Thermodynamics!

Kinetic-molecular theory Specific Heat

Heat & Internal Energy Calorimetry
Thermal Equilibrium Heat Transfer Processes
Temperature Scales Phase changes
Laws of Thermodynamics Thermal Expansion
Entropy Heat Engines & Refrigerators
Latent Heat of Fusion Latent Heat of Vaporization
 Kinetic-Molecular Theory

It was once common belief that heat was an invisible substance.

It even had a name--“caloric,” and it was believed that it could be
transferred between objects but neither created nor destroyed. To
heat up an object this caloric had to flow into it. This, they
thought, explained why objects expanded when heated. But this
theory could not explain, for example, how heat could emanate
from a cold piece of wood once it is set on fire? Where did the
caloric come from? If it had been in the wood in the first place,
the wood should have been hot all along.
The caloric theory was abandoned in the 19th century and replaced
with the kinetic-molecular theory. This new theory stated that all
matter is made up of atoms/molecules in constant motion. The
faster they move, the hotter an object will be.
 Internal Energy
Internal energy (also called thermal energy) is the energy an
object or substance is due to the kinetic and potential energies
associated with the random motions of all the particles that make
it up. The kinetic energy is, of course, due to the motion of the
particles. To understand the potential energy, imagine a solid in
which all of its molecules are bound to its neighbors by springs.
As the molecules vibrate, the springs are compressed and
stretched. (Liquids and gases are not locked in a lattice structure
like this.)
The hotter something is, the faster its
molecules are moving or vibrating, and the
higher its temperature. Temperature is
proportional to the average kinetic energy
of the atoms or molecules that make up a
substance.
 Internal Energy vs. Heat
The term heat refers is the energy that is transferred from one
body or location due to a difference in temperature. This is similar
to the idea of work, which is the energy that is transferred from
one body to another due to forces that act between them. Heat is
internal energy when it is transferred between bodies.
Technically, a hot potato does not possess heat; rather it possesses
a good deal of internal energy on account of the motion of its
molecules. If that potato is dropped in a bowl of cold water, we
can talk about heat: There is a heat flow (energy transfer) from the
hot potato to the cold water; the potato’s internal energy is
decreased, while the water’s is increased by the same amount.
 Units for Heat

Like any type of energy, the SI unit for heat is the Joule.
Another common unit is the calorie, which is approximately
the amount of heat energy needed to raise one gram one degree
Celsius. 1000 calories are in a Calorie, which is used to
measure the energy in foods (that the human body can make
use of). The British thermal unit (BTU) is approximately the
energy needed to raise one pound of water one degree
Fahrenheit.

1 cal = 4.186 J 1 BTU = 1055 J = 252 cal

 Internal vs. “External” Energy
vcm = 7 m/s Suppose a 1 kg block of ice is sliding at 7 m/s.
This is the speed of the center of mass of the
block, not the speed of each individual water
molecule. To calculate the total kinetic energy
of the water molecules of the block directly, we would have to know
the speed of each molecule as it vibrates, all 33.4 trillion trillion of
them! (In practice we would just measure the temperature & mass of
the ice.) The internal energy of the ice does not depend on the
motion of the whole body relative to Earth. What matters is the
motion of the molecules in the reference frame of the block.
Otherwise, it would be impossible for a cold object to move quickly or
a hot one to move slowly. Note: If friction is present, it could do
work on the ice and convert some of the “uniform” kinetic energy of
the block into “random” kinetic energy of its molecules (internal
energy). Regardless, the total energy of the block is the kinetic
energy of the center of mass + the internal energy: Ktotal = Kcm + Eint
 Temperature vs. Internal Energy
Temperature and internal energy are related but not the same thing.
Temperature is directly proportional to the average molecular
kinetic energy*. Note the word average is used, not total.
Consider a bucket of hot water and a swimming pool full of cold
water. The hot water is at a higher temperature, but the pool water
actually has more internal energy! This is because, even though the
average kinetic energy of the water molecules in the bucket is much
greater than that of the pool, there are thousands of times more
molecules in the pool, so their total energy is greater.
It’s analogous to this: A swarm of 1000 slow moving bees could
have more total kinetic energy than a dozen fast moving,
hyperactive bees buzzing around like crazy. One fast bee has more
kinetic energy than a slow one, but there are a lot more slow ones.
*
true for gases, approximately true for solids and liquids whose
molecules interact with each other more. contintued on next slide
 Temperature vs. Internal Energy (cont.)

