Conceptual Physics Phase Changes Thermodynamics

Conceptual Physics Phase Changes Thermodynamics Lana Sheridan De Anza College July 25, 2016

Last time heat capacity thermal expansion heat transfer mechanisms Newton s law of cooling the greenhouse effect

Overview phases of matter and phase change the laws of thermodynamics entropy heat engines

Phase Changes During a phase change, temperature doesn t change, even when heat is added!

Latent Heat latent heat of fusion, L f The amount of energy (heat) per unit mass required to change a solid to a liquid. heat, Q = ml f latent heat of vaporization, L v The amount of energy (heat) per unit mass required to change a liquid to a gas. Q = ml v

Phase Change paths

Regelation This is a phenomenon seen in water because its density is lower in its solid state. High pressure applied to solid water causes it to melt, even at low temperatures. This makes ice skating work.

Evaporation evaporation the process by which a liquid changes to a gas at the liquid surface Since changing from a liquid to a gas requires heat, when a liquid evaporates it takes heat from its surroundings. This is why humans sweat in hot water, pigs wallow puddles, and dogs pant. All are trying to use evaporation of water to reduce body temperature.

The number of molecules having speeds ranging from v Distribution of speeds to of v molecules dv equals at a given the area temperature: of N the tan rectangle, N v v dv. Evaporation and Distribution of Molecular Speeds v mp v avg v rms N v There are always some molecules with more kinetic energy than most molecules: those can vaporize at a lower temperature. dv v

Evaporation Ben Franklin noticed that a wet shirt kept him feeling cool on a hot day. He decided to experiment to see if the temperature of objects could be lowered by this process. In 1758 he and John Hadley took a mercury thermometer and repeatedly wet the bulb with ether while using bellows to keep air moving over it. Despite it being a warm day, they recorded temperatures as low as 7 F ( 14 C) at the bulb of the thermometer. This is the basic idea behind refrigeration!

Condensation condensation the process by which a gas changes to a back into a liquid A glass of ice water in will collect water on the outside of it in hot, humid weather. The drink is heated by the gas in the air, but as it takes heat from the air, water vapor condenses out onto the glass. This is also the process that causes dew to collect overnight.

Boiling boiling the change of a liquid to a gas that occurs not only at the surface but throughout the liquid In a rolling boil, bubbles can be seen to be forming within the middle of water in a pot. These bubbles are steam - gaseous water. It forms randomly in pockets throughout the whole pot.

Melting melting the change of a solid to a liquid As a substance reaches the temperature at which is melts, additional heat energy goes into the internal energy of the atoms / molecules making up the substance. Bonded atoms / molecules are in a state that has low potential energy. In a liquid the rigid bonds between molecules are broken. Breaking these bonds corresponds to increasing the potential (internal) energy of the molecules.

Freezing freezing the change of a liquid to a solid Here heat is lost from the substance, causing molecules to lose potential (internal) energy. The solid material bonds reform.

Phase Diagrams

Practice Problem 2, page 314. The specific heat capacity of ice is about 0.5 cal/g C. Supposing that it remains at that value all the way to absolute zero, calculate the number of calories it would take to change a 1 g ice cube at absolute zero ( 273 C) to 1 g of boiling water. How does this number of calories required to change the same gram of 100 C boiling water to 100 C steam? Reminder: 1 cal is the heat required to raise the temperature of 1 g of water by 1 C. 1 Hewitt, Problem 2, page 314.

Practice Problem 8, page 314. The heat of vaporizations of ethyl alcohol is about 200 cal/g. If 2 kg of this fluid were allowed to vaporize in a refrigerator, show that 5 kg of ice (at 0 C) would be formed from 0 C water. 1 Hewitt, Problem 8, page 314.

Thermodynamics The name of the field literally means movement of heat. Thermodynamics is the study of the relation between heat and work, and volume, pressure, temperature, and entropy. All of the observable variables are macroscopic: they only refer to bulk properties of the fluids under study. When thermodynamics was first developed, there was no understanding at all of atoms or microscopic interactions.

Thermodynamics Motivation Thermodynamics was developed in the 1800 because of a need to understand the relation between work and heat. Steam engines were first experimented with 2000 years ago, and demonstrated practically in the 1600s. By the mid 1800s, these engines were becoming economical. They became the cornerstone of transport and production in the industrial revolution. Better understanding how to design them was crucial.

Some quantities We already introduced internal energy. Reminder: internal energy, E int or U int The energy that an object has as a result of its temperature and all other molecular motions, effects, and configurations. Later we will need another quantity also: entropy.

First Law of Thermodynamics 1st Law The change in the internal energy of a system is equal to the sum of the heat added to the system and the work done on the system. U int = W + Q This is just the conservation of energy written in a different way! It takes into account that heat is energy.

