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Thermodynamics

Lecture notes

Claude Dion

HT-2004
Warning!

These lecture notes are intended to be used by me, your teacher, during class,
to help me remember what I have to say. You are free to use them to prepare
for class, help you study, find out what happened when you weren’t there,
or whatever else, but they should not be used as a substitute for the course
book 1 . They are incomplete (I sometimes may have put just a few words as
reminders for myself) and may contain errors.

1
D. V. Schroeder, An Introduction to Thermal Physics (Addison Wesley Longman, San
Francisco, 1999).
Chapter 1

Energy in Thermal Physics

1.1 Thermal Equilibrium

(Video of balloon expanding.) What is happening? Heat makes the bal-


P
loon expand. Pressure inside. Same as in classical mechanics: F = 0 at
equilibrium.

Exchanged quantity Type of equilibrium


volume mechanical

(Video of milk in coffee.) What is happening? Mixing of the two liquids.

Exchanged quantity Type of equilibrium


volume mechanical
particles diffusive

Relaxation time. Spontaneous. Not shown: temperature.


Temperature from human experience: sensation of hot and cold. How does a
mercury thermometer work? What exactly are we measuring? Just like the
balloon: expansion of a substance.

Exchanged quantity Type of equilibrium


volume mechanical
particles diffusive
energy thermal

1
CHAPTER 1. ENERGY IN THERMAL PHYSICS 2

Equilibrium does not mean that things are static: small fluctuations around
the equilibrium point happen.
Temperature: The tendency of an object to give up energy to another. If
energy flows spontaneously from A to B when they are in contact, then A is
at a higher temperature than B. If no energy flows, then the objects are in
thermal equilibrium.
0th law of thermodynamics: If A is in thermal equilibrium with B, and B is
in thermal equilibrium with C, then C is also in thermal equilibrium with A.
This is why a thermometer works.
Quantification of temperature: the Celsius scale. (Figure 1.3) Pressure goes
to zero at ∼ −273◦ C; absolute zero; absolute temperature scale, unit: kelvin.
Problems: 1.7, 1.8

1.2 The Ideal Gas

The experimental evidence concerning the behavior of gases with respect to


temperature was summarized by the ideal gas law:
PV = N kB T (1.1)
= nRT (1.2)
with kB = 1.3806505(24)×10−23 J/K the Boltzmann constant, R = 8.314472(15) Jmol−1 K −1
the gas constant. One mole is given by Avogadro’s number NA = 6.0221415(10)×
1023 mol−1 .
Validity: low density (average space between molecules  molecule size).
The volume of the molecules themselves is neglected.
Problems: 1.9 – 1.12, 1.17
We now take the example of an ideal gas to show that indeed thermal equi-
librium is reached by an exchange of energy.
(Drawing of a cylinder with a piston, see figure 1.4. Note that this is one of
the favorite systems to study thermodynamics.) Start with a single molecule
of velocity ~v . Collisions with the walls are elastic, so speed is constant. Walls
are perfectly smooth, so mirror-like reflections.
What is the relation between pressure and (kinetic) energy? P = F/A =
F/L2 . What is the force the particle exerts on the piston? Mostly zero,
CHAPTER 1. ENERGY IN THERMAL PHYSICS 3

except when there is a collision. We’ll consider the average pressure.


 
∆vx
F x, on piston −F x, on molecule
m ∆t
P = = =−
A A A
To consider only collisions with the piston, we take
2L
∆t =
vx
i.e., the time for one round-trip. The x component of the velocity changes
from +vx to −vx , so ∆vx = −2vx . We thus get

mvx2 mvx2
!
m −2vx
P =− = =
A 2L/vx AL V

One vx comes from the fact that higher velocity equals stronger collision, the
other from the fact that collisions are more frequent. We see also that the
pressure is related to the kinetic energy.
We consider that we have N identical molecules with random positions and
directions. They do not collide with each other, only with the walls (is that
actually necessary?). We get
2 2 2
P V = mv1x + mv2x + mv3x + ...

or, considering that fluctuations will be small because of the number of


molecules,
P V = N mvx2
If with plug this in the ideal gas law, we get

kB T = mvx2
1 1 2 p2
kB T = mvx = x
2 2 2m
This is just in x, but the same must hold for y and z,

1 2 1 2 1 2 1
mv = mv = mv = kB T
2 x 2 y 2 z 2
so the total average translational kinetic energy is

1 1   3
K trans = mv 2 = m vx2 + vy2 + vz2 = kB T
2 2 2
CHAPTER 1. ENERGY IN THERMAL PHYSICS 4

QED: we have a relation between (kinetic) energy and temperature.


