August 22, 2001

Reading: Chapter One.

Homework: None.

Thermodynamics: Thermo- is a word pertaining to heat; dynamics is a

word pertaining to energy, force, or motion in relation to force. Therefore,
thermodynamics is a subject about the relationship between heat and other forms
of energy; or more generally, about the transformation between different forms of
energy.
One common form of energy is work done by force (mechanical energy). In this
case, thermodynamics deals with the relationship determining how much heat
must be put into a system for it to do a certain amount of work, and how much of
the heat is lost into surroundings. Steam engine and internal combustion engine
are technological examples where heat-work effects are important.
Of course, there are other forms of energies, such as, electrical, magnetic,
chemical, and nuclear energy. Different kinds of power plants are examples of
generating electricity from other different forms of energies, such as mechanical
energy (wind and water), chemical energy (burning coal), and nuclear energy
(fusion).
The energy transformation often creates a change in the system. Sometimes, the
primary interest is in the chemical and physical changes occurring within a system
caused by the exchange processes between heat and work, such as, the phase
transformation, the chemical reaction, and the nuclear reaction.
Thermodynamics is an equilibrium theory;
transformation under equilibrium conditions.

i.e.,

dealing

with

energy

Classical vs. Statistical Thermodynamics: Classical approach provides a

macroscopic view of thermodynamics; statistical approach provides a
microscopic, i.e., atomistic view. We will focus on the classical approach, but also
with some exposure to the statistical approach, which is important to appreciate
the implications of the classical approach.
Classical approach represents the changes that occur in a system pertaining to
energy transfer processes, using measurable macroscopic variables, such as
temperature, pressure, and volume. Statistical approach represents the changes,
using microscopic variables, such as particle (atom) positions, velocities,
densities, and interactions. All matter is made of particles (such as atoms, ions,
and molecules). The macroscopic parameters of a system are obviously a
manifestation of what happens at the particle level. The two representations are

related, as the macroscopic quantities are ensemble averages (over all the particles
in the system) of the microscopic quantitites:

Macroscopic
T (temperature)
V (volume)
P (pressure)

Miscoscopic
Vi (velocity)
Rij (inter-particle distance)
Rij,Fij (forces)

Classical thermodynamics is deterministic. It is based on a few physical laws that

are derived from experimental observations. Statements, such as heat cannot flow
up against a temperature gradient without a change in the surroundings.
Statistical thermodynamics is probabilistic. It is based on certain fundamental
physical laws (such as Newtonian mechanics and/or quantum mechanics) to write
down energetics of a collection of constituent particles and deduce the behavior of
a macroscopic quantity of the material system under study. However, a system of
a macroscopic size contains many particles. In one mole of matter, there are ~1023
particles. It is neither possible nor necessary to know positions and velocities of
all particles at any time. Therefore, a statistical description, i.e., a statistical
average, comes in. Thus, the approach is inevitably probabilistic in nature.
Both descriptions are appropriate and usually required. There are many instances,
in which one must employ statistical mechanics. Nevertheless, despite the
phenomenological approach used in classical thermodynamics, it is a very
powerful tool used in essentially all braches of science and engineering.
Statistical (probabilistic) approach becomes equivalent to classical (deterministic)
approach at the limit of large number of particles:
Consider an ideal gas consisting of N particles, contained in a container of
volume, V, of pressure, p, at temperature, T. Macroscopically, the pressure is
uniform, to be the same everywhere. Consequently, according to law of idea gas,
the number of particles per unit volume, N/V=p/kBT,
is the same everywhere. Microscopically, according
(p,V,T)
to statistically mechanics, the number of particles
V0
varies inside the container, with an average value of
<N>. Let N0 denotes the number of particles inside a
volume element of V0, where V0 is a region defined
by hypothetical boundaries. From statistical mechanics, one can determine the
probability of N0 deviates from <N0> by , i.e., the probability of N0 is grater than
x2

2 1
<N0>+ and <N0>-, is P( x0 ) =
( ) exp( 0 ) , where x0 =
.
x0
2
< N0 >
Assuming V=10 cm3, p=1 atm, and T=273 K (0oC), then the total number
of particles inside the container is N=2.69x1020.

If we choose V0=10-18 cm3, i.e., very small, then the average number of
particles inside V0 is <N0>=27. For a deviation of =5, we have x0=0.96 and
P(x0 ) 0.52. So, there is a 50% probability that N0 deviates from <N0>
appreciably (~20%). Consequently, there is big difference between statistical and
classical approaches.
If we choose a relatively large volume, V0=0.1 cm3, then <N0>=2.6x1018.
For a deviation of =10-4<N0>, i.e., 0.01% variation, we have x0=1.64X105 and

P(x0 ) 105.810 0.
9

So, the probability of N0 deviating from <N0> is

negligible. Consequently, there is little difference between statistical and classical
approaches, at this limit.