Which has more internal energy, a bucket of hot water or a

bucket of cold water? answer:

The bucket of hot water has more internal energy, at least

if the buckets contain the same amount of water.
Internal energy depends on the amount (mass) of
substance and the kinetic energy of the molecules of the
substance.
Temperature only depends on the molecules’ kinetic
energy; it is independent of mass.
 Temperature Scales
Fahrenheit: water freezes at 32 °F; boils at 212 °F
Celsius: water freezes at 0 °C; boils at 100 °C
Kelvin: water freezes at 273.15 K; boils at 373.15 K
A change of 100 °C corresponds to a change of 180 °F. This means
5 C° = 9 F° or 1 C° = 1.8 F° Note that the degree symbol is on the
opposite side of the letter, indicating that we’re talking about
temperature differences. In other words, five steps on the Celsius
scale is equivalent to nine steps on the Fahrenheit scale, but 5 °C is
certainly not equal to 9 °F. Since these scales are linear, and they’re
offset by 32 °F, we get the conversion formula: F = 1.8C + 32
One step on the Kelvin scale is the same as one step on the Celsius
scale. These scales are off by 273.15 K, so: K = C + 273.15
Room temperature is around 293 kelvins, which is 20 °C, or 68 °F.
 Absolute Zero & the Kelvin Scale
The Kelvin scale is setup so that its zero point is the coldest possible
temperature--absolute zero, at which point a substance would have
zero internal energy. This is -273.15 °C, or -459.69 °F. Absolute zero
can never be reached, but there is no limit to how close we can get to
it. Scientists have cooled substances to within 10-5 kelvins of absolute
zero. How do we know how cold absolute zero is, if nothing has ever
been at that temperature? The answer is by graphing Pressure vs.
Temperature for a variety of gases and extrapolating.
P A
ga s
A gas exerts no as B
g
pressure when at
absolute zero.
gas C
T (°C)
-273.15 °C 0 °C
 Thermal Equilibrium
Two bodies are said to be at thermal equilibrium if they are at the
same temperature. This means there is no net exchange of thermal
energy between the two bodies. The top pair of objects are in
contact, but since they are at different temps, they are not in thermal
equilibrium, and energy is flowing from the hot side to the cold side.

hot heat cold

26 °C 26 °C

No net heat flow

The two purple objects are at the same temp and, therefore are in
thermal equilibrium. There is no net flow of heat energy here.
 Heat Transfer Processes
Heat energy can be transferred from one body to another in three
different ways. Upcoming slides will give an example of each.

• Conduction: Energy is transferred when two objects are in direct

contact. Molecules of the hotter object bump into molecules of the
colder object and cause them to speed up, warming the colder object.
• Convection: Energy is transferred from one body to a cooler one
via currents in a fluid (a gas or liquid).
• Radiation: All objects, at any temperature, radiate electromagnetic
radiation (light of visible and invisible wavelengths). Unlike
conduction & convection, no medium (matter of any type) is
necessary for heat transfer through radiation. Objects absorb
radiation as well. At thermal equilibrium it will absorb as much as it
radiates.
 Conduction
Schmedrick decides to become a blacksmith. In order to forge a horse-
shoe for his horse, Bucephalus, Scmedrick heats up the shoe in a fire,
pounds on it with a mallet to shape it, and then cools it by dipping it in
a bucket of water. Because the water is colder, heat flows from the
shoe to the water--quickly at first, and more slowly as the shoe cools.
The water molecules, with little kinetic energy, are in direct contact
with the iron atoms, which are jiggling rapidly and have lots of kinetic
energy. When an iron atom bumps into a water molecule, the iron
atom slows down a bit, while the water molecule speeds up (an elastic
collision). In this way water gains the heat energy that the iron loses.
water molecule

iron atom

zoomed in view
 Convection
The water near the hot horseshoe is warmer than the water further
from the shoe. This warm water is lower in density than the cooler
water, since its molecules are moving faster and taking up more space.
With lower density, the warm water begins to float to the surface,
carrying its heat energy with it. As it rises to the surface it cools and
becomes denser. Then it begins to sink, warmer water from below
taking its place. These convection currents transfer heat from the
horseshoe to the air via the water, which is the convection medium.

If the water were surrounded by

something solid or too viscous to flow,
heat could only be transferred to the air
via conduction, and it would take much
longer. Convection plays a big role in
determining global weather patterns.
 Radiation
The molecules of warm water cooling the horseshoe at the surface of
Schmedrick’s bucket bump into air molecules and transfer heat to the
air via conduction. The water can also transfer energy to the air by
emitting electromagnetic radiation. This is simply light, but usually
it’s light of a wavelength that is too long for us to see--infrared.
Bodies also continually absorb radiation, but when a body is warmer
than its surroundings, it emits more than it
absorbs. Night vision technology takes advan-
tage of this fact by detecting infrared light in
order to “see in the dark.” Radiation can cool
or warm objects even if they are surrounded
by a vacuum. (Even a perfect Thermos bottle
full of hot chocolate will eventually cool
down.) When Schmed’s bucket cools long
enough, it will be in thermal equilibrium with
the air, and the net radiation (emission -
absorption) will be zero.
 Radiation: Power & Temperature
The rate at which a hot object emits radiation is its power output.
Recall, power, P, is the rate at which work is done or energy is
expended or absorbed. P depends on the body’s temp (in kelvin) and
on the amount of surface area it has. Power is directly proportional to
the surface area and proportional to the 4th power of absolute
temperature:
P  AT4
Note that the closer the radiating body gets to absolute zero, the
lower its power output of electromagnetic radiation, meaning the
amount of internal energy it is radiating out in a unit of time is low.
Also, an object with lots of surface area will radiate at a greater rate.