From this, we can also get the “average” (not exactly) speed of molecules in
the gas: s
3k T 3kB T
q
B
v2 = ⇒ vrms ≡ v 2 =
m m
Example for N2 at room temperature:
v
u 3 × 1.381 · 10−23 JK−1 × 298 K
u
vrms =t −26
= 514 m/s
4.665 · 10 kg

Does this mean that a molecule a one wall of the room will hit the opposite
wall in a few hundredth of a second? Lets calculate the mean free path:
the average distance a molecule travels before hitting another one. Consider
all molecules are frozen except one, and are spheres of radius r, or that the
traveling molecule is of radius 2r and the other are point particles (figure
1.17). The molecule sweeps a cylinder of radius 2r, and when the volume of
this cylinder is equal to the total volume divided by number of molecules, it
is likely the molecule will have hit another one, so
V
π (2r)2 ` ≈
N
1 V
` ≈
4πr2 N
For air, lets say r = 1.5 Å = 1.5 × 10−10 m, and

V kB T 1.381 · 10−23 JK−1 × 298 K


= =
N P 1 atm
1.381 · 10−23 JK−1 × 298 K
= = 4.06 · 10−26 m3
101325 Pa
so
1 −26
`≈ −10 2 × 4.06 · 10 m3 = 1.44 · 10−7 m
4π (1.5 · 10 m)
Time between collisions:
` ` 1.44 · 10−7 m
∆t = ≈ = = 2.80 · 10−10 s
v vrms 514 m/s
The molecules are going very fast but they are colliding very frequently with
other, close by molecules.
Problems: 1.19 – 1.22
CHAPTER 1. ENERGY IN THERMAL PHYSICS 5

1.3 Equipartition of Energy

Equipartition theorem: At a temperature T , the average value of each


quadratic term in the expression for the total energy is 21 kB T .
Example: for a harmonic oscillator

p2 1
E= + kx2
2m 2
so its average energy is kB T
Quadratic terms are related to degrees of freedom: translational motion
1 2 1 2 1 2
mv , mv , mv
2 x 2 y 2 z
rotation
1 1 1
Ix ωx2 , Iy ωy2 , Ix zωz2
2 2 2
(with I the moment of inertia around an axis). Note that for a diatomic
molecule there are only two rotational degrees of freedom (because of quan-
tum mechanics).
Vibrations in general count as two degrees of freedom. However, at some tem-
peratures some vibrational degrees of freedom are “frozen out” (no quantum
of vibration). Intermolecular interaction energies are not “nice” quadratic
functions.
For thermal processes (no nuclear, chemical, . . . processes), we get
1
Uthermal = N f kB T
2
where f is the number of degrees of freedom.

1.4 Heat and Work

What is energy? (See Feynman’s description.) Energy is not temperature:


temperature is only the tendency of an object to give out (or receive) energy.
Usually, when an object gains energy, it has a higher temperature, but not
always.
CHAPTER 1. ENERGY IN THERMAL PHYSICS 6

