Introduction to physical chemistry:

John T. Yates, Jr.

Antioch College
Yellow Springs, Ohio Thermodynamics, Kinetic Theory,
and Statistical Mechanics

It
is clearly evident that the standard majors at Antioch. One of the objectives is to
undergraduate senior physical chemistry course of strengthen the training of undergraduate chemistry
a few years ago has been moved forward in the cur- students in physics.
ricula of many colleges and universities. Certainly The course is divided into three major sections:
a primary reason for this trend toward earlier pres- the thermodynamics of pure substances, the kinetic
entation of physical chemistry is the realization that theory of gases, and elementary statistical mechanics.
advanced courses in analytical, inorganic, and organic The design is to proceed from a macroscopic level to
chemistry can be taught more effectively with students a microscopic level of appreciation of the properties of
having some early training in physical chemistry. matter.
An alternative to moving the entire course in phys- I shall not attempt to relate in detail the sequence of
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

ical chemistry ahead is to extract certain basic subjects topics covered in this course; instead I will mention
from physical chemistry and to present these subjects those topics which best illustrate the structure and the
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in an introductory course. Since physics is basic to unique features of this course.

physical chemistry, the topies in the introductory
course which I am about to describe all bear a strong Thermodynamics
relationship to physics, or perhaps better to chemical We begin the first section on thermodynamics with
physics. This course is presently offered at the soph- the usual subjects dealing with the description of
omore or junior level to both chemistry and physics
thermodynamic systems. We consider the concept
of temperature and the use of various types of ther-
Presented before the Division of Chemical Education at the 141st
mometers. The relationship of the international
Meeting of the American Chemical Society, Washington, D, C., temperature scale to ideal gas thermometry is em-
March, 1962. phasized. It is considered important here to show

Volume 39, Number 10, October 1962 / 503

 beginning students some of the experimental diffi- liquid droplets. Also, the superheating of boiling
culties involved in precision temperature measure- liquids may be understood quite easily when one
ment.1 We next consider the general concept of the considers the vapor pressure above the concave liquid-
equation of state of a substance, and here the van der vapor surface in a vapor bubble under a boiling liquid.4
Waals equation is introduced to illustrate an empirical In every case where possible, we introduce the thermo-
attempt to describe departures by gases from ideality. dynamic functions by demonstrating their particular
The concept of thermodynamic work is next intro- utility in understanding various kinds of physical
duced, with particular care to include types of work problems. Finally, by using the Euler criterion for
other than expansion work and electrical work. Then exact differentials, the Maxwell relationships for one
coefficients of cubical expansion and compressibility component systems are formulated. These equations
for ideal and imperfect gases and particularly for are used to derive a large number of representative
solids and liquids are presented. It is then feasible thermodynamic differential relationships.
to calculate for a solid or liquid the expansion work Consider the general differential expression
for various processes other than the usual constant dz =
M(x, y)dx + N(x, y)dy
pressure process.
The first law is now stated and its consequences If there is a function z(x,y), then dz is an exact differ-
are examined. In this connection the various methods ential and,
for measuring the heat capacity of a substance are
discussed with particular emphasis on the Nernst
calorimeter for low temperature
* =

(£)/" +
adiabatic vacuum
heat capacity studies.2 Having studied the internal Now, since order of differentiation is immaterial,
energy as a thermodynamic state function, we invent / O2^ \ _
/ d‘z \
and employ the enthalpy function as an aid to under- \dxdy/ \dybxj
standing topics such as the Joule-Thompson effect, or
the thermodynamics of an open system such as a
/£>AA
turbine, and the Bernoulli effect where the pressure (>y )
=

\i>X J y
of a flowing incompressible fluid is related to its velocity
I

under constant energy conditions. which is the Euler criterion for an exact differential, dz,
At this point, we examine phase equilibria in one in two independent variables, x and y.
component systems, critical phenomena, and the law Now the differentials of all thermodynamic state
of corresponding states. Special emphasis is placed functions are exact differentials, since the state function
on Bridgeman's contribution in the area of high pres- is completely defined except for a constant of integra-
sure phase equilibria studies. In this connection we tion by the values of the independent variables, i.e.,
discuss the P-V-T surface of water over a wide range z —

z(x, y) + constant
of pressure, rather than the often used projection
on the P-T plane.3 From the general differential forms of the state
The second law of thermodynamics is then introduced functions for one component systems, where the only
as a generalization of our experience, and the equiva- work done is expansion work,
lence of the Clausius and the Kelvin statements of dE = TdS pdV -

the second law is demonstrated using reversible en- dH =

Vdp + TdS
gines. This naturally leads us to the Kelvin thermo-
dA =
-pdV SdT -

dG =
Vdp SdT -

dynamic temperature scale.

One of the most important applications of the second we obtain the four Maxwell relations by cross differ-
law is the Clausius-CIapeyron equation which we entiation.
derive both in the exact and approximate forms.
Application is then made to phase diagrams and vapor \3P/v \.*Tjs
pressure problems.
The entropy function is now deduced in the usual \Wjp \dT J s
thermodynamic manner and entropy changes for
various reversible and irreversible processes arc con- (m «
\dVjr \i)T/
=

v
sidered. The Helmholtz and Gibbs free energy func-
tions are devised and utilized in appropriate fashion.
One problem here which is always of interest involves
(m
\dPjT -(dV)
\i>T
=

J p

the calculation of the equilibrium vapor pressure above The two other possible differential entropy ex-
tiny spherical droplets where the influence of surface pressions are obtained from the definitions of Cp and
tension is important. This subject is intimately related Cv.
to supersaturation in a mist containing very tiny
(i>s_\ _ Cj
\df)c T
1
An excellent treatment of this subject may be found in Paul, (bS\ _
Cv
M. A., “Principles of Chemical Thermodynamics,” pp. 1-43, W)P T
McGraw-Hill, New York, 1951.
2
Experimental aspects of this subject arc well-treated in With these six equations, a large variety of useful
White, G. K., “Experimental Techniques in Low-Temperature thermodynamic relationships may be formulated.
Physics,” Oxford University Press, New' York, 1959.
3
Zemansky, M. W., “Heat and Thermodynamics,” McGraw- 4
Paul, M. A., “Principles of Chemical Thermodynamics,”
Hill, New York, 1957, pp. 203-6. McGraw-Hill, New York, 1951, pp. 274-6.