Second Law 2nd Law Unless work is done on a system, heat in the system will flow from a hotter body in the system to a cooler one. This is obvious from experience, but it s not obvious why this should happen. It also indicates there is are processes in the physical world that seem not to be time-reversible.

Entropy Entropy is a measure of disorder in a system. It can also be used as a measure of information content. Intriguingly, entropy was introduced separately in physics and then later in information theory. The fact that these two measures were the same was observed by John von Neumann.

Entropy According to Claude Shannon, who developed Shannon entropy, or information entropy: I thought of calling it information, but the word was overly used, so I decided to call it uncertainty. [...] Von Neumann told me, You should call it entropy, for two reasons. In the first place your uncertainty function has been used in statistical mechanics under that name, so it already has a name. In the second place, and more important, nobody knows what entropy really is, so in a debate you will always have the advantage.

So what is entropy? Consider the Yo. app (valued at $5-10 million in 2014). You can only use it to send the message yo. If you get a message on the app, you can guess what it will say.

So what is entropy? Consider the Yo. app (valued at $5-10 million in 2014). You can only use it to send the message yo. If you get a message on the app, you can guess what it will say. The message has no information content, and it is perfectly ordered, there is no uncertainty. The message is a physical system that can only be in one state.

So what is entropy? But what if the message is only sent with 50% probability? If you get the message, let s meet for drinks, if not, I m still in a meeting and can t join you.

So what is entropy? But what if the message is only sent with 50% probability? If you get the message, let s meet for drinks, if not, I m still in a meeting and can t join you. Now you learn something when you get the message. The information content is 1 bit.

So what is entropy? (Shannon) Entropy of a message m: H(m) = i p i log p i where p i is the probability of receiving message i.

So what is entropy? (Shannon) Entropy of a message m: H(m) = i p i log p i where p i is the probability of receiving message i. For the fully-determined message yo : H(m) = 1 log 1 = 0 bits

So what is entropy? (Shannon) Entropy of a message m: H(m) = i p i log p i where p i is the probability of receiving message i. For the fully-determined message yo : H(m) = 1 log 1 = 0 bits For the yo -or-no message: H(m) = 1 2 log 1 2 1 2 log 1 2 = log 2 = 1 bit

Entropy in Thermodynamics In physics, we express entropy a little differently: S = k B p i ln p i i k B is called the Boltzmann constant. k B = 1.38 10 23 J K 1 Notice that this gives the units of entropy as J / K.

Entropy in Thermodynamics Consider the atmosphere, it is mostly Oxygen and Nitrogen. Have you ever walked into a room and been unable to breathe because all of the oxygen in on the other side of the room? a b c As more oxygen molecules are added, the probability that there is oxygen is on both sides increases.

the molecules are oxygen and the other half are nitrogen. At any given moment, the probability of one molecule being in the left part of the container shown in Figure 22.15a as a result of random motion is 1 2. If there are two molecules as shown in Figure 22.15b, the probability of both being in the left part is 1 1 2 2 2, or 1 in 4. If there are three molecules (Fig. 22.15c), the probability of them all being in the left portion at the same moment is 1 1 2 A macrostate is something 2 3, or 1 in 8. For 100 independently moving molecules, the probability that the 50 oxygen molecules we can will observe be found onin a the large left scale. part at any moment is 1 1 2 2 50. Likewise, the probability that the remaining 50 nitrogen molecules will be found in the right part at any moment is 1 1 2 2 50. Therefore, the probability of Macrostates and Microstates The macrostates here could be: a b c all oxygen on the left all oxygen on the right oxygen mixed throughout the room. Figure 22 tions of ide container. exist only t guish amo (a) One m has a 1-in-2 the left sid have a 1-in the left sid (c) Three m chance of b at the same

of a 4 on a pair of dice is only three times as probable as a macrostate of 2. The ratio of probabilities of a worthless hand and a royal flush is significantly larger. When we are talking about a macroscopic thermodynamic system containing on the order of Avogadro s number of molecules, however, the ratios of probabilities Macrostates and Microstates can be astronomical. A microstate is a state too small / complex to easily observe, but Let s explore this concept by considering 100 molecules in a container. Half of represents the molecules one are way oxygen a macrostate and the other half canare be nitrogen. achieved. At any given moment, the probability of one molecule being in the left part of the container shown in Figure 22.15a as a result of random motion is 1 2. If there are two molecules as shown in Figure 22.15b, the probability of both being in the left part is 1 1 2 2 2, or 1 in 4. If there We want to consider the number of microstates for each macrostate. are three molecules (Fig. 22.15c), the probability of them all being in the left portion at the same moment is 1 1 2 2 3, or 1 in 8. For 100 independently moving molecules, the probability that the 50 oxygen molecules will be found in the left part at any moment is 1 1 2 2 50. Likewise, the probability that the remaining 50 nitrogen molecules will be found in the right part at any moment is 1 1 2 2 50. Therefore, the probability of The macrostates here could be: all oxygen on the left 1 microstate a all oxygen on the right 1 microstate oxygen mixed throughout the room 6 microstates b c more disordered tha sample. We will not order approach in th watch for it in other Figure 22.15 Poss tions of identical mo container. The color exist only to allow u guish among the mo (a) One molecule in has a 1-in-2 chance o the left side. (b) Two have a 1-in-4 chance the left side at the sa (c) Three molecules chance of being on at the same time.