Energy is one of the fundamental concepts of physics. The total energy of


the universe never changes: law of conservation of energy. If an object
gains energy, another one must lose energy. However, energy can take many
forms: kinetic, electrostatic, gravitational, mass (E = mc2 ), . . .
There are many ways a system can gain or lose energy, and in thermody-
namics we classify these processes in two classes: heat and work.
Heat is the flow of energy coming from a difference of temperature, e.g., a
radiator that heats the room, the Sun that heats the Earth (although the
mechanism is very different). Conduction is by molecular contact; convec-
tion by the bulk motion of a gas or a liquid; radiation by electromagnetic
waves.
Work is every other way of putting energy in a system. Some examples:
pushing a piston (remember the model of figure 1.4), stirring a cup of coffee,
running a current through a resistor. It goes both ways: pushing the piston
to compress the gas is doing work on the system; the piston being pushed
out by the gas is the system doing work on something else (the atmosphere,
perhaps: think of the balloon expanding).
Heat and work refer to the transfer of energy. A system has energy, not
“heat” or “work”.
Using U for the total energy of a system, Q for the heat entering the sys-
tem and W for work being done on the system, we have from the law of
conservation of energy
∆U = Q + W
This relation is called the first law of thermodynamics.
Problems: 1.26–1.29

1.5 Compression Work

We will often consider work in the form of compression of a gas, for instance
by a piston. From classical mechanics:

W = F~ · d~r

which, for the piston, we start with

W = F ∆x
CHAPTER 1. ENERGY IN THERMAL PHYSICS 7

where ∆x is positive when the piston moves inwards. We want to express the
force as a pressure, i.e., to use P A. We must assume that the gas is always
in internal equilibrium, i.e., that pressure is well defined at all times. This is
only the case if the piston does not move too fast (relaxation time small with
respect to the movement of the piston). This slow volume change is called
quasistatic. Thus
W = P A∆x = −P ∆V
if the pressure doesn’t change: infinitesimal changes in volume. The pressure
must change for a large enough ∆V , so what do we do? We accumulate a
series of infinitesimal changes, i.e., we integrate.
Z Vf
W =− P (V )dV
Vi

Problems: 1.31, 1.33, 1.34

Compression of an Ideal Gas

If you pump air in a tire, you will feel its temperature rise, because of the
compression of the gas. If you pump very slowly, heat will escape to the
surroundings and the temperature will not rise as much. We will consider
two extremes: isothermal compression, where the temperature doesn’t
change (heat flows out quickly) and adiabatic compression, where there
is no exchange of heat (e.g., the system is isolated or insulated).
Isothermal compression is most likely also quasistatic, so we can use the
previous formula with the ideal gas law P = N kB T /V . (See isotherm as P
vs V , figure 1.11.) The work done is
Z Vf 1 Z Vf
W = − P (V )dV = −N kB T dV
Vi Vi V
Vi
= −N kB T (ln Vf − ln Vi ) = N kB T ln
Vf
Since we are doing work on the gas and the temperature stays the same,
heat must be flowing out. According to the equipartition theorem, for an
ideal gas (no interaction, only translational degrees of freedom) U is directly
proportional to T . So
Vf
Q = ∆U − W = 0 − W = N kB T ln
Vi
CHAPTER 1. ENERGY IN THERMAL PHYSICS 8

The work we do by compressing the gas ends up as heat in the environment.


If we now consider adiabatic compression (but still in a quasistatic way), then

∆U = Q + W = W

so the internal energy goes up. Again, for an ideal gas U ∝ T , so T %.


(Show adiabat on P vs V curve, figure 1.12.)
Problems: 1.37

1.6 Heat Capacities

We go further on the relation between heat and temperature.


Heat capacity definition:
Q
C≡
∆T
It depends on the quantity of matter, so we use the specific heat capacity
C
c≡
m
Problem: it depends on what happens when the heat is transferred (work or
no work)
Q ∆U − W
C= =
∆T ∆T
One possibility: consider W = 0, so no expansion/compression −P ∆V = 0.
We get the heat capacity at constant volume
!
∆U ∂U
 
CV ≡ =
∆T V ∂T V

In most real life cases, objects expand as they are heated. They do work
on the surroundings, so W < 0 ⇒ C > CV . We thus consider the heat
capacity at constant pressure
! ! !
∆U − (−P ∆V ) ∂U ∂V
CP ≡ = +P
∆T P
∂T P
∂T P

Last term “compensates” for energy lost as work. For solids and liquids
∂V /∂T is usually small.
CHAPTER 1. ENERGY IN THERMAL PHYSICS 9

