THERMAL PROPERTIES

Introduction

Allow room for

thermal expansion

Glass-Metal seal

Chinese porcelain kiln

Useful Invar alloys

for clock making

The incredible
Ceramic Hobs

Bimetal switch
Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
The ideal gas
Boyles law (1662): A fixed amount of gas at T=Cons obeys 

Gay-Lussacs law (1809): A fixed volume of gas obeys

Charles law (1787): At constant pressure a gas obeys

=8.314J/molK

and

Hot

Heat and Heat Capacity

Cold

Heat = Thermal energy in transit

How much heat needs to be supplied to an

object to raise its temperature by dT?

 

Heat Capacity per unit of mass = Specific Heat =

 

C is the Heat Capacity in J/K

in J/(kgK)

Heat Capacity per unit of mol = Heat Capacity of 1 mol of the substance in J/(molK)

In a gas,

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
Microstates, macrostates
If the coins are distinguishable, each of the 210 possible states have the
same probability
A particular configuration is a microstate of the system
If the coins are IN-distinguishable, we can only distinguish when the
number of tails and heads is different.
A particular configuration here is a macrostate and they do not have the
same probability
Number of states with 5 heads and 5 tails =
Number of states with 4 heads and 6 tails =
Number of states with 8 heads and 2 tails =

= 252
= 210
= 45

Number of states with 9 heads and 1 tails = = 10

Total
252
210u2
45u2
10u2
784

Number of states with 10 heads and 0 tails = 1

-The system could be described by a very large number of equally likely microstates
-What we measure is the property of a macrostate of the system and they are not equally likely
Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
Statistical definition of temperature

The system with energy is in one of the microstates

for that energy

When both are in thermal contact, the whole system can be in any one of the microstates
In thermal equilibrium the system will appear to choose a configuration that maximizes number of microstates

Assumptions that we have to make:

-Each one of the possible microstates of a system is equally likely to occur.
-The systems internal dynamics are such that the microstates of the system are continually changing.
-Given enough time, the system will explore all possible microstates and spend an equal time in each of
them.
-Therefore, the system will be most likely found in a configuration represented by the most microstates.
For large number of particles, the phrase most likely becomes absolutely, overwhelmingly likely

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
Statistical definition of temperature

The system with energy is in one of the microstates

for that energy

When both are in thermal contact, the whole system can be in any one of the microstates
In thermal equilibrium the system will appear to choose a configuration that maximizes number of microstates

As the total energy is constant , then

and

Note
As the entropy is defined as

, this quickly leads to

This condition defines the most likely division of energy

or being at the same temperature

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
The Boltzmann distribution



The system is so small that microstate for each

Since T is related to microstate and we can Taylor expand
around E, or ,

Neglecting higher terms of the expansion (see problem 6),

So the probability function describing the system is then,

Boltzmann distribution

The probability has to be normalized with all the possible microstates,

Where is called the partition function

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
The Boltzmann distribution Exercise for computer freaks
20 x 20 matrix with random changes between locations,

Initial state is unlikely as it has

only 1 microstate associated
=1

Number of possible
microstates like this
=400*399=19600

The Bloltzmann distribution is

simply a matter of probability

7
Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
The Boltzmann distribution Exercise for the computer freaks
20 x 20 matrix starting with 2 quanta per site
(i.e. more energy in the initial state)

Final distribution of a
1000 x 1000 matrix

8
Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
The Maxwell - Boltzmann distribution
Assume a monoatomic gas where the only energy available to the particles is the kinetic energy,
, )

+

For a given direction, say x, the number of particles between

and will be proportional to,

And we need to normalize this function so

(see appendix at the end of the lesson),

The 3 directions are indistinguisable, so the number of particles between and is

proportional to,

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
The speed distribution (see Appendix with solutions to the different integrals)
Fraction of molecules between and
 

O course we have to normalize this function by making

So that,

Maxwell-Boltzmann speed distribution

10

Thermal and Magnetic Properties of Materials

The speed distribution

THERMAL PROPERTIES
Kinetic Molecular Theory
We can calculate easily and

and

The maximum of comes easily by differentiating,

The experimental justification of the Maxwell-Boltzmann velocity distribution,

11
Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
Number of molecules travelling in a certain directions at a certain speed



The solid angle corresponding to particles

travelling between  and d is the shaded area,

Fraction of particles whose trajectories lie in

an elemental solid angle is,

So,

And the number of particles in that direction with speeds between v and v+dv,

 

Number of molecules hitting a wall

 

Volume swept in a dt,

So the number of particles hitting a wall of area A,

  

And the number of particles hitting a wall per unit of time and unit
of area, having speeds between v and v+dv, and travelling at angles
between  and d,

  

12

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Kinetic Molecular Theory
The ideal gas law
Deduction of the equation from the kinetic molecular theory.
Linear momentum change perpendicular to the wall transferred
by every particle collision

Adding the contribution of each of the particles we can calculate the pressure on the container,


Using the integral

we have that,

Using the total number of molecules , and that ,

13

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Molecular velocity and energy distribution

For a monoatomic gas, 

{Number of particles between E and E+dE} = {Number of particles between v and v+dv}=
Proportion of particles per unit of energy

Substituting f(v) by Boltzmann distribution function,

and ,

Boltzmann factor

{Probability of being between E and E+dE} =

If the gas is not monoatomic (translational + rotational +
vibrational energy)


For virtually all practical purposes, activation energies E A >>kT and dominates the function

14

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Thermally Activated Processes
The role of EA
Example: If a molecule bond breaks in collisions giving 1eV of energy and another breaks more
easily, needing only 0.8 eV. What are the relative chances of each kind to break at 300 K?


