|
As the title implies, this new physical chemistry
textbook interweaves the statistical-molecular view with
classical thermodynamics. For the most part this book is
extracted from the 31 chapters of a recent comprehensive
physical chemistry text by the same authors. Titles of the 14
chapters in Molecular Thermodynamics give an immediate sense of
its organization as well as its content: The Energy Levels
of Atoms and Molecules; The Properties of Gases; The
Boltzmann Factor and Partition Functions; Partition Functions and
Ideal Gases; The First Law of Thermodynamics; Entropy and
the Second Law of Thermodynamics; Entropy and the Third
Law of Thermodynamics; Helmholtz and Gibbs Energies;
Phase Equilibria; Solutions I: Liquid-Liquid Solutions; Solutions
II: Solid-Liquid Solutions; Chemical Equilibrium;
Thermodynamics of Electrochemical Cells; and
Nonequilibrium Thermodynamics. The chapter on nonequilibrium
thermodynamics is an exceptional resource in a
non-monograph. Interspersed with the first six numbered chapters are
five lettered "Math Chapters" that provide essential
mathematical material.
This book effectively develops statistical
thermodynamic ideas and equations in an accessible way and then uses
them to reinforce and deepen the presentation of
thermodynamics. Another notable feature of the book, as in its longer
source book, is the frontispiece for each chapter, which is a
photograph of a famous contributor to thermodynamics, such as
Planck, Clausius, Gibbs, Helmholtz, Lewis, and Onsager,
and a vignette about the person's principal contribution and
life. An abundance of worked and end-of-chapter problems
is another strong feature, as is the near absence of errors, a
sine qua non for a useful physical chemistry text. The tone of
the writing is friendly and accessible. A manual with
solutions to all the problems is available.
What is the audience for this text? In the preface
the authors indicate that this book is suitable for an
undergraduate physical chemistry course, presumably for a
one-semester presentation since no development of kinetic processes, of
the principles of quantum mechanics or of spectroscopy
is included. Using the book in this way would be a
strenuous undertaking and, even then, would require a careful
selection of material. For an undergraduate physical
chemistry course, I find two features missing that are important in
my opinion. No figures or descriptions tell how
experimental measurements are made even though many data are cited
and used. With a very few exceptions the book contains no
citations of the sources of data, of other texts, or of the literature.
Consequently, students have no leads to supplementary
material and may conclude that physical chemistry is a
settled, classical subject.
There are other disappointments. The zeroth law is
not mentioned. Thus, the operational definition of
temperature through experimental measurements is not well grounded
or fully explained. The authors make a point of taking
the modernizing step of using IUPAC units and
symbols throughout the book, a choice that I applaud.
Regrettably, they have not taken the same forward step with respect
to "heat". In the development of the first law, heat is
carefully defined as a particular process by which energy is
transferred. Elsewhere, however, "heat" is often used as though it
were an energy content, as in "heat of reaction" and "heat
bath". The explanation of quantities like
rHo is inconsistent
with IUPAC usage. We read that
" rH
is an extensive
quantity, whereas rHo
is an intensive quantity." The "°" standard
state designation does not confer such a per-mol distinction.
We also read that
rHo
refers to the enthalpy change
associated with one mole of a specified reagent." The "°" does not
confer this distinction either. In the IUPAC recommendations,
the extent of reaction variable, ,
carries units of mol. Thus,
the per-mol aspect of
rHo or
rH
refers to any reaction as written, even to those with no unit stoichiometric
coefficient. A rHo
or a similar quantity only has full meaning when
a state-specific chemical equation is clearly associated with it.
|