INTRODUCTION TO STASTICAL

MECHANICS

PRESENTATION
Prepared by:
Farishta Ahmad
Yousra Noor
Tanzeela Gul
Contents

1. Introduction

2. Statistical distribution and mean values

3. Mean free path

4. Distribution of molecular speeds and energies

HISTORY

 Mathematical structure of statistical mechanics was established by

American physicist Josiah Willard Gibbs in his book Elementary
Principles in Stastical Mechanics in 1902.

 Two earlier physicists James Clerk Maxwell of Great Britain and Ludwig
E. Boltzmann of Austria are generally credited with having developed the
fundamental principles of the field with their work on thermodynamics.
Introduction

 Mechanics:
 Study of position, velocity, force and energy
 Classical Mechanics (Molecular Mechanics)
• Molecules (or molecular segments) are treated as rigid object (point, sphere,
cube,...)
• Newton’s law of motion
 Quantum Mechanics:
• Molecules are composed of electrons, nuclei, ...
• Schrodinger’s equation  Wave function
1.Definition

Statistical mechanics:
 Branch of physics that combines the principles and procedures of
statistics with the laws of both classical and quantum mechanics,
particularly with respect to the field of thermodynamics.
Explanation

 It aims to predict and explain the measurable properties of macroscopic systems on

the basis of the properties and behaviour of the microscopic constituents of those
systems.

 Statistical mechanics interprets, for example, thermal energy as the energy of

atomic particles in disordered states and temperature as a quantitative measure of
how energy is shared among such particles.

 Statistical mechanics draws heavily on the laws of probability so that it does not
concentrate on the behaviour of every individual particle in a macroscopic substance
but on the average behaviour of a large number of particles of the same kind.


Stastical Distribution

 What is a distribution in statistics?

 When we use the term normal distribution in statistics, we usually mean a
probability distribution. Good examples are the Normal distribution, the Binomial
distribution, and the Uniform distribution.

 Definition:
 A distribution in statistics is a function that shows the possible values for a variable
and how often they occur.
Mean free path

 Definition:
 In physics, the mean free path is the average distance travelled by a moving particle
(such as an atom, a molecule, a photon) between successive impacts
(collisions), which modify its direction or energy or other particle properties.

 Explanation:
 Imagine gas leaking out of a pipe. It would take a while for the gas to diffuse and
spread into the environment. This is because gas molecules collide with each other,
causing them to change in speed and direction.
 Therefore, they can never move in a straight path without interruptions. Between
every two consecutive collisions, a gas molecule travels a straight path.
 The average distance of all the paths of a molecule is the mean free path.
Mean free path

 Analogy:
 Imagine a ball traveling in a box ; the ball represents a moving molecule. Every time
the ball hits a wall, a collision occurs and the direction of the ball changes (Figure1).
 The ball hits the wall five times, causing five collisions. Between every two
consecutive collisions, the ball travels an individual path. It travels a total of four
paths between the five collisions; each path has a specific distance, d. The mean free
path, \lambda, of this ball is the average length of all four paths.
 Mean free path

Each path traveled by the ball has a distance, denoted dn:

λ=d1+d2+d3+d4÷4 ……………(1)

Calculations
In reality, the mean free path cannot be calculated by taking the average of all the
paths because it is impossible to know the distance of each path traveled by a
molecule. However, we can calculate it from the average speed (⟨c⟩) of the molecule
divided by the collision frequency (Z).
The formula for this is:

λ=⟨c⟩÷Z. ……….(2)
Because Z is equal to 1/t, where t is the average time between collisions, the
formula can also be:

λ==⟨c⟩÷1÷t ………..(3)

=⟨c⟩×t ………..(4)
In addition, because
λ=2–√πd²⟨c⟩(N/V). ……….(5)
where
•d is the diameter of the molecule and
•(N/V) is the density,

The formula can be further modified to:

l==⟨c⟩÷√2πd²⟨c⟩N/V ……….(6)

1÷√2πd²(N/V) ………………(7)
Factors affecting mean free
path

 Density:
 As gas density increases, the molecules become closer to each other.
Therefore, they are more likely to run into each other, so the mean free path
decreases.
 Increasing the number of molecules or decreasing the volume causes
density to increase. This decreases the mean free path.
 Radius of molecule:
 Increasing the radii of the molecules decreases the space between them,
causing them to run into each other more often. Therefore, the mean free
path decreases.
 Pressure, temperature, and other factors that affect density can indirectly
affect mean free path.
Distribution of Speed &Energy

 Maxwell’s speed (v) distribution

Maxwell Speed Distribution ΙvΙ

 Maxwell velocity distribution

 Where

 let’s turn this into a speed distribution.

 F(v) dv = the probability of finding a particle with speed
between v and v + dv.

One cannot derive F(v) dv (i.e. a distribution of a scalar entity) simply from f(v) d3v
(the velocity distribution function, i.e. a distribution of vectors and their
components), we need idea of phase space for this derivation
 Idea of phase space, to count how many states there are
 Suppose some distribution of particles f(x, y, z) exists in normal three-
dimensional (x, y, z) space.

 The distance of the particles at the point (x, y, z) to the origin is

 the probability of finding a particle between

• The most probable speed v*, the mean speed , and the root-mean-square speed vrms are all
different.
 Most probable speed (at the peak of the speed distribution), simply plot the
function, take the derivative and set it zero, derive the consequences:

 Average (mean) speed, will be an expectation value that we calculate from on an

integral on the basis of the speed distribution function
 average (mean) of the square of the speed, will be an expectation value that we
calculate from another integral on the basis of the speed distribution function

 We define root mean square speed on its basis

 which is of course associated with the mean
kinetic energy

 We can also calculate the spread (standard deviation) of the speed distribution
function in analogy to quantum mechanical spreads

 Note that σv in proportional to

 So now we understand the whole function, can make calculations for all T
Straightforward: turn speed distribution into kinetic energy (internal energy of ideal gas)
distribution
Some Important Chemical
Applications of Statistical Mechanics

1. The basic equations connecting the translational, rotational, vibrational,

and electronic properties of isolated (i.e., gas-phase) molecules to their
thermodynamics.
2. The most basic descriptions of the vibrations of ions, atoms, or molecules
within crystals.

3. The most elementary models for describing cooperative behavior and

phase transitions in gas-surface and liquid-liquid systems.

4. The contributions of intermolecular forces to the thermodynamics of gases.