504 / Journal of Chemical Education

Kinetic Theory of Gases course are therefore concerned with the calculation

At this point the basic principles of thermodynamics of the internal energy and the heat capacity of gaseous
have been introduced and examined in some detail. diatomic molecules and the relationship which these
The students have become aware of some of the types thermodynamic quantities bear to molecular spec-
of problems which may be handled by means of thermo- troscopy.
This introductory course5 forms the base upon
dynamics. This is an appropriate time therefore
to introduce the kinetic theory of gases, so sharply which an additional two-term senior physical chemistry
contrasted to thermodynamics in method and scope. sequence is built. With students having a strong
Some of the topics which we cover are Maxwell’s
foundation in thermodynamics, the transition to
derivation of the velocity distribution, the use of chemical thermodynamics is swiftly and easily ac-
distribution functions for averaging, intcrmolccular complished. The economy of time thus achieved in
senior physical chemistry makes possible a rather
potential energy functions, molecular beams, transport
properties, equations of state for gases, and the heat thorough treatment of subjects such as statistical
capacity of gaseous polyatomic molecules. The topics thermodynamics and quantum chemistry, in addition
dealt with by means of kinetic theory are related to the usual subject matter.
back to thermodynamics wherever possible, and a Evaluation of the Course
deeper understanding of the properties of matter is
therefore achieved via molecular theory. What are the advantages in this approach in teaching
physical chemistry? Foremost is the fact that this
Statistical Mechanics arrangement permits the beginning chemistry student
to perceive the flavor of physical-chemical endeavors
before his last or next-to-last year in college. In
The stage has now been set for the third and final
addition, it is also felt that the three basic disciplines
major discipline to be covered in this course—ele- of this course are treated in somewhat greater depth
mentary statistical mechanics. Here we are concerned than is normally possible in two terms of senior physical
with calculating the macroscopic equilibrium prop-
erties of a system from a knowledge of the microscopic chemistry. Finally, the introductory course produces
some of the advantages which are proclaimed by
situation. We begin with classical Maxwell-Boltz-
those who would move the entire course in physical
mann statistics and the fundamental assumption of
statistical mechanics that all conceivable microstates chemistry to the early years.
At the present time there is no regular laboratory
of an assembly are equally probable. The general
associated with the introductory course. By the
expression for the thermodynamic probability of a time the students have completed this course they
given macrostate is then statistically formulated, are at a theoretical level sufficient to enable them to
the most probable macrostate is selected, and the
do rather sophisticated experimental work in certain
general Boltzmann distribution function is derived. areas of thermodynamics and the kinetic theory of
The entropy function is now connected to the thermo-
gases. An elective laboratory course for chemistry
dynamic probability of this most probable macrostate. and physics majors has therefore recently been insti-
The internal energy function can then be expressed
in terms of the partition function for the assembly. tuted. At the present time the plan is to offer ex-
At this state of the development the students are able perimental work in areas such as: low temperature
to see the real power of statistical mechanics in relation calorimetry; vapor pressure of solids by effusion
to thermodynamics, since it is now possible in principle studies; crystal energy of solids from the vapor pres-
to calculate the magnitude of the thermodynamic sure; the thermodynamics of physical adsorption;
state functions from a knowledge of the microscopic
thermal conductivity of gases; thermal diffusion;
situation. Previously, using thermodynamics alone, gas viscosity. This elective laboratory program will
enable students who are particularly interested in
only differences in the magnitude of state functions
could be obtained. experimental chemical physics to undertake laboratory
We apply classical statistical mechanics to an ideal problems which are designed to precede and supplement
the required laboratory in senior physical chemistry.
monatomic gas, evaluate the translational partition
The introductory course in thermodynamics, kinetic
function by integration, and arrive at the Maxwell-
Boltzmann distribution function for molecular veloc- theory, and statistical mechanics has been offered
to chemistry majors at Antioch College for the past
ities. The same function had been obtained earlier
five years, and it is a required course for all B.S. can-
by different methods in the kinetic theory section. didates in chemistry and physics. The course is
An interesting problem which can be handled quite
nicely at this point is the Boltzmann distribution of taught alternately by members of the chemistry or
physics departments. Chemistry majors who have
particles in a force field; one particular example of taken this course seem to be more mature scientifically
this gives the barometric formula for an isothermal
during their college days than those trained in the
atmosphere. conventional fashion.
The transition from classical statistical mechanics
to the statistical mechanics of systems containing s
At the present we are using as a text Sears, F. W., “An In-
diatomic molecules which have rotational and vibra- troduction to Thermodynamics, The Kinetic Theory of Gases,
and Statistical Mechanics,” Addision-Wesley, Reading, Mass.,
tional degrees of freedom is easily accomplished if 1953. Another text with a similar approach is King, A. L.,
the quantum mechanical expressions for the allowed “Thermophysics,” W. H. Freeman, San Francisco, 1962. A
energy levels are accepted. The last lectures in this syllabus is available upon request.

Volume 39, Number 10, October 1 962 / 505