Don’t forget that bodies radiate and absorb energy at the same time.
The same equation describes absorption, except we use the temp of
the surroundings. Pnet = 0 when a body is in thermal equilibrium.
 Black Body
A black body is an ideal absorber. It absorbs any radiation that is
incident upon it (any light that hits it). It exists only in theory.
Suppose Schmedrick has Bucephalus is all shoed up and ready to
run. Schmed hops on the back of his trusty steed, and with a mighty
“Hi ho Bucephalus! Away!” he heads off into the sunset. Before
falling off, Schmedrick ponders the sunlight streaming through the
atmosphere from 93 million miles away. Not all of the light that
reaches Earth makes it to the surface. The atmosphere reflects
some of it back into space and absorbs some of it. (It scatters away
more of the blue light than the red, which is why sunsets look red.)
It is the same story for the light hitting Bucephalus: his coat absorbs
some of it (and warms him); and some is reflected (otherwise he
would be called Bucephalus the Invisible Horse).
All real-world objects interact this way with light. Only a black
body would absorb all light, including wavelengths we can’t see.
 Thermal Conductivity, k
Heat transfer via conduction was described a few slides back. Thermal
conductivity, k, refers how easily heat can move through a material.
Metals have high thermal conductivity, meaning heat passes through
them readily. Wood is a fairly good insulated of heat, and styrofoam is
even better. These materials have low thermal conductivities. k is
very low for air as well. (Attic insulation and styrofoam cups trap air,
making them good insulators.) Heat from a boiler passes through all
sides of its metal enclosure. The rate at which heat is transferred is
given by:
H= k A ( T2 - T 1 )
L
A = area of side wall
T2 T1 L = thickness of wall
k = thermal conductivity of the metal
heat T2 - T1 = temperature difference
H is simply power, and its SI unit is the Watt.
 SI Units for Thermal Conductivity
k A (T - T )
H= 2 1
L
k must have units that cancel out all the units on the right,
leaving only the units for H. The units are:

W or equivalently, W
m·K m · °C

Since one kelvin is as big a change in temp as one degree

Celsius, these units are equivalent.
Note: k for thermal conductivity is not the same as the k
in Hooke’s Law in which it represents the spring
constant!
 Cold Tootsies
Have you ever gotten out of bed in the wintertime and
walked barefoot from a carpeted floor to a tile bathroom
floor? The carpeting feels much warmer than the tile.
But, assuming the house is in thermal equilibrium, the
carpet and tile are at the same temp. So why does the tile
feel colder? answer:

The tile has a greater thermal conductivity constant than

the carpeting does. That is, the carpet is a better insulator.
So, even though their temps are the same, the tile draws
body heat away from your tootsies more quickly than the
carpet does. Thus, it feels as if the tile is colder.
 Thermopane Windows
In a house we often want to prevent heat from getting
in or getting out. Windows can be problematic.
Thermopane windows have two or more panes of
heat glass with air or some other gas between the panes.
Which type of window, a double pane or a thick
single pane, is better for minimizing heat transfer, if
the total thickness is the same?

answer:
There is more glass in the single pane window to
block the heat, but the air in between the panes of the
double pane window has thermal conductivity that is
heat
about 35 times lower than that of the glass itself. So
much more heat would be transferred through the
single pane.
 Triple pane vs. Double pane
If they are of the same total thickness and pane
thickness, which is better at minimizing heat
transfer, a double or triple pane window?
heat
answer:
The double pane window has more air between the
outer panes, so its thermal conductivity is lower.
However, air is a mobile medium, and convection
currents can shuttle warm air from the warm side to
the cold side. On the warm side the air rises, moves
across the the cold side, and sinks, moving in a loop
heat and carrying its energy from the warm side to the
cold side. The middle pane in the triple pane window
reduces the energy transfers due to convection and is
the better window (but probably more expensive).
 R Value
The R value of a material is its “thermal resistance” and refers to
how good an insulator is. Here’s how it’s defined:

R = L
k
As in previous equations:
L = the thickness of the material
k = thermal conductivity of the material

Note that the R value is inversely proportional to thermal

conductivity, meaning good heat conductors have a low R value
and are poor insulators. Also, the R value is directly proportional
to the thickness of the material, meaning the thicker it is, the better
it insulates. Thus, more insulation in the attic can save energy.
 Wind & Heat Loss
A breeze can cool us off in the summer, and wind can make us feel
colder in the winter. Why is this?
answer:
When we sweat the perspiration absorbs body heat, and when it
evaporates, it takes this heat with it. This is called evaporative
cooling. A steaming cup of hot chocolate cools in the same way.
The reason a coat keeps us warm in the winter is because it traps air
that is heated by our bodies. (Wearing layers is like having a triple
pane window.) A thin layer of stagnant air also surrounds the outside
walls of buildings and helps insulate them. Wind tends to blow this
warm air away, along with its heat. The windier it is, the colder it
feels to us, and the greater the heat loss from a building.
Trees around you home can save energy in two ways: blocking wind
in the winter; and shielding your home from excess solar radiation in
the summer.
 Laws of Thermodynamics
(examples upcoming)
• Zeroth Law: If object A is in thermal equilibrium with object B,
and if object B is in thermal equilibrium with object C, then objects
A and C are also in equilibrium. This is sort of a “transitive
property of heat.”
• First Law: Energy is always conserved. It can change forms:
kinetic, potential, internal etc., but the total energy is a constant.
Another way to say it is that the change in thermal energy of a
system is equal to the sum of the work done on it and the amount
of heat energy transferred to it.
• Second Law: During any natural process the total amount of
entropy in the universe always increases. Entropy can be defined
informally as a measure of the randomness or disorder in a system.
Heat flows naturally from a hot to cooler surroundings as a
consequence of the second law.
 Zeroth Law