Heat capacities can be measured, or taken from tabulated data, or theoreti-


cally predicted. Lets see if we can do it for an ideal gas.
Consider a system that stores energy only in quadratic degrees of freedom
1
U = N f kB T
2
so ! !
∂U ∂ N f kB T N f kB
CV = = =
∂T V
∂T 2 2
For a monoatomic gas f = 3, so CV = 32 N kB ; for one mole we get CV =
3
2
R = 12.5 J/K. (Compare to tabulated values.)
For a diatomic or polyatomic molecule, f is bigger; consider also that some
degrees of freedom are frozen at some T (see figure 1.13).
For a solid, there are six degrees of freedom per atom (3 kinetic + 3 potential),
so we have 62 R = 3R per mole. This is the rule of Dulong and Petit. All
degrees of freedom freeze out at low T , so CV → 0 as T → 0. (See figure
1.14.)
Lets look at CP for an ideal gas. First term is the same. Second is
! !
∂V ∂ N kB T
P =P = N kB
∂T P
∂T P P

so
CP = CV + N kB = CV + nR
For one mole of a monoatomic gas
5
CP = R = 20.786 J/K
2
which is exactly the value obtained for noble gases1
Problems: 1.41, 1.44
1
See P.W. Atkins, Physical Chemistry, 4th ed. (Freeman, New York, 1990), table 2.10,
or C. Nordling and J. Österman, Physics Handbook for Science and Engineering, 7th ed.
(Studentlitteratur, Lund, 2004), table 1.5 (with the proper conversion for 1 mole).
CHAPTER 1. ENERGY IN THERMAL PHYSICS 10

Latent Heat

Adding heat does not always increase temperature. During a phase trans-
formation (s ↔ l ↔ g) ∆T = 0, so
Q Q
C= = =∞
∆T 0
Then, the amount of heat needed to make the phase transition is the latent
heat
Q
L≡
m
By convention it is assumed that P = const. (usually 1 atm) and no other
work.
Some numbers: latent heat for melting ice is 333 J/g, for boiling water
2260 J/g (energy for bringing water from 0◦ C to 100◦ C is 420 J/g).
Problems: 1.47, 1.48

Enthalpy

Constant-pressure processes are very common and it can be bothersome to


always have to consider compression or expansion work.
Lets take the example of the combustion of hydrogen:
1
H2 + O2 → H2 O
2
The chemical energy is easy to consider: we break a H–H bond and half a O–O
bond, and form two O–H bonds. But is that the only thing to consider? Look
at the number of molecules. We have to consider the fact that in addition
to the energy of the chemical reaction, we have the atmosphere doing some
work while collapsing to take the place of the “missing” molecules (and the
fact that water is liquid at room temperature).
So in addition to the internal energy U of a system, lets consider also the
work needed to make room for it, P V . We thus define enthalpy:

H ≡ U + PV

Its the total energy needed to crate the system ab nihilo.


CHAPTER 1. ENERGY IN THERMAL PHYSICS 11

Like for U , it is interesting to consider changes in enthalpy. At constant


pressure, we get

H + ∆H = U + ∆U + P (V + ∆V )
= (U + P V ) + (∆U + P ∆V )
= H + (∆U + P ∆V )

so
∆H = ∆U + P ∆V

From the first law of thermodynamics

∆U = Q + W = Q + (−P ∆V ) + Wother

so
∆H = Q + Wother
So if no other work is done, enthalpy gives directly the heat added to the
system.
Raising the temperature of a system at constant pressure:
!
∂H
CP =
∂T P

Going back to the combustion of hydrogen, we have from a table that the
reaction as an enthalpy of formation ∆H = −286 kJ (at room temperature
and pressure). This is how much energy you can get out of the combustion.
You can also find the enthalpy change for phase transformations. For in-
stance, for boiling water ∆H = 40660 Jmol−1 . 1 mole H2 O is 18 grams, so
for 1 gram we have 2260 J (same as latent heat). Not all the energy ends up
in the steam:
RT
 
P ∆V = P (Vf − Vi ) ≈ P −0 = RT
P
= 8.314 JK−1 × 373 K = 3100 J

which is ∼ 8% of the energy.


Problems: 1.50, 1.51, 1.52, 1.54