heat is transferred during the adiabatic portions of the zigzag cycle. This is often a sufficient definition of entropy if you don't need to know about the microscopic details. Now. AP3290 54 . When the isothermal processes (ab. is developed in the 1850s by German physicist Rudolf Clausius. This result proves that the function defined as is a state function.. When these isothermal processes become infinitesimal. imagine the cycle divided into a very large number of strips of very narrow Carnot cycles.Thermodynamics Y Y Shan Q1 Q2 + =0 T1 T2 Then for the next Carnot cycle “efgh”.

3 An “ entropy generator”: Joule paddle wheel apparatus It is instructive to calculate a unit of entropy. 1. Consider the Joule paddle wheel apparatus shown in the following. AP3290 55 . the internal energy is unchanged. The system is 1kg water at T=300K T. The falling mass does work on the system. and the paddle wheels. Entropy generator The change of entropy of the reservoir is given by: ∆S reservoir = ∫ dQ Q = T T Since the state of the water (temperature and volume) is unchanged at the end of the process.Thermodynamics Y Y Shan B dQ A T ∆S BA = S B − S A = ∫ For the case of an isothermal process(constant temperature) it can be evaluated simply by ∆S = Q/T. also at T=300K. the diathermic bottom in contact with a heat reservoir. The surroundings are the adiabatic cylindrical wall. in order to gain a feeling for this new thermodynamic variable. J/K. which causes an increase in the temperature of the water. However. the diathermic bottom prevents the temperature from rising by removing heat energy Q from the system into the reservoir. A slowly falling mass m causes the paddle wheels to turn. The unit for entropy is Joules/Kelvin (J/K) or eV/K.

4 The entropy version of the second law : principle of entropy increasing: There are different versions. If the paddle wheel is driven by a mass of 29. the second law in its heat engine formulation. Here the universe is defined as: AP3290 56 . a process can occur only if it increases the total entropy of the system” Thus. done by the falling mass.9kg × 9.” And in its heat formulation by Clausius is: “Heat cannot spontaneously flow from a material at lower temperature to a material at higher temperature. this the principle of entropy increasing. is: “It is impossible to convert heat completely into work. or undergo some physical process that increases its entropy. Therefore. but all equivalant to each other. Thus. by Lord Kelvin.0( J / K ) T 300 K The entropy is generated by the conversion of work (done by the mass) into heat (entering the reservoir). ∆S mass = 0 Then the change of entropy is given by: ∆S = ∆S reservoir + ∆S water + ∆S mass = Q 29. the paddle wheel apparatus serves as an entropy generator. the work W. equals the heat Q that enters the reservoir. In chapter 3. we can say: the entropy of the universe tends to increase. Q = W = mgh The entropy of the mass turning the paddle wheels is not changed during the process. 1.” The version of the second law that refers to entropy directly is due to Rudolf Clausius “In an isolated thermodynamic system.9 kg that falls 1 meter. because no heat enters or leaves the mass. the thermodynamics system can either stay the same.Thermodynamics Y Y Shan ∆S water = 0 ∆U water = W − Q = 0 Thus.8 N / kg × 1m = = 1. of the second law of thermodynamics.

consists of the 'surroundings' (the hot room) and 'system' (glass. whereas the entropy of the surroundings decreases. The entropy of the “system” will change by the amount: dS system = dQ dQ = Tice 273K The entropy of the “surroundings” will change by an amount: dS surrounding = − dQ − dQ = Troom 300 K So in this example.Thermodynamics Y Y Shan “universe”(isolated thermodynamic system) = ”a system” + ”its surroundings” ∆S (universe) ≥ 0 Ice melting . In this universe. The heat dQ for this process is the energy required to change water from the solid state to the liquid state.a classic example of entropy increasing described in 1862 by Rudolf Clausius A small 'universe'. ice. some heat energy dQ from the warmer “surroundings”(at 300K) will spread out to the cooler “system” of ice and water at its T of 273 K . cold water). the entropy of the system increases. the melting temperature of ice. AP3290 57 .

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