In math we have a transitive property of equality: If a = b

and b = c, then a = c. The zeroth law of thermodynamics
works the same way with temperature.
Suppose some firewood is brought in from the cold and an
apple pie is removed from a hot oven. Both are placed in the
same room. With time the firewood and the room with reach
thermal equilibrium, as will the pie and the room. This means
the firewood and the room are at the same temp. The pie and
room are at the same temp too. Therefore, by the zeroth law,
the firewood and pie are at the same temp, meaning they too
are in thermal equilibrium.
 First Law
Schmedrick is cruising around in dune buggy daydreaming about
thermodynamics. When he hits the gas, a mixture of fuel and air
is injected into a cylinder and ignited by a spark-plug. The
gasoline contains chemical potential energy, meaning when it is
burned by combining it chemically with O2, the products of the
reaction are mainly small molecules (CO2, H2O, & pollutants) that
contain less potential energy than the reactants. Some of this
energy goes into kinetic energy of the dune buggy. The wheels
have both rotational & translational kinetic energy. Some may go
into gravitational potential energy, if Schmed drives up hill. Most
of the energy is actually wasted. The exhaust gas is very hot, and
thus contains internal energy that Schmed would have preferred to
have gone into propelling his vehicle. Some of the energy also
heated up the engine. The 1st Law guarantees that all the original
chemical potential energy is accounted for.
continued on next slide
 First Law (cont.)
As Schmedrick cruises around, he becomes too engrossed in his
daydream and crashes into a street light and putting a big, ole dent in
it. The 1st Law has something to say about the crash too:
In order to dent the pole, work has to be done on it. That is, a force
must be applied to the pole over some distance. The force is from the
dune buggy. The work done on the pole is energy transferred to it by
the buggy, which quickly dissipates as heat. If the pole were made of
some material that could spring back into its normal shape after
impact, it would store some energy during the collision as elastic
potential energy, rather than simply generating heat.
Here’s the point: If you need to do work, the 1st Law demands that
you have at least as much energy available as the amount of work you
need to do. If Schmed had been going slower, his kinetic energy
would have been less, and he wouldn’t have been able to do as much
work on the pole, and the dent would have been smaller.
 Second Law
While his dune buggy is being repaired, Schmedrick decides to take
a to the Alps to practice his yodeling up in the mountains. As fate
would have it, one of his yodels touches off an avalanche, and
thousands of tons of snow crash down in a distant valley. The
gravitational potential energy the snow had before falling is now
thermal energy, as the 1st Law requires. Is it possible for an
avalanche to happen in reverse? answer:

The first law does not prohibit the snow from suddenly rising, so long
as it the potential energy is regains comes from somewhere, such as
the thermal energy of the surrounding air. In other words, the 1st Law
allows a “reverse avalanche” if the surroundings become cooler.
Thermal energy is converted into potential energy, and energy is
conserved. The 2nd Law forbids this, however, since a reverse
avalanche would mean a decrease in entropy in the region around the
valley. There is more about entropy on upcoming slides.
 H H H H 4 heads
Entropy:
Statistical Approach T H H H
H T H H
Entropy is related to probability. Let’s H H T H 3 heads
look at the possible outcomes of flipping H H H T
four coins, of which there are sixteen
(2 4 = 16). The outcomes are grouped into T T H H
macrostates according to the number of T H T H
heads. Each macrostate is made up a T H H T
2 heads
microstates. For example, the 3-heads H T T H
macrostate is comprised of 4 microstates, H T H T
because there are 4 combinations that H H T T
yield 3 heads. One microstate in the 3-
T T T H
heads macrostate is H H T H. The number
T T H T
of microstates in a macrostate determines 1 head
T H T T
how likely that state is to exist.
H T T T
continued on next slide
T T T T 0 heads
 H H H H
Entropy (cont.)
Macrostate # of Microstates Probability T H H H
0 1 1 / 16 H T H H
1 4 1/4
H H T H
2 6 3/8
3 4 1/4 H H H T
4 1 1 / 16
T T H H
Macrostate 3 (the group w/ 3 heads) is the most T H T H
probable since it contains the most microstates (com- T H H T
binations). Macrostate 2 has 6 microstates, so its
H T T H
probability is 6 / 16 = 3 / 8. This macrostate is the most
H T H T
random, or disordered, since there are so many ways 2
H H T T
heads can come up in 4 flips. Entropy is a measure of
disorder, and for this system it’s at a max when in T T T H
macrostate 2. Minimum entropy occurs when the coins T T H T
are in macrostate 0 or 4, since there is a high degree of T H T T
order in these states--only one microstate each. These H T T T
are the least likely microstates to occur. continued T T T T
 Entropy (cont.)
Suppose our coin system is in macrostate 4 (all heads). This
represents maximum order, minimum entropy. Every so often one of
the coins is chosen at random and flipped. With each flip there is a
50-50 chance that the macrostate will change. With time (after
enough flips), it is doubtful that the system will still be in the
minimum entropy state. It is much more likely to be in macrostate 2,
the state with the most entropy.
The 2nd Law states that during any process the universe moves toward
more probably states--states with more entropy. It is possible to
decrease the entropy of our coin system by physically turning all tails
over so that there are all heads, but in doing this we must expend
energy. This energy expenditure increases the entropy of our
surroundings more than it decreases the entropy of the system. Thus
the entropy of the universe is increased.
continued on next slide
 Entropy (cont.)

