Williams 1955
Williams 1955
Williams 1955
43
Doolittle’s experience and personality come to light in his treatment of such questions
as the factors that influence viscosity, the theory of solvent action, and the mechanism of
plasticization. As is proper, he emphasizes those complications, such as slowness of
attainment of equilibrium, which have led him to his mechanistic picture of solvent ac-
tion. His extensive work on the solvent action of homologous series containing specific
groups is summarized. This work deserves special attention, because it gives a clear
demonstration that a given content, in moles per liter, of a n active solvent group is not
as effective with the lower members of a homologous series as it is with the higher mem-
bers. The conventional thermodynamic approach t o solvent action, contributed by
Paul Doty, is as concise and yet understandable as any familiar to the reviewer.
Unfortunately, Doolittle is not a master of the sweeping generalization. For this
reason, a concept sometimes gets lost in the discussion. This is nowhere more
evident than in the discussion of plasticizer action. The role of plasticizer viscosity was
undoubtedly appreciated, for there are graphs of the viscosity-temperature behavior
for all the common plasticizers, and the concept of “internal viscosity” is mentioned.
I t is also demonstrated that “internal plasticization,” by chemical attachment of a group
that lowers attraction between chains, is not nearly as en’ective as solvent plasticization.
Still, the obvious generalization was missing that the flexibility and extensibility of a
composition is governed by the freedom of movement of a segment of a polymer chain;
that this freedom is governed by the viscosity of the mixture of plasticizer and segments
of other chains in the immediate vicinity; that this viscosity is greatly influenced by the
viscosity of the plasticizer itself; that the plasticizer must be compatible with the poly-
mer, but too high a degree of solvent action is undesirable because then the plasticizer
is too tightly bound to the polymer chain and behaves like an “internal plasticizer.”
Valuable generalizations of a more empirical nature are given, but they might have
been better emphasized. Examples are: fluidity, not viscosity, of mixtures tends to be
additive; long-chain flexible molecules have a lower viscosity for the same vapor pres-
sure than do more compact molecules.
Another small defect is that sources are not given for any of the hundreds of graphs.
Much of the material has not been published before, but this is by no means universally
true.
Summarizing, this book is complete and reliable in matters of factual information.
The theoretical treatment is very good as far as it goes. Above all, the more theoreti-
cally minded no longer have an excuse for neglecting the complications in actual polymer
systems. These complications are treated in detail, and an excellent start has been
made in their interpretation.
I€. M.Spurlin
of the treatment. I t follows the customary approach of texts for courses in colloid
chemistry; a volume replete with general statements, and as such subject t o the faults
which are always inherent in them. Perhaps “theoretical speculation” has been avoided
in order to keep down the mathematical apparatus which would otherwise have been
required.
The reviewer will agree it is well to avoid speculation, but a t the same time he would
argue that much of the subject now has been brought to the point where better under-
standing has come tlirough the application of fundamental laws of physics and chemistry
and that this situation might have been made more apparent for the serious student and
research worker. Thus, it would have been our preference to avoid the use of the word
“solvation,” along with its “determination,” in Chapter 14, especially since in many
places in the text the authors have used the word “solution” when writing about protein
and high polymer behavior. We no longer see need for a stability theory of lyophilic sols
which “depends more or less both on the charge and on the solvation of the particles.”
Making allow-ancefor the fact that there are distinguishing features between the solution
behavior of micromolecules and macromolecules, it is nonetheless true that these sub-
stances which long have been classified as lyophilic colloids pass spontaneously into a
dispersed form t o give solutions that meet the various criteria of thermodynamic stability.
Thus, by the application of thermodynamics, solubility and solvent-solute interactions
are described in a logical fashion and certain solute molecular characteristic data, such
as molecular weights and activity coefficients, are made available. Also, with the recog-
nition that such intrinsic colloids are macromolecules in true solution have come satis-
factory explanations of behavior in viscosity, diffusion, sedimentation velocity, electro-
phoresis, and other common experiments.
The reviewer found Chapter 11 to be attractive. It has to do with the determination
of particle size, form, and structure, using x-rays and electrons. The section on the
x-ray analysis of organic gels, Chapter 15. also has its appeal. Yet, in a book with pub-
lication date 1954 and in which proteins are so often mentioned, it seems unfortunate
that no survey is made of the 1951 contributions of Pauling and Carey which have t o do
with the hydrogen-bonded helical configuration of the polypeptide chains and its rela-
tion t o the structure of proteins. Again, the application of x-ray data t o the calculation
of molecular weights, presumably for crystalline proteins, is mentioned in a single sen-
tence.
Chapter titles art:: First Part: 1 . ‘The History and Scope of Colloid Chemistry;
2 . Classification of Colloids. The Basic ‘Terms in Colloid Chemistry; 3. Some Simple,
Basic Methods in Experiments with Colloids; Second Part: 4. The Kinetic Properties
of Disperse Systems; 5. Interfacial Phenomena; 6. The Optical Properties of Colloids;
7 . The Electrical Properties of Colloids; 8. The Viscosity of Colloidal Solutions; 9. The
Determination of Particle Size; 10. Determination of Particle Shape; 11. The Deter-
mination of Particle Size. Form. and Structure Using X-Rays and Electrons; 12. The
Preparation of Colloidal Solutions; 13. The Coagulation of Lyophobic Colloids; 14. The
Stability of Lyophilic Sols: 13. Gels, Jellies and Membranes; 16. Emulsions; 17. Dis-
persions of Gases and Foarns; 18. Aerosols: Fog, Dust, Smoke; 19. Solid Sols.
What one will discover from this book is that no branch of science offers more varied
behavior, more intriguing experiments, and more practical applications. The long
familiarity of the authors with the subject has enabled them to present a broad and valu-
able panorama. The account is often reasonably detailed, and for the most part up-to-
date. We predict that the book will be found valuable not only to chemists, but also
t.o many others who have an interest in the general subject.
.I. W. Williams