CHAPTER 10

First and Second Laws of Thermodynamics

10.1. Introduction: Entropy and the Arrow of Time

Earlier we stressed the fundamental importance of the conservation of energy. However, there are many processes that conserve energy but we never observe. For example of when a hot object is placed next to a cold one, heat ows from the hot object to the cold object, but never the reverse. Why? It would still conserve energy. What about when you drop a rock. As it is falling the potential energy is converted into kinetic energy, and after it falls the kinetic energy is converted to thermal energy (molecules move faster, and temperature rises slightly). We never see the reverse. Why? There is nothing in the laws of Mechanics that would prevent this from happening. It would still conserve energy, etc. There are many examples. A drop of ink disperses in glass of water, but no matter how much we stir the mixture, we never see all the ink come back to a single blob.1 Similarly, if we have a layer of salt on top of a layer of pepper in a jar.2 If we shake it, the salt and pepper all mix together. We will never see it separate again, no matter how long we shake the jar. It would be obvious if we ran a movie of these things backwards. That is, we can tell the dierence between before and after. We could tell what is the direction of time: these things are said to be irreversible.
1 2

demo: drop of ink in water demo: shake a jar of salt and pepper

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Introduction: Entropy and the Arrow of Time

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Irreversibility
Irreversibility can be stated in many equivalent ways called the Second Law of Thermodynamics.

This irreversibility can be stated in many ways called the second law of thermodynamics. There are many ways to state the law:3

There are many ways to state the 2nd law: Heat ows from a hot object to a cold one Heat is not completely availible to do work The total amount of disorder (entropy) always increases

Figure 10.1: Irreversibility.

The second law gives a statement about the arrow of time. This is remarkable since microscopically things are reversible. For example, for the molecules of the ink and the water or the salt and pepper particles, all the collisions are reversible. We couldnt look at a movie of a single collision and tell if it is running forward or backward. Something is dierent when there are many particles. The key to the dierence between before and after is the entropy. Entropy is our next great idea. Entropy is more abstract concept than energy, though it is just as real. The concept of entropy and irreversibility was actually developed through general considerations about the availability of heat to do work, how to describe the ow of heat. In fact it has its roots in developing more ecient engines, but what developed was also a deep and general statement about nature and the direction of the arrow of time.

10.2.

Thermodynamics

Thermodynamics is concerned with processes where energy is transferred as heat or work. We focus on some kind of system and consider transfer of energy into or out of that system.

10.3.

First Law of Thermodynamics

The rst law of thermodynamics is that energy is conserved. The internal energy is a another thermodynamic state variable. The energy of a system can change from 1. ow of heat

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First Law of Thermodynamics

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Isolated Systems

A system is isolated if the total energy is conserved. If heat can ow in or out, a system is not isolated.

QIN

System is not isolated

(Heat ows in and out)

System

System + Environment is isolated

(no heat ow, total Energy Constant)

QOUT Environment

Figure 10.2: Isolated systems.

2. work Heat owing into system increases the energy. Heat owing out of system decreases the energy. Work done by the system decreases the energy. Work done on the system increases the energy.

For example, constant pressure expansion of a gas does work. The total change in internal energy of the gas is Q = QIN W

Figure 10.3: First law of thermodynamics.

10.4.

The Second Law of Thermodynamics

There are many equivalent statements of the second law. They are all equivalent: pick one, the others are consequences. Our rst statement of the second law: Second law of Thermodynamics Heat ows from spontaneously from a hot object to a cold object. Heat never ows spontaneously from a cold object to a hot object.

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Engines: work and the ow of heat

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10.5.

Engines: work and the ow of heat

Combining the rst and second law we can begin to understand how engines work: some of the energy from the ow of heat can be used for work.
Cartoon of Heat Flow
HTR TH
High Temperature Reservoir

Heat ows from high to low temperature reservoir

LTR TL

Low Temperature Reservoir

Figure 10.4: Flow of heat.

If the system takes some of the (heat) energy and does some work, this is called a heat engine. We actually can get heat to ow from cold to hot, but this requires work. This is called a heat pump. Refrigerators must dump at high temperature. (Feel bottom of a refrigerator, or the back of an air conditioner.)

Figure 10.5: Heat pumps.

Heat engines and

In both cases (heat engines and heat pumps), the energy is conserved. The rst law of thermodynamics tells us that EnergyIN = EnergyOUT QH QL + W = QL + W = QH Heat Heat Engine Pump (10.1) (10.2) (10.3) (10.4) In both cases QH = QL + W (10.5)

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Engines: work and the ow of heat

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All engines (and refrigerators) are examples of heat engines (or heat pumps). Lets look a little closer at the system for a heat engine and a heat pump.

Heat pump (refrigerator) Compressor pumps High P High T Vapor into the condenser Condenser removes heat: gas to liquid Low P, Low T liquid absorbs heat: liquid to gas Back into Compressor
Figure 10.6: Example of a typical heat pump.