In our coin example we only dealt with four coins. In real life even a
quadrillion atoms or molecules might not be very much. (A single
bacterium contains about 100 billion atoms.) How much more likely
is it for a system to be in its highest entropy state than in its lowest?
It depends on how big the system is:

Number of Ratio of This means that if 100 coins were

Coins Probabilities dumped on the floor it is about 100
4 6:1 billion billion billion times more
10 252 : 1 likely for half the coins to come up
20 184,756 :1 heads than for all of them to be
50 ~1014 : 1 heads!
100 ~1029 : 1
See next slide to see how these ratios are calculated.
 Entropy: Statistics Formula
We’ve seen that there are six ways to get exactly two heads in four flips.
There were only sixteen combinations of four heads and tails, so we just
listed them and counted how many had exactly two heads. But you
wouldn’t want to have to list all the combinations in fifty flips, since
there are 250 combos—over a quadrillion lines of 50 H’s and T’s! So
we’ll use some math instead. The number of ways to place 50 H’s in
100 spots is “100 choose 50,” which is written like this: 100
( )
50
n !
In general, ( )
n
r =
r ! (n – r ) !
Let’s try out the formula with 2 heads in 4 flips:

( )
4
2
= 4!
2 ! (4 – 2) !
=
4·3·2·1
(2 · 1) (2 · 1)
= 6, as we showed by
listing combinations
 Entropy & Fluids
Suppose a beaker of very hot water is poured into an aquarium of cool
water. Conservation of energy would not be violated if all the hot
water remained right at the spot where it was poured. But the 2nd Law
demands that the thermal energy eventually become evenly
distributed. The cool water has molecules moving at a wide range of
speeds (red = fast; blue = slow). Since the water is cool, there are
more blues than reds. The hot water poured in has mostly red. The
aquarium has less disorder (entropy) when all the fast molecules are in
one spot than when they are mixed in. With time a much more likely
situation exists, with a much higher entropy. continued

time
 Entropy & Fluids (cont.)
Imagine how many different ways you could take 100 blue balls and
paint 8 of them red. There are about 1.86 · 1011 ways to do this.
Many, many more of those ways look like the picture on the right
than on the left. The diffusion of perfume from an open bottle
throughout a room is also a consequence of the 2nd Law. Unlike
diffusion, though, the “hot” water molecules don’t necessarily have
to move so that they are spread out evenly. Convection currents will
allow some to move, but it is really the heat energy rather than the
molecules themselves that must distribute itself equally throughout
the aquarium.
 Entropy Example 1
Stooges build a card house. Inevitably, Moe smacks Curly upside the
head, and Curly bumps the table, knockings down the cards. The
potential energy the cards had before falling is converted into thermal
energy, and the room is warmed up ever so slightly. The 2nd Law
prohibits the room from cooling a little so that the card house can
spontaneously rebuild itself, even though energy would be conserved.
As a card house the cards are very organized. They’re in a low entropy
state. In a jumble on the table, they are very unorganized and in a high
entropy state. Moreover, the air in the room has more entropy when
heated because thermal energy is just the random motions of molecules.
The hotter the air, the more random motion the
molecules have. The stooges could decrease
the entropy of the cards by rebuilding the house,
but in doing so they would expend energy,
which would heat up the room a little. The
cards’ entropy would decrease, but the air’s
would increase even more. Overall, entropy
 Entropy Example 2
Moe kicks a football in quintessential Stooge fashion. While the ball
is flying through the air, its got kinetic as well as thermal energy.
When it lands on the ground the ball no longer has kinetic energy,
which goes into increasing the thermal energy of the air, ground, and
ball. Energy is conserved, but there is a net gain of entropy for the
universe. The kinetic energy the ball had was very organized: All the
molecules in the ball were pretty much moving in the same direction.
The thermal energy, on the other hand, is not organized at all, since
it is a consequence of random molecular
motions. The 2nd Law guarantees that
the ball won’t suddenly absorb heat
from its surroundings and come flying
back at Curly’s head, since this would
mean a decrease in the total entropy of
the universe.
 Most Probable = Least Useful
Kinetic energy, with many molecules moving in the same direction,
represents an “organized form of energy.” Chemical potential energy,
such as that contained in oil, is organized as well, since oil is comprised
of long hydrocarbons with very specific arrangements of atoms.
Gravitational potential energy is organized too, as in the card house.
All of these energies can be used to do useful work, such as lifting
objects, generating electricity, etc. Thermal energy is always
disordered unless there is a separation of temperatures. If hot water is
separated from cold water, heat can flow and work can be done.
An object or fluid with uniform temperature has uniformly distributed
thermal energy and can’t do any useful work. Unfortunately, this high
entropy state is the most probable. Many scientists believe that the
ultimate fate of the universe is a “heat death” in which the whole
universe is at one uniform temp. This would represent maximum
entropy. No life could exist, since life requires energy uptake and
expenditure. This can’t happen if the universe has only thermal energy.
 Change in Entropy Equation
Because most systems are many up of so many particles, calculating
entropy via probabilities would be very difficult. Fortunately, we are
normally concerned only with changes in entropy. If we have a
system in which energy is not changing forms, the change in entropy
is defined as:

Q
S =
T
 S = change in entropy
 Q = change in internal energy (heat flow)
T = absolute temperature
The 2nd Law of Thermodynamics says that during any process:

 Suniverse =  Ssystem +  Ssurroundings  0

 Change in Entropy Example
A glass rod is heated and then blown by a
glassblower. When it is at 185°C it is brought
outside to cool. 3200 J of heat are transferred
from the glass to the air, which is at 18°C.
Find the change in entropy of the universe:
 Suniverse =  Ssystem +  Ssurroundings
=  Sglass +  Sair
 Qglass  Qair
= T +
glass Tair
-3200 J 3200 J
= +
458 K 291 K
= -7 J / K + 11 J / K = + 4 J / K
 Change in Entropy Example (cont.)
As the glass cooled we assumed that the air temp didn’t go up
appreciably due after the heat transfer, which would have compli-
cated the problem. Important points:
• The temps were converted to kelvins.
• The glass lost as much thermal energy as air gained, as the 1st Law
requires.
•  Qglass is negative since the glass lost thermal energy so  Sglass is
also negative.
•  Qair is positive since the air gained thermal energy so  Sair is
also positive.
• Even though the  Q’s are the same size, the  S’s aren’t, since the
temps are different.
• The positive  S is greater than the negative  S, as the 2nd Law
requires.
 Second Law Consequences
• Heat will not flow from a cold body to a hot body.
• “Reverse diffusion” is a no-no (such as smoke from a fire
isolating itself in a small space).
• An object or fluid of uniform temperature (no matter how hot)
cannot do useful work. (There must be temperature difference
so that there will be a heat flow, which can be used to do work.)
• The various forms of energy tend to degrade over time to
thermal energy. This represents useful, low probability forms of
energy converting into an unusable, high probability form.
• Without input of energy, bodies tend to reach thermal
equilibrium. (We can maintain temperature differences via
refrigerators or heating units, but this requires energy.)
continued on next slide
 Second Law Consequences (cont.)

• Any time we do something that decreases the entropy of a

system, the energy we expend in doing it increases the entropy
of the surroundings even more.
• A perpetual motion machine is impossible to make. A
perpetual motion machine is a device that would absorb thermal
energy from a hot body and do as much work as the energy it
absorbed. (See pics on next slide.)
• During any process the entropy of the universe cannot
decrease. Expending energy to decrease the entropy of a system
will lead to an increase in entropy for the surrounding by a
greater amount.
 Heat Engines
A heat engine takes advantage of temp differences to produce useful
work. The amount of work done depends on the size of the reservoirs,
engine efficiency, and the temp difference (TH - TC). QH is the heat that
flows from the hot region; QC is the heat flowing into the cold region.
W is the useful work done by engine. The smaller QC is, the more
efficient the engine is. The engine on the right satisfies the 1st Law but
violates the 2nd Law, i.e., 100% efficiency is unattainable.

Hot Reservoir, T H Hot Reservoir, T H

QH QH
W W
Engine Engine
QC QC = 0

Cold Reservoir, T C Cold Reservoir, T C

Real engine. QH = QC + W Impossible engine. QH = W
 Refrigerators
A refrigerator forces heat from a cold region into a warmer one. It
takes work to do this, otherwise the 2nd Law would be violated. Can
a fridge be left open in the summer to provide a make shift air condi-
tioner? Nope, since all heat pumped out of the fridge is pumped
back into the kitchen. Since QH > QC because of the work done,
leaving the refrigerator open would actually make your house hotter!

Hot Reservoir, T H Hot Reservoir, T H

QH QH
W W=0
Engine Engine
QC QC

Cold Reservoir, T C Cold Reservoir, T C

Real fridge. QC + W = QH Impossible fridge. QC = QH
 Specific Heat
Specific heat is defined as the amount of thermal energy needed
to raise a unit mass of substance a unit of temperature. Its
symbol is C.
For example, one way to express the specific heat of water is
one calorie per gram per degree Celsius: C = 1 cal / (g · ºC), or
4.186 J / (g · ºC). This means it would take 20 cal of thermal
energy to raise 4 grams of water 5 ºC.
Water has a very high specific heat, so it takes more energy to
heat up water than it would to heat up most other substances (of
the same mass) by the same amount. Oceans and lake act like
“heat sinks” storing thermal energy absorbed in the summer and
slowing releasing it during the winter. Large bodies of water
thereby help to make local climates less extreme in temperature
from season to season.
 Specific Heat Equation

Q = m C T
Q = thermal energy
m = mass
C = specific heat
T = change in temp

Ex: The specific heat of silicon is 703 J / (kg · ºC). How

much energy is needed to raise a 7 kg chunk of silicon 10 ºC ?
answer:
Q = 7 kg ·703 J ·10 ºC = 49 210 J
kg · ºC
Note that the units do indeed work out to be energy units.
 Calorimetry
Schmedrick takes another horseshoe out of the fire when it’s at
275 ºC, drops in his bucket of water, and this time covers the bucket.
The bucket and cover are made of an insulating material. The bucket
contains 2.5 L of water originally at 25 ºC. The 1.9 kg shoe is made
of iron, which has a specific heat of 448 J / (kg · ºC). Let’s find the
temp of the horseshoe and water once equilibrium is reached.
Let’s assume that the container allows no
heat to escape. Then the 1st Law implies
that all heat the shoe loses is gained by the
water. Since one milliliter of water has a
mass of one gram, the bucket contains
2.5 kg of water. At thermal equilibrium
the water and shoe are at the same temp.
The total thermal energy in the bucket
does not change, but it is redistributed.
continued on next slide
 Calorimetry (cont.)
Let T = the equilibrium temperature.
Q lost by iron = Q gained by water
miron Ciron Tiron = mwater Cwater Twater

(1.9 kg) (448 J / kg · ºC) (275 ºC - T) = (2.5 kg) (4186 J / kg · ºC) (T - 25 ºC)

Note how the T terms are written so that

each side is positive. We’ve got a simple
linear equation with T on both sides.
Solving it gives us T = 43.8 ºC. This is
the equilibrium temp--the final temp for
both the shoe and water. If T had come
out over 100 ºC, the answer would have
been invalid, since the specific heat for
steam is different than that of water.
 Latent Heat
The word “latent” comes from a Latin word that means “to lie
hidden.” When a substance changes phases (liquid  solid or
gas  liquid) energy is transferred without a change in
temperature. This “hidden energy” is called latent heat. For
example, to turn water ice into liquid water, energy must be
added to bring the water to its melting point, 0 ºC. This is not
enough, however, since water can exist at 0 ºC in either the liquid
or solid state. Additional energy is required to change 0 ºC ice
into 0 ºC water. The energy increases the internal energy of the
water but does not raise its temp. When frozen, water molecules
are in a crystalline structure, and energy is needed to break this
structure. The energy needed is called the latent heat of fusion.
Additional energy is also needed to change water at 100 ºC to
steam at 100 ºC, and this is called the latent heat of vaporization.
 Latent Heat Formula

Q = m Lf or Q = m Lv
Q = thermal energy
m = mass
L = heat of fusion or vaporization
L is the energy per unit mass needed to change the state
of a substance from solid to liquid or from liquid to gas.
Ex: Lf (the latent heat of fusion) for gold is 6440 J / kg.
Gold melts at 1063 ºC. 5 grams of solid gold at this
temp will not become liquid until additional heat is
added. The amount of heat needed is:
(6440 J / kg) (0.005 kg) = 32 J. The liquid gold will still be
at 1063 ºC.
 Latent Heat / Specific Heat Example
Superman vaporizes a 1800 kg ice monster with
his heat ray vision. The ice monster was at
-20 ºC. After being vaporized he is steam at
135 ºC. How much energy did Superman expend?
Substance Specific Heat (in J / kg · ºC)
ice 2090
liquid water 4186
steam 1970
For water : Lf = 3.33 ·105 J / kg; Lv = 2.26 ·106 J / kg
Q = (1800 kg) (2090 J / kg · ºC) (20 ºC) heating ice to melting pt.
+ (1800 kg) (3.33 ·105 J / kg) ice to water, const. temp of 0 ºC
+(1800 kg) (4186 J / kg · ºC) (100 ºC) heating water to boiling pt.
+ (1800 kg) (2.26 ·106 J / kg) water to steam, const. temp of 100 ºC
+ (1800 kg) (1970 J / kg · ºC) (35 ºC) heating steam to 135 ºC
= 5.62 ·109 J total energy expended by Superman
 Latent Heat & Entropy
Schmedrick is enjoying a cool glass of soy milk while relaxing on a
cot on a winter morning in his backyard. Suddenly his dog, Rover,
barks at a squirrel and startles Schmed, who drops his drink. A 10 g
ice cube at 0 ºC falls to the ground and melts. The temp outside is
10 ºC. Calculate the change in entropy of the universe due to the
melting of the ice only. answer:
For the cubie: Q = m Lf = (0.01 kg) (3.33 ·105 J / kg) = + 3330 J.
This is the energy absorbed by the ice from the surroundings.
Sice = Qice / Tice = +3330 J / 273 K = +12.198 J / K.
For the surroundings: Q = -3330 J, since the surroundings lost as
much thermal energy as the cubie gained. The temperature of the
backyard does not decrease significantly, though, with such a small
energy loss. Ssurr = Qsurr / Tsurr = -3330 J / 283 K = -11.767 J / K.
For the universe: Suniv = Ssurr + Sice = 12.198 J / K - 11.767 J / K
= +0.431 J / K. Thus, the 2nd Law is satisfied.
 Internal Energy, Work, & Heat
The internal energy, Eint, of a substance or object can be changed
in two ways:
1. by letting heat flow in or out of the substance, Q
2. by the substance doing work or having work done on it, W
In summary: Eint = Q - W, which is one way to state the 1st Law.

