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 systD, 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#

158
Remember

CHAPTER

20. E I"ROPY AArD THE SECOI\rD LAW OF THERMODYNAMICS

that Cv is energy per kelvin per mole, and c is energy per kelvin per kg, so these two equations

are very similar.

EXAMPLE
A 30 g ice cube at -5"C is placed in 508 g of 23" C water. Find the change in entropy A,S of the water and ice as the ice melts and the system comes to equilibrium.

T\rtor:
cools,

Student: What's equilibrium?

After the ice has melted, it will be OoC. The melted ice will then warm as the cooled water further until they are all the sarne temperature. Student: What is that temperature? Tutor: We don't know. We have to figure it out. How much energy does it take to warm the ice?

Student:

The mass times the specific heat times the temperature change. Q

- mcLT -

(0.030 kg)(4180 Jlkg-K)(5

K)

627 J

Tutor:

Student:

Good. You saw that a change of 5"C is the same as 5 K. Yes. Now I need to find the energy to melt the ice. Q

- Lm -

(333 kJlkg)(0.030 ke)

- e.ee J

Tutor:

Uh, that's kilojoules.

Oops.

Student:

- Lm -

(333 kJlkg)(0.030 kg)

- e.ee kJ :

eee0 J

Tutor:

Student: I was wondering

Q

why it took so little heat to melt the ice. It's good to see whether your answer makes sense. How much will the water cool while the ice melts?

- mcLT -+

(627 + 9990) J

(0.508 ke)(4180

Jlke.K)AT -> LT:

5K

The water is cooled to 18'C as the ice melts. Good. Now find the equilibrium temperature. The heat that the melted ice gains is equal to the heat that the cooled water loses, until the temperatures are equal. Student: But I don't know the temperature. Tutor: Then make up a variable.

Tutor:

Student:

- Ql - Qz: m2/LT2 (0.030 ks) g - 0o) : (0.508 kg)(18' - r) (")(0.030 ks * 0.508 kg) - (0.508 kg)(18") (0.508 kg) (18')ff\\^ / (o.o3o kg * 0.508 kg) - r.o
m1/LT1

T\rtor:

Student: And we still haven't done the entropy. Student:

Now we can. What is the change in_entropy of the ice as Can we use ASrorid,tiquid - TTLCIn fi?
Yes.

it warms to 0"?

T\rtor:

o,"t:":K)

rn

rtrtor:
T\rtor:

How are you going

Student: I must have made a mistake,

."*T

"j[:ff:::
yes?

Yes. When you found the heat to warm or melt the ice,

it was a temperature

difference. . .

159

Student:

. . . so

could use Celsius, but when

I divide temperatures I

need to use kelvin.

AS

(0.030 ks)(4180 Jlkg.K)ln

, ry_5+t

2.32 JIK

T\rtor: I don't have a good explanation for that, just like I don't have a good one for entropy.
Student: Ok y. Then the ice melts,
and that happens at a constant temperature.

Student: What kind of unit

is a joule per kelvin?

AS: 9T
Student: And then the melted
S
ice warms. (0.030 kg)(4180

ry:36.ss JIK 273K

J lks.K), In

IUzs

o+2n -7.58J/K

T\rtor:

Student: And the water cools. Student:

Remember to include the cooling that happens as the ice melts. Oh ys, the initial temperature of the water was 23".

As

(0.508 kg)(4180 Jlkg.K)

is:

' l' Y23+273

JIK):3.01 JIK

Student:

Then the total change in entropy

As

(2.32 JIK) + (36.5e JIK) + (7.58 JIK) + (-43.48

Tutor:

Good.

T\rtor: Correct. Student: But I could put 30 g of the water in the freezer and turn it into ice again, and 23"C is room temperature, so if I leave it sitting out it will warm again. I'll be back where I started, so the entropy will
be the same as it was. That's what being a "state function" means, right? Tutor: AII true. The change in entropy of the water as you move it back to the initial conditions will be -3.01 J lK. But the freezer will use electrical energy, and the water will absorb energy from the room, and if we include that in our system the change in entropy will be positive. You can reduce the entropy only by bringing work or energy in from outside the system. 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 3.01 J lK.

Student:

The change in entropy is positive. That means that this process is irreversible.

Tutor:

Yes.

The effect of entropy is to limit the efficiency of thermodynamic processes. In the last chapter, we said that
we could not recover the heat

out. Now we tell why.

First we need to know about reservoirs. A reservoir is an external body at a particular temperature. The reservoir is large enough that we can add heat or take heat out and not change the temperature of the reservoir. Though not perfectly true, it works well for doing calculations. To make a heat engine an engine that turns heat into work requires two reservoirs. Find a liquid that boils at a temperature that is lower than the hotter of the two reservoirs. When the "working fluid" is in contact with the hotter or higher temperature reservoir, it boils into gas or steam. When the working fluid is in contact with the colder or lower temperature reservoir, it either condenses to liquid or is still ges, but lower temperature gas with a lower pressure. If we put a turbine or propeller or fan between the two reservoirs, the higher pressure from the hotter side will spin the turbine. We can connect this turbine to a generator and get electricity, or use the torque directly. If we had only one reservoir, then both sides of the turbine would be at the same pressure and the turbine wouldn't spin or do work.

