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Chapter 20

Entropy and the Second Law of
Thermodynamics
I'd like to explain entropy in a clear, intuitive manner. Unfortunately I don't have such an explanation.
Robert Jones, in his book Common-Sense Thermodynam'ics, writes:
No simple "intuitive reason" can be given to explain why a state functi,on results when a quantity . . . is divided by the temperature. And indeed Clausius [one of the pioneers of thermodynamics] himself took 15 years in developing a concept of entropy that satisfied his own
doubts. So what can we say about entropy? Entropy is a state function, which means

of heat

p,I/, and T there is a well-defined value for the entropy ,S. Being a state function also means that if we can
find even a single way to calculate the entropy, then any other way to calculate the entropy must give the
same result.

that for any combination of

We are typically interested only in changes in the entropy AS. While usually the change is both easier to calculate and more meaningful.

it is possible to calculate

the entropy,

To decrease the entropy requires work or energy from outside the system. For a closed syst€D, the entropy can never decrease. A reversible process is one where the entropy change is zerol so that a positive entropy change means that the process can't be reversed, at least without some outside source of energy.
Reversible processes happen infinitely slowly (and are therefore no fun to watch). We don't have a good way to calculate AS for an irreversible process, so we find a reversible path that goes from the starting configuration to the final one, then we can calculate the change in entropy for the reversible process.

The change in entropy is

As

:

ln'#
nCy m* tt

Two important special cases are adiabatic and isothermal processes. They are important because they are easy to calculate. For an adiabatic process, LQ : 0, so AS - 0. For an isothermal process, ? is a constant so AS - LQ lT. Lengthier calculations include an ideal gas
ASia".r
gas

- nRmY * V,;

and for a solid or liquid, with no volume change
ASsolidliquid

:

I#

Student: What is that temperature? Tutor: We don't know.030 ke) . so these two equations are very similar.Lm - (333 kJlkg)(0.(0.mcLT - (0.030 kg) .o3o kg * 0. How much will the water cool while the ice melts? . until the temperatures are equal.ee kJ : eee0 J Tutor: Student: I was wondering Q why it took so little heat to melt the ice. Student: Q .508 kg)(18") (0.tiquid . You saw that a change of 5"C is the same as 5 K.r. .mcLT -+ (627 + 9990) J : (0. .S of the water and ice as the ice melts and the system comes to equilibrium. The melted ice will then warm as the cooled water further until they are all the sarne temperature.508 kg) . T\rtor: cools. Q . Yes.Qz: m2/LT2 (0. E I"ROPY AArD THE SECOI\rD LAW OF THERMODYNAMICS that Cv is energy per kelvin per mole.508 kg) . Now I need to find the energy to melt the ice.e.ee J ? Tutor: Uh."*T + ? "j[:ff::: yes? Yes.Ql ."t:":K) rn rtrtor: T\rtor: How are you going Student: I must have made a mistake. The heat that the melted ice gains is equal to the heat that the cooled water loses. When you found the heat to warm or melt the ice.Lm - (333 kJlkg)(0.508 kg) (18')ff\\^ / (o. that's kilojoules. We have to figure it out.e. Student: Now we can.158 Remember CHAPTER 20.K)AT -> LT: 5K The water is cooled to 18'C as the ice melts. It's good to see whether your answer makes sense. EXAMPLE A 30 g ice cube at -5"C is placed in 508 g of 23" C water.0o) : (0. Student: But I don't know the temperature. it warms to 0"? T\rtor: o.o m1/LT1 T\rtor: Student: And we still haven't done the entropy.TTLCIn fi? Yes. Find the change in entropy A.030 kg)(4180 Jlkg-K)(5 K) - 627 J Tutor: Student: Good. Oops. Tutor: Then make up a variable. What is the change in_entropy of the ice as Can we use ASrorid.030 ks) g . it will be OoC. it was a temperature difference.r) (")(0. How much energy does it take to warm the ice? Student: The mass times the specific heat times the temperature change. Now find the equilibrium temperature.508 ke)(4180 Jlke. . Q . Student: What's equilibrium? After the ice has melted. . and c is energy per kelvin per kg. Good. Tutor: Student: .030 ks * 0.508 kg)(18' .

