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Book Review Chemische Thermodynamik (Chemical Thermodynamics). By A. Mfnster

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without any marked strain only when the resulting ring contains at least 10 members. ( I ) , (21, and (41 can be prepared,
inter ulia, from ethylene glycol, 1,3-propanediol, and pyrocatechol, respectively, and tetramethylcyclobutene-l,2-diol;
(3) is formed by cyclization of theether formed from 3-chloro1,2,3-trimethyl-4-methylenecyclobutene and the monosodium salt of 1,4-butanediol. (1)-(4) each gave two (endoiexo)
monomeric ozonides; for example, the ozonide (5) was formed from ( I ) . A cis-linkage in (I)-(4) is deduced from the
ozonide formation. On heating the tetramethyl-1 ,Zcyclobutenediols with acids in inert solvents the authors obtained
three isomeric tricyclic compounds, of which (6) (m.p.
171 “C) is converted into the dioxabishomocubane derivative
(7) on irradiation. Chem. Ber. 103, 50 (1970). / -Kr.
a
mm2. The average S-N bond length of 1.55 is indicative
of considerable double bond character. / Chem. Commun.
1969, 1187 /-Ma.
[Rd 149 IE]
Synthesis of y-lactones from alkenes has been described by
P. Boldr, W. Thielecke, and .
I
Etzemiiller.
.
Addition of bromodicyanomethane to alkenes in methylene chloride leads,
on irradiation, to 1-bromo-2-dicyanomethylalkanes ( I ) ,
which can be converted directly by hydrolysis and decarboxylation into y-lactones in good yield. Cyclohexene gives the
[Rd 147 IE]
Preparation and structure of the cyclopentasulfur pentanitride
cation ( I ) are reported by A . J. Banister, P . J. Dainty, A . C .
Hurell, R. G . Huzell, and J. G . Lomborg. The sulfur nitrides
S ~ N ZS4N4,
,
and (SN), can be considered as members of the
series SN’, S2N2, S3N3+, S4N4, S,-N5+, S6N6. . . (SN),. The
first cation of this series to be obtained was the cation SsNs+;
it was prepared in the form of the tetrachloroaluminate,
SsN5AlC14 (yellow prismatic crystals, m.p. 181 “C), by
adding S4N4 to a solution of AIC13 in SOClz over a period of
48 h with stirring at room temperature followed by fractional
crystallization (by concentration). According to X-ray
crystallographic investigations, ( l j forms a ten-membered
ring that is almost planar and has an approximate symmetry
a160 %
0
?bo
H
(4)
cis-lactone stereoselectively. The lactones (2)-(5) can be
obtained from propene, 2-methyl-2-butene, l-methylcyclopentene, and trans-1,2,3,4,4a,5,8,8a-octahydronaphthalene
in 78, 68, 66, and 81 ”/o yields, respectively. Compounds (6)
likewise give y-lactones on hydrolysis and decarboxylation. /
Chem. Ber. 102, 41 57 (1 969) ,’ -Ma.
[Rd 152 IE]
BOOK REVIEWS
Chemische Thermodynamik (Chemical Thermodynamics).
By A . Miinster. Verlag Chemie GmbH, Weinheim
Bergstr. 1969. 1st Edit., x, 261 pp., 34figs., paper, D M
29.-.
A new book on thermodynamics is assessed by how much it
is better than the others. The principles of thermodynamics
should be explained with impeccable logic, and the applications should be real ones.
That the good points of the present book outweigh its failings
is due to the pedagogic experience of the author, who follows
Cibbs’ method consistently, introduces the main laws as (experimentally validated) axioms, and derives all further relations by relatively simple mathematics.
To find a successful description of CarathCodoric axiomatics
in such a small booklet is surely sensational. On a second
reading of the relevant chapter the reader recognizes the
pedagogic value of Curathiodory’s work, which is presented
in a considerably more readable form by Miinster than in the
original. It is shown that Curufhiodory’s first law (anywhere
near a given state of a system is a neighbor state that is not
accessible from it by an adiabatic route) becomes equivalent
to the second law only after addition to it of a further law
(one of experience).
Description of the general conditions for equilibrium and
stability is followed by the customary applications of thermodynamics to phase equilibria, chemical equilibria, critical
phases, electrochemical equilibria, matter in a gravitational
and in a centrifugal field.
178
The paragraph o n the Nernst heat law in the chapter o n
chemical equilibria deserves special mention. Munster has
here not only explained the various formulations of this law
critically, but he has also consistently avoided the usual recourse to statistical considerations.
The book’s weaknesses perhaps result from its advantages.
Thus in the classical formulation of the main laws, Munsfer
avoids the classical introduction of heat and temperature,
possible though this is, and reserves it for the later section o n
CarathCodoric axiomatics. This applies also to the clear
definitions of the concepts “adiabatic” and “quasistatic”.
The tendency to express physical connections in mathematical
terms has adverse effects on the readability, particularly for
the beginner who has not acquired perspective; unusual
+
--t
symbolisms (rot R = grad x R) are partly to blame for this.
The more experienced reader will turn gladly to this book for
advice on presenting the axiomatics of thermodynamics.
KI. Schufer
[NB 850 IE]
Differentialthermoanaiyse (Differential Thermal Analysis).
By D. Schultze. Verlag Chemie GmbH, . W e i n b c k t ~
Bergstr. 1969. 1st Edit., 335 pp., 196 figs., 42 tables,
plastic cover, D M 58.-.
Chemical changes of materials usually go hand in hand with
thermal effects. Since thermal effects can be measured with a
considerable degree of accuracy by modern electronic methAngew. Chem. internat. Edit. ,IVol. 9 (1970)
NO. 2
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