160

CHAPTER

20, E]VTROPY AATD THE SECOIVD LAW OF THERMODYNAMICS

The process must lose heat to the lower temperature reservoir. When the working fluid is in contact with the high-temperature reservoir, it absorbs heat from the reservoir. After going through the turbine, the fluid comes in contact with the low-temperature reservoir, 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.

Heat engine

The efficiency is the ratio of the work out efficiency is

Tr.

to energy in. The highest possible

Tn

Ts

- Tr,
Tn

which is obtained
isotherms.

"Carnot cycle," consisting of adiabats and

heat pump takes heat from the low-temperature reservoir and moves it to the high-temperature reservoir. Heat does not normally flow this w&y, so we need to put energy in to the heat pump in the form of work. The coefficient of performance for a heat pump is the ratio of heat extracted to work supplied, and is also limited by the laws of thermodynamics:

r..

r'E lQrl <' rH-rL - [, -.

Tr

Air conditioners and refrigerators are heat pumps. A refrigerator takes heat out of the colder inside and puts it into the warmer room, typically through coils on the back. An air conditioner moves heat from the
cooler room to the hotter outdoors. To do so takes work, and we use electricity to power an electric motor to do this work.

How can work move heat from a cold reservoir to a hot one? Imagine that you have a box of gas, designed so that you can push in one side to change the volume, and so that heat can flow through the sides of the box. Standing inside, you pull out the side of the box, expanding the gas. As it expands, the gas cools. It is now colder than the room, and heat flows from the room to the box. You now walk outside while pushing in on the box, compressing it. As the gas in the box compresses, it becomes hotter, so that it is hotter than the outside air. Heat now flows from the box to the air. As you walk back inside, you expand the box again, repeating until the inside air is cool enough. The second law of thermodynamics can be expressed in many ways. You can't turn all of the heat into work, heat doesn't go from cold to hot on its own, and AS"rored-syste* 2 0 are just some expressions of the second law of thermodynamics.

EXAMPTE
A solar pond uses salt to trap the heated water at the bottom of the pond, so that the energy does not escape to the atmosphere. Such a pond can achieve
80"C temperature water in this bottom, heated layer. This water is used to make steam out of a working fluid with a suitably low boiling point. Use 450 W l^' for the intensity of solar radiation, with the Sun shining only 6 hours per d.y. 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. About enough for an American city of half a million people. Student: Why is the Sun shining for only 6 hours per day? T\rtor: The Sun is not always directly overhead. Take a piece of paper (or this book) and turn it so that

161

you are looking somewhat along the page, rather than normal to the page. The area you see is less than the area of the page. When the Sun is not directly overhead, we need to include a factor of cos 0, wherc 0 is the angle between the Sun's rays and the normal to the surface. It averages out to about 6 hours a day, 7 or 8 in Arizona, S in Ohio. Student: Okuy. If I need 1GW of power, then I need 4 GW for 6 hours aday, because Iget nothing for the other L8 hours a day. T\rtor: You haven't taken the efficiency into account. You can't collect all of the energy that reaches the pond. That comes from the second law of thermodynamics.

Tutor: Multiply the power reaching the pond by the efficiency to see how much power you can get.
P1rrxe-Po.rt-4GW Student:
To calculate the efficiency, I need the high and low temperatures. The high temperature is 80"C,

Student:

So

need

to multiply by the efficiency.

but what's the low temperature?

Thtor: Tutor:

Student:

Take something rea.sonable. Okay. The average temperature of the Earth is 15oC.

I'll

use that.

Good choice.
difference.

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.

e_rr_T,Tn
Tutor:
Probably not even that much.

(80+2Iq) _(15+273) (80 + 273)

_0.18:

t8%

Student: I can get only 18% of the power out?

Pin

x (0.1S):
rn

Pout

4 GW

n^-19 0.18

-22cw

L r-!-+ ' tA-!-'3450W1^' Il9: Y-4.exLorm2 A I

About 19 square miles. So one of these "solar ponds" could power a city with an area of 4 miles x 5 miles? Ttrtor: Theoretically. There are issues involved with doing so. For example, you're collecting 5.5 GW, or average, but generating 1 GW, so you need a reservoir where you can dump 4.5 GW of waste heat. Student: Do coal and nuclear plants have the same problem? Tutor: Yes, but they operate at higher temperatures and are about 33% efficient, so they only have 2 GW of waste heat to dump. Most power plants are located by rivers or lakes so that they can dump the waste heat into the water. Remember that water has a high specific heat and can store a lot of energy.

T\rtor:

Student: