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 INdistinguishable, 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 = = 252 Total
! !

Number of states with 4 heads and 6 tails =

!
= 210 252
! ! 2102
!
Number of states with 8 heads and 2 tails = = 45 452
! !
102
!
Number of states with 9 heads and 1 tails = = 10 784
! !

Number of states with 10 heads and 0 tails = 1

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
Assumptions in a large room with many particles and enough temperature

-The number of possible microstates that the system can reach depends on the energy available.

-Each one of the possible microstates of a system is equally likely to occur.

…. So you need enough temperature

Cold Hot
-The system’s internal dynamics are such that the microstates of the system are continually changing.

…. Shake the box continuously

-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” 2
Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Kinetic Molecular Theory
Statistical definition of temperature

The system with energy is in one of the Ω microstates

Ω Ω for that energy

When both are in thermal contact, the whole system can be in any one of the Ω Ω microstates

In thermal equilibrium the system will appear to choose a configuration that maximizes number of microstates

Ω Ω 0

Ω Ω
Ω Ω 0

As the total energy is constant , then and ⁄ 1

1 Ω 1 Ω ln Ω ln Ω
Ω Ω Note
This condition defines the most likely division of energy As the entropy is defined as
or “being at the same temperature” , this quickly leads to
1
≡
ln Ω

3
Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Kinetic Molecular Theory
The Boltzmann distribution

The “system” is so small that Ω 1 microstate for each

Ω ∝Ω 1
reservoir at system Since T is related to ln Ω microstate and ≪ we can Taylor expand
around E, or 0, 1 ln Ω

ln Ω
ln Ω ln Ω ⋯ ln Ω ⋯

Neglecting higher terms of the expansion,

⁄
Ω Ω
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
∑

Call β ≡ 1⁄ and you can easily see that

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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 Number of possible The Bloltzmann distribution is

only 1 microstate associated microstates like this simply a matter of probability
Ω=1 Ω=400*399=19600

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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

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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Kinetic Molecular Theory
The Maxwell - Boltzmann distribution Let’s apply all we know to a room full of gas.

System that can borrow energy from the

“reservoir” = “The rest of the room”

Boltzmann statistics are applicable!

We only consider kinetic energy in

each particle
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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 1

(see appendix at the end of the lesson),

⁄ 2 ⁄
⁄2 2

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

proportional to,
⁄ ⁄ ⁄
∝

⁄
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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Kinetic Molecular Theory
The speed distribution (see Appendix with solutions to the different integrals)

What is the fraction of molecules between and (i.e. The probability of having
velocity between and )?

⁄
∝ 4

O course we have to normalize this function by making 1

/
1
4 ⁄2

So that,
⁄
4 ⁄
2

Maxwell-Boltzmann speed distribution 9

Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Kinetic Molecular Theory
The speed distribution

We can calculate easily , and

8 ⁄

3 3
and

The maximum of comes easily by differentiating,

2
0

The experimental justification of the Maxwell-Boltzmann velocity distribution,

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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
The temperature of the Moon and why it has no atmosphere

2410 m/s
 
3.33·10−27 kg

3 3 1.38 10 400
3.33 10

2230 m/s
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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Kinetic Molecular Theory
Number of molecules travelling in a certain directions at a given speed

Fraction of particles whose trajectories lie in Ω

an elemental solid angle Ω is, 4

The solid angle corresponding to particles

travelling between θ and dθ is the shaded area, Ω 2

Ω 1
So,
4 2
1
And the number of particles in that direction with speeds between v and v+dv,
2
Number of molecules hitting a wall

Volume swept in a dt, A cos

So the number of particles hitting a wall of area A,
A cos
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 θ and dθ,
cos 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
∆ 2

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

/ /
1
2
2
/
Using the integral we have that,
1
3
Using the total number of molecules , and that 3 ⁄ ,

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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Molecular velocity and energy distribution

For a monoatomic gas, →d

{Number of particles between E and E+dE} = d {Number of particles between v and v+dv}=

→
Proportion of particles per unit of energy

Substituting f(v) by Boltzmann distribution function,

and d ,
⁄
2 1 ⁄

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

For virtually all practical purposes, activation energies EA>>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?