For T=300 K


The term in changes much slower than so lets assume it constant

For 0.8eV

For 1eV

A decrease of 20% implies that now it is more than 2000 times more likely to break the bond
Example: Compare the number of atoms in a gas having E>1eV at 1000 K and 300 K

For 1000K

For 300K

What it takes 15000 years at room

temperature is done in 1 second at
1000K

15

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Thermally Activated Processes
Even if E A >>3/2kT, there is a probability
of jumping the barrier

Probability of jumping

Number of times an atom

tries to jump per sec.,

Probability of having
energy > E A

Probability of having energy > E A

Rate of jumps = Frequency of jumps

Arrhenius rate equation (rate of a
thermally activated process)

16

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Thermally Activated Processes
The role of EA

  

E A =1
E A =5

E A =10

17

kT (arbitrary units)

Thermal and Magnetic Properties of Materials

THERMAL PROPERTIES
Thermally Activated Processes
Using Arrhenius plots

Example: A hot-curing single-part epoxy glue called TickY TackA, sets in 6 minutes at 137C, 10
minutes at 127C or 30 minutes at 100C. Calculate the activation energy E A and the proportionality
rate A.
The slope of the  vs. 1/T is,

Taking k=8610-6 eVK-1 , EA=0.49 eV

And A can be calculated from the line equation,

18

Thermal and Magnetic Properties of Materials

PROBLEMS
1.- The worlds oceans contain approximately 1021 kg of water. Estimate the total heat capacity of the
worlds oceans. c water=4.18103 J/(kgK). Calculate the increase in its T if we could use 10 years of the
total energy burned by the entire world (World Energy Consumption 131012 J/s)
2.- With the energy that Spain burns in 1ms (Spanish power consumption 2,67108 MWh/year) you
want to increase the temperature of all the gold in the US federal Fort Knox reserve (4000 tons of gold).
What would be the temperature increase of all that gold? Cm(Au)=25.4 J/(molK) and M(Au)=197.
3.- Calculate the rms speed of hydrogen (H2 ), helium (He) and oxygen (O2 ) at Room Temperature (300
K). The atomic masses of H, He and O are 1, 4 and 16 respectively. Compare these speeds with the
escape velocity on the surface of i) the Earth (11.2 Km/s), ii) the Sun (617 Km/s). Proton Mass 1.6710-27
Kg and k B =1.3810-23 J/K. Discuss the results.
4.-Why does the Moon have no atmosphere? During the 13 days of sunlight, the surface of the Moon
can reach a temperature of 500K. Knowing that the escape velocity of the Moon is 2410 m/s, calculate if
a molecule of Hydrogen (m=3.3310-27 kg) escapes after hitting the Moon surface. Explain what would
happen to heavier molecules and why there is no atmosphere. k B =1.3810-23 J/K.
5.- Two bodies, with heat capacities C1 and C2 (assumed independent of temperature) and initial
temperatures T 1 and T 2 respectively, are placed in thermal contact. Show that their final temperature Tf is
given by
6.- In the overhead 5 we neglected the second term onwards of the Taylor expansion, which is
Show that this term equals

and hence show that it can be neglected compared with the first

19

two terms if the reservoir is large.

Thermal and Magnetic Properties of Materials

PROBLEMS
7.- In a very simple two state-system where there are only two states, one with energy 0 and the other
with energy . What is the average energy of the system?
8.- Find the average energy for:
a) A n-state system, in which a given state can have energy .
b) A harmonic oscillator, in which a given state can have energy
Hint: Assume very small so a discrete sum can be solved like an integral.
9.- How many molecules of gas fit inside a 30 liters ultra high vacuum (UHV) chamber at 10-10 torr
and room temperature. 1 torr = 133.3 N/m2

10.- A chemical reaction has an activation energy . Compare the rates of the reaction when you

pass from T=300K to T=310K

20
Thermal and Magnetic Properties of Materials

The Gaussian integral:

APPENDIX

It can be proved by
evaluating the 2-D integral,

Using polar coordinates,

Which with the substitution ,

..and more
Differenciate the Gaussian integral by , as x does not depend on , so

and so that,

Repeating the process you could reach the general formula,

As all these functions are even, the integral 0 to is of the one from to

To integrate from to is easy as the function is odd and so the integral is zero. To

integrate from 0 to , start off with , which can be evaluated by noticing that is

almost what you get when you differentiate .

The following powers differentiate with
respect to as before

21

Thermal and Magnetic Properties of Materials