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N. A. Gokcen and R. G. Reddy. Plenum: New York,
1996; ISBN 0-306-45380-0; $59.50 (hb).
In Gocken and Reddy's
Thermodynamics, the emphasis is placed firmly on the practical application of
thermodynamics to describe real systems. The development of
the fundamental principles is done in a traditional style
based on ideas of practicality and measurement. The subject
material is almost entirely limited to classical
thermodynamics, with very little reference to microscopic models or
statistical concepts. While this takes away somewhat from
the interconnectivity of modern physical chemistry, it keeps
the book well focused and allows a considerable amount of
detail to be presented without becoming unwieldy. The
level of mathematics is kept relatively low, aside from the
inevitable differential equations, and a separate chapter
summarizes all of the math to be encountered, at a level
appropriate for students in a first-year calculus course.
Following the first two introductory chapters,
roughly one-third of the book is devoted to a standard
presentation of the three laws of thermodynamics, definition of the
Gibbs and Helmholtz energies, and introduction of the
chemical potential. Most of the remaining text is devoted to examples
and applications of chemical equilibrium, including
discussions of activities and real solutions, colligative
properties, chemical reactions, electrolytes and cell reactions,
and phase equilibria.
This book would be suitable for the
thermodynamics component of an introductory physical chemistry course
in which more depth is sought than would be typically
found in a comprehensive introductory text. At a more
advanced level, the lack of statistical models is a limitation;
however the material could be useful in a more applied course
for students interested in chemical engineering or
materials science. The book contains a good selection of problems
and examples, and is quite well referenced with numerous
footnotes.
The strongest element of the book, in my opinion, is
a very thorough treatment of phase diagrams, which does
a good job of linking the topology to thermodynamic
principles (although a more unified discussion of Maxwell
constructions and critical points would be welcome). This
material includes a good discussion of liquid-vapor curves and
partial pressures, and culminates in a large selection of
real examples. Another prominent feature of the book is the
inclusion of a large number of empirical formulas and
approximation schemes, allowing each concept to be
immediately extended to describe real systems. But this is also
a weakness, since some key ideas can be drowned in a sea
of parameters, with no further physical insight being
provided.
The biggest difficulty, however, stems from the fact
that the book's empirical emphasis is somewhat at odds with
the axiomatic approach employed. This can lead to some
awkward definitions, which are presented with little
justification. For example, temperature is defined as an
unspecified function of pressure and volume arising from a
constraint on the number of degrees of freedom due to thermal
equilibrium. Not only is this not very intuitive, it isn't even
correct since T(P,V) is not a single-valued function. Also,
the chemical potential is defined solely as the partial
molar Gibbs energy (which in turn is a "purely convenient"
function), analogous to other partial molar quantities,
rather than as a fundamental intensive variable on an even
footing with temperature and pressure. This not only
obscures the important role that it plays, but leads to
unnecessarily convoluted definitions of chemical equilibrium.
As a final note, the book comes equipped with a
diskette containing a software package for
thermodynamic simulation. The program provides a graphical display
of c(sub)p, (Delta)(sub f)H(std), and (Delta)(sub f)G(std)
as functions of temperature, using empirical formulas
provided in the references. While potentially useful as a database
of such information, the software adds very little to the
pedagogical value of the book and is unlikely to be of much
interest to students. From a practical point of view,
the readme.txt file was not in fact readable without
additional software, the interactive help is not yet available, and
the program crashed several times while being tested.
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