and that happens at a constant temperature. Student: Ok y.01 J lK. but lower temperature gas with a lower pressure.K). First we need to know about reservoirs. When the "working fluid" is in contact with the hotter or higher temperature reservoir. the higher pressure from the hotter side will spin the turbine. Student: What kind of unit is a joule per kelvin? AS: 9T Student: And then the melted S ice warms.01 J lK. then both sides of the turbine would be at the same pressure and the turbine wouldn't spin or do work. AS - (0. but when I divide temperatures I need to use kelvin.030 ks)(4180 Jlkg. or use the torque directly. so the entropy will be the same as it was.01 JIK Student: Then the total change in entropy As - (2. the initial temperature of the water was 23". In the last chapter.32 JIK) + (36. it boils into gas or steam. (0. and the water will absorb energy from the room. We can connect this turbine to a generator and get electricity. I'll be back where I started. That means that this process is irreversible. Tutor: Yes.48 Tutor: Good. just like I don't have a good one for entropy. Student: So if I take the water back to the initial conditions. the change in entropy of the freezer and the room must be positive and greater than 3. A reservoir is an external body at a particular temperature. If we had only one reservoir. and if we include that in our system the change in entropy will be positive. . . Student: The change in entropy is positive. Then the ice melts.159 Student: .K) is: ' l' Y23+273 JIK):3. When the working fluid is in contact with the colder or lower temperature reservoir.32 JIK T\rtor: I don't have a good explanation for that.58 JIK) + (-43. The effect of entropy is to limit the efficiency of thermodynamic processes. so if I leave it sitting out it will warm again. ry_5+t 2. If we put a turbine or propeller or fan between the two reservoirs.K)ln . As - (0. Now we tell why.5e JIK) + (7. The change in entropy of the water as you move it back to the initial conditions will be -3. right? Tutor: AII true. Find a liquid that boils at a temperature that is lower than the hotter of the two reservoirs. In - IUzs o+2n -7. Oh y€s. Though not perfectly true. Student: But I could put 30 g of the water in the freezer and turn it into ice again. we said that we could not recover the heat out. That's what being a "state function" means.508 kg)(4180 Jlkg.ss JIK 273K J lks.030 kg)(4180 ry:36. and 23"C is room temperature. it works well for doing calculations. . T\rtor: Correct.58J/K T\rtor: Student: And the water cools. Student: Remember to include the cooling that happens as the ice melts. You can reduce the entropy only by bringing work or energy in from outside the system. But the freezer will use electrical energy. so I could use Celsius. it either condenses to liquid or is still ges. To make a heat engine an engine that turns heat into work requires two reservoirs. The reservoir is large enough that we can add heat or take heat out and not change the temperature of the reservoir.