b c guish among the mo (a) One molecule in has a 1-in-2 chance o the left side. (b) Two have a 1-in-4 chance the left side at the sa (c) Three molecules chance of being on at the same time. Suppose all of the microstates are equally likely. If so, even with only 3 molecules, we would expect to find the oxygen distributed throughout the room (75% probability). S = k B p i ln p i Entropy of the all on the left macrostate: S L = k B ln 1 = 0 Entropy of the mixed macrostate: i S M = k B ln 6 1.8k B The entropy of the mixed macrostate is higher!

Boltzmann s formula The entropy of a macrostate can be written: S = k B ln W where W is the number of microstates for that macrostate, assuming all microstates are equally likely. W is the number of ways the macrostate can occur.

Entropy and disorder A macrostate that has very many microstates can be thought of as a disordered state. If all the oxygen is on the left of the room, all the nitrogen on the right, the room is organized, or ordered. But this is very unlikely! Even if a room starts out ordered, you would expect it to become disordered right away, because a disordered room is more probable.

Entropy example Problem 8, page 331. Construct a table of all the possible combinations of numbers that can come up when you throw 2 dice. The score of the dice will be the sum of the two numbers on the dice. Why is 7 the most likely score?

Second Law of Thermodynamics This gives us another way to state the second law: 2nd Law In an isolated system, entropy does not decrease. equivalently: S t 0 Heat must flow from hotter to colder because there are more ways to distribute heat evenly than to keep it in one place only. As time goes by, things tend to disorder.

Third Law of Thermodynamics 3rd Law As the temperature of a material approaches zero, the entropy approaches a constant value. The constant value the entropy takes is very small. It is actually zero if the lowest energy state of the material is unique. Another way to express the third law: 3rd Law - alternate It is impossible to reach absolute zero using any procedure and only a finite number of steps.

Heat Engines Steam engines and later incarnations of the engine run on a very simple principle: heat is transferred from a hot object to a colder object and mechanical work is done in the process. Usually, some chemical energy (burning fuel) is used to raise the temperature of one object, and the colder object remains at the ambient temperature.

Heat Engines 1 Diagram from http://www2.ignatius.edu/faculty/decarlo/

Efficiency of a Heat Engine Efficiency: e = Q H Q C Q H = W Q H An ideal engine, one that has the highest possible efficiency, has efficiency: (T is measure in Kelvin!) e = T H T C T H It is not possible for any engine to have efficiency higher than this without violating the 2nd law.

Perfect but Impossible Engine It would be nice if all heat energy Q H could be converted to work.

Perfect but Impossible Engine X But this is not possible. It would be nice if all heat energy Q H could be converted to work. That would require T C = 0, so that W = Q H. Cannot happen.

Second Law and Heat Engines We can state the second law also as a fundamental limitation on heat engines. Second Law of Thermodynamics (Heat Engine version) It is impossible to construct a heat engine that, operating in a cycle, produces no effect other than the input of energy by heat from a reservoir and the performance of an equal amount of work.

Heat Engines 1 Diagram from http://www2.ignatius.edu/faculty/decarlo/

Heat Engine question Problem 2, page 331. Consider and ocean thermal energy conversion (OTEC) power plant that operates on a temperature difference between deep 4 C water and 25 C surface water. Show that the Carnot efficiency of this plant is 7%.

Heat Pump Refrigerators work by taking electrical energy, converting it to work, then pumping heat from a cold area to a hotter one. 1 Diagram from http://hyperphysics.phy-astr.gsu.edu

Question Suppose you have a house with very excellent insulation. If you leave the door to your refrigerator open for the day, what happens to the temperature of your house? (A) It increases. (B) It decreases.

