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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

P

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

equilibrium.

volume mechanical

volume mechanical

particles diffusive

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.

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

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

∆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 + ...

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

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

= =

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

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.

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

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

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

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

∆U = Q + W = W

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

Problems: 1.37

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

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

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

CHAPTER 1. ENERGY IN THERMAL PHYSICS 11

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

∆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

Problems: 1.50, 1.51, 1.52, 1.54

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