Statistical Ensemble

Prof. Leena Sinha

Department of Physics
University of Lucknow
Lucknow

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 Ensemble

Instead of taking time averages, Gibbs suggested to visualize in a group of similar systems but suitably
randomized and take average is over this group at one time.

An ensemble of systems is made up of very many systems all designed in the same way. Each system in
the ensemble is equivalent to the actual system for all practical purposes.

The ensemble is randomised in the sense that every configuration of coordinates and velocities accessible
in the actual system in the course of time is represented in the ensemble by one or more system at one
instant of time.
 If the system to be represented by an ensemble is in thermal equilibrium, then we require the
ensemble average to be independent of time.

A system for which time averages and ensemble averages are equal is said to be ergodic.

An ensemble average of a quantity will give us the average value of that physical quantity for the
actual system.

There are three main types of ensembles:

1. Micro‐Canonical Ensemble
2. Canonical Ensemble
3. Grand Canonical Ensemble
If the system is isolated ⇒not interacting with any other system, then the ensemble is called the
microcanonical ensemble.
Energy of the system is a constant
Example – (i) an ideal gas. Each gas particle be a ‘system’.
Each system/ particle is isolated and doesn't interact with any other particle/system.
(ii) Tea in an insulated thermal flask.

If the system is in thermal equilibrium with a heat reservoir the ensemble is called a canonical
ensemble.
Energy of the system is not a constant
Temperature is constant.
Example – (i) small block of copper immersed in a large container of liquid helium at 4.2 K -

If the system is in contact with a heat reservoir and a particle reservoir, then the ensemble is
called a grand canonical ensemble.
Energy and number of particle are not constant
Temperature and the chemical potential are constant.

Chemical potential is the energy required to add a particle to the system.

Thermodynamic limit-
Limit of a system with
a large volume, with
the particle density
held fixed
𝑁 → ∞; 𝑉 → ∞
𝑁
= 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉
 Do not exchange energy or particles with the surroundings

Have fixed energy, fixed volume and fixed number of particles

Useful for theoretical purposes – energy equation of state for ideal gas

1
Probability of finding a member of ensemble in a given microstate P=𝑊
 Free to exchange heat energy with reservoir
No definite energy we consider mean or average energy

System characterized by temperature T of Heat reservoir

small fluctuations in energy

a convenient way to calculate thermodynamic quantities

important use of Canonical ensemble is the derivation of Kinetic theory of gases Maxwell
distribution for speed of particles
 exchange energy and number of particles with the reservoir
Mean or average energy and number of particles

System characterized by temp T and chemical potential of Heat reservoir

Fluctuations In energy and number of particles

convenient way to deal with Quantum Statistics

Reference Books:

1. Elementary Statistical Physics

C. Kittel
2. Foundations of statistical mechanics
O. Penrose
3. Statistical Physics
L.D. Landau and E.M. Lifshitz