1,38 10 8,617 10 For T=300 K 0,026

⁄ ⁄

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

For 1eV ⁄ .
1 2 10 ⁄ 6.2

. ⁄ . ⁄
For 0.8eV 0.8 4 10 5.54

A decrease of 20% implies that now it is more than 2000 times more likely to break the bond

Probability of having energy > EA ⁄

Rate of jumps = Frequency of jumps ⁄ ⁄ Arrhenius

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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Archaea, salt lovers, methane makers, thermophiles

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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Archaea, salt lovers, methane makers, thermophiles

Genetic distance

Bacteria Archaea

Similar genetic distance

Toadstool Whale
UV light energy ~300
3 10
What is the mutation rate? 6.6 10
300 10

Energy that WILL induce a mutation 6.6 10 J ~ 4 eV

But wait not that long and  1 will likely cause mutation 17
Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Archaea, salt lovers, methane makers, thermophiles

Genetic distance

Bacteria Archaea

Similar genetic distance

Toadstool . J ~ eV Whale

⁄
What is the mutation rate due to T for Eucarya? ∝
We love living at 20ºC

⁄
What is the mutation rate due to T for Archaea? ∝
We love living at 100ºC Living Archae ~10 ⟺ 10
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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Archaea, salt lovers, methane makers, thermophiles

Genetic distance

Bacteria Archaea

Similar genetic distance

Toadstool . J ~ eV Whale

What is the mutation rate due to T for Eucarya?
We love living at 20ºC ~ 3000
 
What is the mutation rate due to T for Archaea? A mutation that may happen in 1
We love living at 100ºC year at 100ºC takes 3000 years 19
at 20 ºC
Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Why my cooking tends to burn in the summer?

Winter 20ºC Summer 32ºC

Compare the rate at which a protein degrades just by changing from 20ºC to 32ºC
• Energy to denaturalize bonds in a protein ~0.5 eV
• Temperature in the oven Toven=150ºC in winter and 162ºC in summer

. ⁄ .
∝ .
~ 1.5 50% increase!!!
. ⁄ .
∝
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Thermal and Magnetic Properties of Materials
 THERMAL PROPERTIES
Thermally Activated Processes
The role of EA

⁄ ⁄ 1

N 3H ⇌ 2NH heat

EA=1
EA=5

EA=10
⁄

kT (arbitrary units)
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Thermal and Magnetic Properties of Materials
 APPENDIX
The Gaussian integral:

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

Using polar coordinates,

1
Which with the substitution ,
2
..and more

Differenciate the Gaussian integral by , as x does not depend on , so 1

⁄ and ⁄ ⁄ ⁄2 ⁄ so that, 2

2 !
Repeating the process you could reach the general formula,
!2

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 .
22
!
The following 2 1 powers differentiate with
2
respect to as before

Thermal and Magnetic Properties of Materials

 Some Problems
1. The Moon cannot have atmosphere because its gravitational pull is too weak to hold
the molecules. During the 13 days of sunlight, the surface of the Moon can reach
500 K. Knowing that the escape velocity of the Moon is 2410 m/s, calculate if a
molecule of Hydrogen (m=3.33·10-27 kg) escapes after hitting the Moon surface. Is
there a chance that heavier molecules may escape? kB=1.38·10-23 J/K.
2. A system has only two energy states, one with energy 0 and the other with
energy 0. What is the average energy of the system?
3. Find the average energy for a system with n states, separated by equal gaps
of energy , so the energy can take any of the values 0, , 2 , … , , which is the
Einstein model for the average energy of n oscillators. Also find the average energy
for a system with infinite states, also separated by gaps of energy , so the sum can
be solved as an integral.
4. A process has an activation energy 0.8 . Compare the rates for the process
from winter T=280K to summer T=305 K.
5. A uniform field is acting on a system of particles at T=300K. The concentration of
particles measured at two points in the direction of the field 10 cm apart, differ by a
factor of 5. Find the force F acting on the particles.
6. Imagine you want to push a spacecraft with the solar wind. Close to Earth the solar
wind is mainly hydrogen atoms travelling at 3·104 m/s. Assume a flux of atoms of
1012 at/s·m2. Calculate the acceleration of a 100 m2 and 10 g aluminum foil sail,
normal to the flux of atoms (MH=1.67·10-27 kg). (Assume elastic collisions). 23
Thermal and Magnetic Properties of Materials
 Some Problems

7. Consider a system with five possible energy estates 0, , ,  and 2. If the system is
in equilibrium with a reservoir at a temperature kBT= eV. Find the average energy
of a particle using the partition function.

8. A very tall and thin column of gas at a temperature T is subject to the gravitational
pull (potential energy mgh). Find the average potential energy of the molecules.

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Thermal and Magnetic Properties of Materials