Heat Engine Pump: High pressure water pumped into boiler Boiler: heat added exits boiler as high pressure steam Turbine: Work Stem turns turbine. Some of the work used to run the pump Condenser: heat removed steam condenses to liquid
Figure 10.7: Example of a typical engine.

Another example of an engine: Internal combustion engine (like used in your car). These examples illustrate that engines and a heat pumps work in a cycle:4 . Heat is added at one stage, and heat is removed at a dierent stage.5
4 5

demo: a piston working to see cycle For example in a thermal wheel, in which a wire around a wheel is heated a one point. Since the

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Engines: work and the ow of heat

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Internal combustion engine This cycle involves four steps and is called a four-stroke engine. While dierent in detail, it involves adding heat, removing heat, and doing work, just like before. At the end of the four steps, the system is ready to start over again: It works in a cycle. Since: QH = QL + W , couldnt we get more work if we didnt remove the heat? (If we didnt have to exhaust QL into the LTR, we could convert all the QH into work.) The second law says this is impossible (another statement of the second law). For example, a thermoelectric motor6 requires a HTR and a LTR to work. Both hot and cold water have energy. Energy from hot water is partially converted to work (by a thermocouple). If we mix the hot and cold water together, there is the same energy as before, but now there is no temperature dierence. Motor doesnt work.

wire tends to straighten when heated, the wire is pulled around the wheel. Note the heat exchange and the HTR and LTR. 6 demo

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Engines: work and the ow of heat

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Why is the LTR needed to do net work? As an example, lets look closer at a piston. Consider the work done by a piston: Hot steam expands the piston (system does work) Later piston needs to return back (cycle) If steam was at the same temperature then it would require the same amount of work to compress: no net work. So, we need a low temp reservoir:

Figure 10.8: Illustrations of the second law and engines.

This is actually another statement of the second law: In a cyclic process, a low temperature reservoir (and transfer of heat) is always required to do work. Why is this important? Because QH = QL + W , some heat must be diverted to the LTR, that is: In a cyclic process, not all heat is available to be converted to work. This is a fundamental statement about the nature of heat, and another statement of the second law.

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Engines: work and the ow of heat

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Example: Can QL be zero? No. Which way should it point? Towards LTR If QH = 400J and W = 100J, what is QL ? 300J
Figure 10.9: Example of heat ow and entropy.

Perpetual Motion Machines

It is tempting to think that the work generated could be used to to bring the system back to its starting point. This would be a perpetual motion machine. Since some heat must be discharged, this is always a violation of the second law.

It may be a perpetual motion, but it will take forever to test it.

Cartoon by Donald Simanek

Figure 10.10: Perpetual motion machine is always a violation of the second law.

10.6.

Entropy and the Availability of Energy

Irreversible (real) processes always reduce our ability to use heat to do work. We say that heat energy is degraded. Heat energy at a lower temperature is degraded more: the energy is less available to do work. This denition reects that heat energy added at a lower temperature is less available for work. This means that whenever heat spontaneous ow, the total entropy increases. For Example:

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Entropy and the Availability of Energy

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Entropy was developed to describe the availability of energy. Entropy is a relative quantity: only changes are important. The change in entropy can be written a Q S = (10.6) T where - is for heat loss and + is for heat gained at temperature T.

Entropy and the Availability of Energy

The idea of entropy was introduced to describe the availability of energy to do work: Greater entropy means energy is less available Less entropy means energy is more available Only Changes are important The change in entropy can be written as

- is for heat loss + is for heat gain

Figure 10.11: Entropy and the availibility of heat energy.

Entropy spontaneously increases Example

HTR TH = 600K Q = 30 kJ LTR TL = 300K

QC = 30000 J, TC = 300K, TL = 600. No work just let heat ow

Figure 10.12: Heat ow, entropy, and the availibility of energy.

We can do the same thing if we used some of the energy for work; the result is always Stot > 0. So, we arrive at another equivalent statement of the second law: The total entropy of any system plus that of its environment increases as a result of any natural process. [Note: Parts of the system may reduce its entropy, but this must be compensated by greater gains in entropy of the other parts of the system or environment.

10.7.

Thermal Equilibrium

If we consider the whole universe, this must be an isolated system. So when applied to the Universe, the second law states that as time goes on the whole universe

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Thermal Equilibrium

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Thermal Equilibrium

An isolated system eventually comes to equilibrium: entropy is at a maximum and can no longer increase.

An isolated system eventually comes to thermal equilibrium Heat no longer ows as temperatures become equal. No more work can be done. Entropy stops increasing

At thermal equilibrium, entropy is at a maximum

Figure 10.13: rium.

Thermal equilib-

will eventually come into equilibrium The entropy of the universe will be at its maximum, and can no longer increase. All change will cease. All energy will have been degraded to thermal energy. This is called the heat death the universe. Is universe a closed system? Is this too much extrapolation?7

7 There are many cases where things are not progressing towards equilibrium. When a system is not isolated, for example the earth which absorbs energy from the sun, non-equilibrium states can be sustained.