It is now colder than the room. to energy in. r'E lQrl <' rH-rL . As you walk back inside.. expanding the gas. and heat flows from the room to the box. so that the energy does not escape to the atmosphere. Take a piece of paper (or this book) and turn it so that . compressing it. When the working fluid is in contact with the high-temperature reservoir. repeating until the inside air is cool enough. You can't turn all of the heat into work. To do so takes work. The second law of thermodynamics can be expressed in many ways. you expand the box again. you pull out the side of the box. Heat engine The efficiency is the ratio of the work out efficiency is Tr. How large a solar pond would be needed to make a 1 GW power plant? T\rtor: Student: One gigawatt seems like a lot of power. it absorbs heat from the reservoir. and we use electricity to power an electric motor to do this work. Use 450 W l^' for the intensity of solar radiation. As it expands. so we need to put energy in to the heat pump in the form of work. and is also limited by the laws of thermodynamics: A r. Standing inside. so that it is hotter than the outside air. You now walk outside while pushing in on the box.Tr. Heat now flows from the box to the air. the gas cools. typically through coils on the back. "Carnot cycle. heated layer. After going through the turbine.160 CHAPTER 20.y. and heat comes from the working fluid to the reservoir. Not all of the heat taken from the high-temperature reservoir can get turned into work. This water is used to make steam out of a working fluid with a suitably low boiling point.[. Tn which is obtained isotherms. -. An air conditioner moves heat from the cooler room to the hotter outdoors. EXAMPTE A solar pond uses salt to trap the heated water at the bottom of the pond. As the gas in the box compresses. designed so that you can push in one side to change the volume. How can work move heat from a cold reservoir to a hot one? Imagine that you have a box of gas. The coefficient of performance for a heat pump is the ratio of heat extracted to work supplied. Heat does not normally flow this w&y. Student: Why is the Sun shining for only 6 hours per day? T\rtor: The Sun is not always directly overhead. The highest possible Tn : Ts . the fluid comes in contact with the low-temperature reservoir. About enough for an American city of half a million people. E]VTROPY AATD THE SECOIVD LAW OF THERMODYNAMICS The process must lose heat to the lower temperature reservoir. Such a pond can achieve 80"C temperature water in this bottom." consisting of adiabats and heat pump takes heat from the low-temperature reservoir and moves it to the high-temperature reservoir. heat doesn't go from cold to hot on its own. with the Sun shining only 6 hours per d. A refrigerator takes heat out of the colder inside and puts it into the warmer room. and so that heat can flow through the sides of the box. it becomes hotter. Tr Air conditioners and refrigerators are heat pumps. and AS"rored-syste* 2 0 are just some expressions of the second law of thermodynamics.

For example. so you need a reservoir where you can dump 4.161 you are looking somewhat along the page. difference. Good choice.rt-4GW Student: To calculate the efficiency. you're collecting 5. T\rtor: Student: And I need to use kelvin because it's not a temperature Really you only need to use kelvin in the denominator. but it doesn't hurt. then I need 4 GW for 6 hours aday. 7 or 8 in Arizona. You can't collect all of the energy that reaches the pond. The average temperature of the Earth is 15oC. so they only have 2 GW of waste heat to dump. we need to include a factor of cos 0. S in Ohio. The area you see is less than the area of the page. wherc 0 is the angle between the Sun's rays and the normal to the surface. but what's the low temperature? Thtor: Tutor: Student: Take something rea. That comes from the second law of thermodynamics. If I need 1GW of power. but they operate at higher temperatures and are about 33% efficient. or average. Student: Okuy. When the Sun is not directly overhead. but generating 1 GW. Remember that water has a high specific heat and can store a lot of energy. P1rrxe-Po.5 GW. I'll use that. Student: Do coal and nuclear plants have the same problem? Tutor: Yes. The high temperature is 80"C. (80+2Iq) _(15+273) (80 + 273) _0. because Iget nothing for the other L8 hours a day. rather than normal to the page. I need the high and low temperatures.exLorm2 A I About 19 square miles. e_rr_T. T\rtor: You haven't taken the efficiency into account. Student: So I need to multiply by the efficiency.Tn Tutor: Probably not even that much.18 -22cw L r-!-+ ' tA-!-'3450W1^' Il9: Y-4.5 GW of waste heat. T\rtor: Student: . Tutor: Multiply the power reaching the pond by the efficiency to see how much power you can get.sonable. So one of these "solar ponds" could power a city with an area of 4 miles x 5 miles? Ttrtor: Theoretically. It averages out to about 6 hours a day. Okay. Most power plants are located by rivers or lakes so that they can dump the waste heat into the water.18: t8% Student: I can get only 18% of the power out? Pin x (0. There are issues involved with doing so.1S): rn Pout - 4 GW n^-19 0.