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Thermodynamics Notes PDF
Thermodynamics Notes PDF
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
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
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 + ...
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
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
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.
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
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
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
∆U = Q + W = W
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
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
H ≡ U + PV
H + ∆H = U + ∆U + P (V + ∆V )
= (U + P V ) + (∆U + P ∆V )
= H + (∆U + P ∆V )
so
∆H = ∆U + P ∆V
∆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