In a gasoline engine, six processes occur in each cycle; they are illustrated in Figure 22.12. In this discussion, let s consider the interior of the cylinder above the piston to be the system that is taken through repeated cycles in the engine s operation. For a given cycle, the piston moves up and down twice, which represents a four-stroke cycle consisting of two upstrokes and two downstrokes. The processes in the cycle Car Engines Car can be engines approximated work by the Otto by cycle burning shown in fuel the PV indiagram cylinders Figure with 22.13 pistons. (page 666). In the following discussion, refer to Figure 22.12 for the pictorial representation of the strokes and Figure 22.13 for the significance on the PV diagram of the letter designations below: The four stroke cycle: 1. During the intake stroke (Fig. 22.12a and O S A in Figure 22.13), the piston moves downward and a gaseous mixture of air and fuel is drawn into the The intake valve opens, and the air fuel mixture enters as the piston moves down. The piston moves up and compresses the mixture. The spark plug fires and ignites the mixture. The hot gas pushes the piston downward. The exhaust valve opens, and the residual gas escapes. The piston moves up and pushes the remaining gas out. Spark plug Air and fuel Exhaust Piston Intake Compression Spark Power Release Exhaust a b c d e f Figure 22.12 The four-stroke cycle of a conventional gasoline engine. The arrows on the piston indicate the direction of its motion during each process.

Car Engines Air and fuel The intake valve opens, and the air fuel mixture enters as the piston moves down. Spark plug Piston Intake

b Car Engines The piston moves up and compresses the mixture. g n Compression

s downward and a gaseous mixture of air and fuel is drawn into the Car Engines alve the air enters moves Spark plug The piston moves up and compresses the mixture. The spark plug fires and ignites the mixture. The hot gas pushes the piston downward. The exha opens, an residual g Piston e Compression Spark Power Relea

gaseous mixture of air and fuel is drawn into the Car Engines n moves ompresses ure. The spark plug fires and ignites the mixture. The hot gas pushes the piston downward. The exhaust valve opens, and the residual gas escapes. The pis up and remain ssion Spark Power Release Exha

e of air and fuel is drawn into the Car Engines spark plug and ignites ixture. The hot gas pushes the piston downward. The exhaust valve opens, and the residual gas escapes. The piston moves up and pushes the remaining gas out. Exhaust Spark Power Release Exhaust c d e f

2.13), the piston rawn into the Car Engines t gas the piston ard. The exhaust valve opens, and the residual gas escapes. The piston moves up and pushes the remaining gas out. Exhaust ower Release Exhaust d e f

PV Diagrams and Adiabatic Processes 666 Chapter 22 Heat Engines, Entropy, a The 4-stroke cycle can be represented plotting pressure against volume of the gas in the cylinder. P cylinder at T A T C energy ent C as potentia Adiabatic from V processes 2 to sion stroke Q h from V 1 to 2. During th ton moves B D Q c volume V 1 O A work done V 2 V 1 V area unde 3. Combustio Adiabatic process Figure 22.13 PV diagram for 22.13). Th short time the Otto cycle, which approximately isrepresents not transferred the processes into or out of the working Process in which heat fluid. occurring in an internal combus- tion repre in chemica

22.12. In this discussion, let s consider the interior of the cylinder above the piston to be the system that is taken through repeated cycles in the engine s operation. For a given cycle, the piston moves up and down twice, which represents a four-stroke Car Engines cycle consisting of two upstrokes and two downstrokes. The processes in the cycle can be approximated by the Otto cycle shown in the PV diagram in Figure 22.13 (page 666). In the following discussion, refer to Figure 22.12 for the pictorial representation of the strokes and Figure 22.13 for the significance on the PV diagram of the letter designations below: The four stroke cycle: 1. During the intake stroke (Fig. 22.12a and O S A in Figure 22.13), the piston moves downward and a gaseous mixture of air and fuel is drawn into the The intake valve opens, and the air fuel mixture enters as the piston moves down. The piston moves up and compresses the mixture. The spark plug fires and ignites the mixture. The hot gas pushes the piston downward. The exhaust valve opens, and the residual gas escapes. The piston moves up and pushes the remaining gas out. Spark plug Air and fuel Exhaust Piston Intake Compression Spark Power Release Exhaust a b c d e f Figure 22.12 The four-stroke cycle of a conventional gasoline engine. The arrows on the piston indicate the direction of its motion during each process.

Jet Engines Jet engines are even simpler and more efficient than car engines. However, they require more advanced materials... 1 Turbofan schematic from Wikipedia by K. Aainsqatsi.

Advanced Jets: Scramjet...and higher speeds of operation. 1 Scramjet schematic from Wikipedia by User:Emoscopes.

Summary phases of matter and phase change Laws of thermodynamics entropy absolute zero heat engines practical engines Homework Hewitt, Ch 17, onward from page 312. Exercises: 1, 11; Problems: 1 Ch 18, onward from page 329. Exercises: 3, 7, 11, 17, 25, 29. Problems 1, 5, 7.