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Tutorial Chemistry Texts, No 5. The Royal Society
of Chemistry: London, 2001. 181 pp. Figs., tables. ISBN 0-85404-647-X. $15.00.
On my bookshelf are two earlier books by Jack Barrett:
Introduction to Atomic and Molecular
Structure, published in 1970, and Understanding
Inorganic Chemistry, published in 1991. I have always liked
his treatment of the bonding in the water molecule,
and so I naturally turned to the discussion of the
water molecule in this new book, Section 5.3.1, pp
94-100. The treatment is very tight, including a
comparison between the bent and the hypothetical linear
molecule. The results of the MO treatment are
supported by a photoelectron spectrum of water vapor.
Barrett shows how symmetry properties determine
which atomic orbitals can combine to give bonding
molecular orbitals; that the p orbital perpendicular to the
H-O-H plane is nonbonding in character; and (most important) that the energy gap between the 2s
and 2p orbitals on oxygen is so large that the 2s orbital
is essentially nonbonding. The level of the treatment
of bonding is thus clearly defined: this is not for
freshmen, but for sophomore to senior students. (In
fact the approach is similar in flavor to that in
Inorganic Chemistry by Miessler and Tarr.)
Chapter 1 takes the student through a very condensed treatment of Bohr atom, atomic
orbitals, quantum numbers, and electron configurations.
Only Allred-Rochow electronegativity coefficients
are considered (p 13) on a 3-dimensional bar graph,
but with no table of numeric values.
The heart of the book begins with Chapter 2,
Molecular Symmetry and Group Theory. The
pedagogical aims are clearly stated. The diagrams are clear
and attractive, some in two colors. There is a
good section of Worked Problems, plus further
problems (whose answers are at the end of the book). This
is clearly meant to be a text for the student to use
and learn from. (There is a minor cultural problem in
one question about point groups on page 32: the object
is a rugby ball.)
Diatomic molecular orbitals are treated
conventionally, with energy data from photoelectron spectra
to support the results of the MO treatment (e.g. data
for N2 and CO in Table 4.3). The photoelectron
spectra themselves are not given, which I feel is an
unfortunate omission.
VSEPR is revised in two pages. The MO treatment
of CO2 and XeF2 is discussed in some detail and
is followed by that of NO2+,
NO2, NO2-. Barrett
very explicitly points out how the s-p energy gaps on
the atoms govern the extent of orbital mixing no
matter what the symmetry properties may indicate:
an important point.
Chapter 6 is about Covalent Bonding in
polyatomic molecules; it incorporates VSEPR, point
group symmetry, and molecular orbitals. Although the
MO treatment of methane is covered very tersely, it
is supported by a good figure of methane's
photoelectron spectrum. The bonding and shapes of
BF3, NF3, and
ClF3 are discussed nicely. The terms HOMO
and LUMO are used (p 134); I could find neither term
in the index but they are defined on p 101.
There is an interesting and unusual use of the VSEPR approach to predict the molecular shapes of products of successive dehydration reactions
(Figs. 6.18 to 6.21).
Chapter 7 deals with metallic and ionic bonding.
The ionic-covalent transition is discussed in terms
of Fajans' rules. There is a reference to
Pyykkö's Chemical Review of 1988 about relativistic effects
but not to his later Review of 1997.
One must now ask: what is the place for this book?
It is not meant to be a comprehensive text
about bonding in molecules: for example, ozone is
not mentioned nor are the two singlet forms of
dioxygen. It is part of the RSC series of Tutorial Texts aimed
at first- and second-year students in British
universities, who have completed the UK A-level syllabus.
The text is very compressed. A student would profit
by reading it after a more leisurely introduction
during lectures. A lecturer who knows the subject will
gain some new ideas and insight from a different point
of view. It is well worth having a copy in your library.
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