Q is positive if heat flows in. W is the

weight work done by the substance. If the gas
expands because of the added heat, it
gas will do work by lifting the weight up.
membrane
Then W would be positive, and the
heat

work the gas does would decrease its

internal energy.
 Internal Combustion Engine
In the carburetor of your car, air and fuel are mixed. The gaseous
mixture is injected into a cylinder, compressed by a piston, and
ignited by a spark plug. (If your car has fuel injection, which is more
efficient, there is no carburetor; instead fuel is sprayed into the
cylinders at appropriate times, where it vaporizes.) The fuel mixture
contains internal as well as chemical potential energy. After burning
most of the potential energy is released. This energy heats the gas in
the cylinder, raising its internal energy. The burning gas also does
work on the piston as it expands. The force applied to the piston
causes the crankshaft to rotate. The crankshaft is hooked up to the
transmission. The exhaust gases are expelled from the cylinder so
that the cycle can begin again. Cars are very inefficient, since most
of the chemical potential energy in the gasoline goes into heating the
exhaust gases, which pollute our atmosphere and contribute to global
warming. Only a small amount of the chemical potential energy
does useful work.
 Calorimetry & Tigger
Tigger greets Pooh in his usual enthusiastic manner.
When he realizes that Pooh is storing a large vat of
honey, Tigger bounces around the Enchanted Forest,
and with one last, mighty bounce propels himself
into the vat. Tigger’s mass is m. His tail has
a spring constant k and compresses a
distance x. The honey’s mass is M, and its
specific heat is C. Assuming the honey
gains all of Tigger’s energy, how much does
the honey’s temperature rise? answer:
The elastic potential energy stored in Tigger’s tail is converted to
thermal energy in the honey:
E0 = E f ½ k x 2 = M C T T = ½ k x 2 / MC
In real life T would be slightly less since some of Tigger’s original
energy would have gone into heating the air and Tigger himself. Note
that Tigger’s mass and the height of his bounce matter not.
 Thermal Expansion
As a material heats up its atoms/molecules move or vibrate more
vigorously, and the average separation between them increases. This
results in small increases in lengths and volumes. Buildings, railroad
tracks, bridges, and highways contain thermal expansion joints to
prevent cracking and warping due to expansion. The amount of expan-
sion depends on the original length/volume, the type of material, and
the change in temp. L is length, V is volume, T is temp,  is the coef-
ficient of linear expansion, and  is the coef. of volume expansion.
When a solid of a single material expands, it does so proportionally in
all directions. Since volume has 3 dimensions and length is only 1,
 = 3 . Length expansion:
L
=  T
L
Volume expansion:
V
cold solid hot solid =  T
V
Top view
Bimetallic Strip

handle steel (brass on other side)

A bimetallic strip is a strip of two different metals—often steel on one

side and brass on the other. When heated the strip curves because the
metals have different coefficients of thermal expansion. Brass’s
coefficient is higher, so for a given temperature change, it expands
more than steel. This causes the strip to bend toward the steel side.
The bending would be reversed if the strip were made very cold.
steel side

Side view brass side

Click for Internet Demo

 Thermostats
Bimetallic strips are used in thermostats, at least in some older
ones. When the temperature changes, the strip bends, making or
breaking an electrical circuit, which causes the furnace to turn
on or shut off. In this model when the strip bends it tilts a bulb
of mercury, which then bridges two wires and allows current to
flow.
 Thermal Expansion & The Concorde
The Concorde is a supersonic jet made of a heat tolerant aluminum
alloy. Its nose tilts down on takeoff and landing so the pilot can see
the runway. In flight the nose comes up to reduce drag, but at a
speed of around 1,350 mph, friction with the air causes significant
heating of the plane,
enough to make the
Concorde grow in
length by 7 inches!
(To maintain this
speed for one hour, the
Concorde must burn
over 6,700 gallons of
fuel.)
 L V
=  T Thermal Expansion Example =  T
L V
Schmedrick takes his dune buggy to the gas station and fills it up to
the very brim. His tank is a steel cylinder of radius 23 cm and height
45 cm (big enough to hold about 20 gallons). He burns a liter of gas
getting to the beach, where both the tank and the gas heat up by 20 ºC.
Both the tank and the gas expand. For steel  = 1.1 · 10-5 / ºC. For
gasoline  = 9.6 · 10-4 / ºC. Does the tank overflow? Hints:
1. Use the linear expansion formula to calculate the increase in radius
5.06 · 10 -3 cm
2. Use thetank:
of the linear expansion formula to calculate the increase in
height 9.9 · 10 -3 cm
3. For a cylinder,
of the tank: V =  r 2 h. Calculate the increase in volume of the
tank: 49.3694 cm 3
4. Calculate the volume of gasoline at the beach before expansion.
(1 cm 3 = 1 mL) : 73 785.613 cm 3
5. Use the volume expansion formula to calculate the increase in
volume of the gasoline: 1 416.684 cm 3
6. Conclusion: Schmed will be kicked out for spilling gas at the beach!
 Credits

Thermostat: http://www.phys.virginia.edu/Education/outreach/8thgradesol/ThermostatFrm.htm