7.

Third law of thermodynamics and consequences (định

luật 3 của nhiệt động lực học và hệ quả)
8. Define number of microstate and statistical entropy
• Foundations
 we have described the macroscopic properties of matter
phenomenologically with the aid of equations of state which had been
derived empirically. For thermodynamics it is of no importance, in
this connection, how a certain equation of state comes about.
 The macroscopic quantities of state result from taking mean values of
microscopic properties.
 It is now the task of statistical physics to define in an exact way the
process of taking mean values, which leads from the microscopic
quantities (momenta, coordinates), thus providing a connection
between the atomistic, microscopic theory of matter and macroscopic
thermodynamics.
The key to this connection is entropy
• Phase space (Không gian pha)
what has to be understood under the notion microstate?
 For a classical system it is sufficient to know at a time t all generalized
coordinates q(t) and momenta p(t) to uniquely fix the state of motion of
the system. Thus for a mechanical system we can interpret the set (q , p
),  = 1, ..., 3N as the microstate of this system.

 The set (q , p ) can now be understood as a point in a 6N-dimensional

space which is called the classical phase space. A six-dimensional space
for each atom is called -space
 A definite point in this phase space exactly corresponds to one
microscopic state of motion of the whole system.
 The temporal evolution of the system corresponds to one curve (q (t), p 
(t)) in phase space, which is called the phase-space trajectory. It is
determined by Hamilton's equations of motion

 The Hamiltonian H(q (t), p  (t)) corresponds to the (possibly time-

dependent) total energy of the system. It is a function of the phase-space
 point (q , p ) and of time, and according to Hamilton's equations it
determines the temporal evolution of the system.
 In a closed global system, in which the Hamiltonian does not depend
explicitly on time, the total energy is a conserved quantity,

Example: Harmonic oscillator

• The Hamiltonian of a harmonic oscillator in one dimension reads

p2 1 2
H (q, p)   Kq  E
2m 2 (2.1)

 To Equation (2.1) there corresponds a two-dimensional phase space, as

shown in Figure
 The phase-space trajectory is just an ellipse in one-particle phase space
which is determined by the value of E (the energy hypersurface). During
its temporal evolution the actual phase-space point (q(t), p(t)) of the
system can move only on this ellipse. It never intersect itself, because the
solution to the equation of motion is unique.
 In the figure we have drawn two such ellipses which differ only slightly
in energy. Each point on the ellipses corresponds to a concrete state of
motion (snapshot) of the oscillator with an energy between E and E + E
at a given moment.
 Each such phase-space point can be identified with a copy of the actual
oscillator in a certain state of motion.
 This means that the hypersurface also reflects the phase-space
distribution of many equal systems at one moment.
  A collection of such phase-space points (systems) which are consistent
with certain macroscopic properties (here: total energy between E and E
+  E) is called an ensemble.
• We can subdivide a high dimensional phase space into volume elements,
which is called a phase-space cell.

• Let (E, V, N) be the total phase-space volume, the boundary of which is

given by the energy hypersurface E = H(q, p) and the walls of the
container in coordinate space.

For small E, the volume between two energy surfaces with energies E and E +
E is given

• The volume between two neighboring surfaces with area (E) and
distance E is given by
 (2.4)
which by comparison with Equation (2.4) gives

We assume the number of microstates, (E, V, N) to be proportional to this

surface,

where 0 is the constant of proportionality and 0=

9. Establish canonical phase space density
• The microcanonical ensemble is especially suited for closed systems with
the natural variables E, V, and N. However, the microcanonical ensemble
contains considerable mathematical difficulties.
• Therefore we now want to describe a system at temperature T, (a system
S in a heat bath R).
The total energy of the whole system

has a constant given value.

• By definition, the heat bath is very large compared to the system itself, so
that

• Since now it is no longer the energy ES which is fixed,

but the temperature, the system S will be able to assume all possible microstates
i with different energies Ei, with a certain probability distribution. We ask for
the probability pi, of finding the system S in a certain microstate i with the
energy Ei.
• If S is a closed system, pi, will be proportional to the

number of microstates
 • Analogously, pi is proportional to the number of microstates in the total
closed system for which S lies in the microstate i with the energy Ei.
Obviously this is just equal to the number of microstates of the heat bath
for the energy
E-Ei, since S only assumes one microstate i:

• We expand the entropy SR of the heat bath,

(2.9)
• However,

(2.10)
• Insertion of Equation (2.10) into Equation (2.9) and exponentiation yields

Here the sum i extends over all microstates (phase-space points).

Here the sum i extends over all microstates (phase-space points).

 • In continuous notation Equation (2.11) reads

(2.12)

Here we have abbreviated the frequently appearing factor .

. Equations (2.11) and (2.12) yield the canonical phase-space density,
which we denote by the index c
• A statistical mean value of all energies Ei , which are actually
assumed in the ensemble,