Nov. 5, 1963
BOOKREVIEWS
Burgess and Kahler9 found that precipitation of sodium amide poisoned a metallic catalyst for the sodiumammonia reaction. The slower rate for lithium as compared to potassium was expected. We have studied lithium and potassium reductions of ethanol in ammonia under conditions similar to those used for sodium reductions already reportedlo in the previous paper in this series. In (9) W. M Burgess and H. L. Kahler, J A m Chem. Soc., 60, 189 (1938). (10) E J . Kelly, H. V. Secor, C. W. Keenan, and J . F. Eastham, ibid., 84, 3Gl1 (1962)
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these reaction mixtures at - 3 3 O , the rate of the reaction of lithium with the solvent was found to be much slower than the rates of potassium or sodium Acknowledgment.-We thank the National Science Foundation for financial support through Grants G14596 and GE-3-25. D A V I D Y P CHOU OF CHEMISTRY M A R YJ o PRIBBLE DEPARTMENT THEUNIVERSITY OF TENNESSEE DONALD C JACKMAS KNOXVILLE 16, TENSESSEE CHARLESLV KEESAN RECEIVED.IUCLST 28, 1963
B O O K REVIEWS Representation d e s 6quilibres d e Solubilitks e t Utilisation d e s Diagrammes. By ROBERT BERTHON, Ingenieur Chimiste ( I . C . N.), Docteur es Sciences Physiques, Chef d u Service d e Kecherches des Mines Domaniales d e Potasse d’Xlsace. Gauthier-L’illars e t Cie, Quzi des Grands-Xugustins, 55, Paris ( V I e ) , France, 1963. 269 pp. 16.5 X 21.5 cm. Price, 38 F. This monograph deals with a special aspect of t h e representation a n d application of t h e quantitative relations in t h e phaseequilibria of aqueous salt systems. T h e “representation” is treated purely a s a problem in analytical geometry in three dimensions; t h e mathematical relations a r e considered graphically, in superposed a n d juxtaposed combinations of projections, a n d a t t h e same time a n d equivalently, they a r e expressed analytically in t h e form of vectorial equations. T h e first 160 pages a r e given over entirely t o a general, systematic, almost excessively elaborate exposition of t h e modes of plotting a n d of t h e interrelation of frames of reference a n d of systems of units ( a m o u n t of salt per fixed a m o u n t of water, or t h e reverse, or t h e percentage of each substance, a n d with variation between use of moles a n d use of weights), with most of the relations reexpressed in each set of units. T h e point of view is so purely mathematical t h a t t h e ideas of t h e phase rule a r e n o t used a t all; t h e author decided t o d o witho u t t h e phase rule a s i t would only “introduce complications in t h e reasoning.” Consequently, m a n y relations of equilibrium diagrams which a r e already known o n t h e basis of t h e phase rule meaning of these diagrams are elaborately derived a s purely mathematical theorems or “rules.” Although this seems t o be a waste, it is done deliberately for t h e sake of generality a n d consistency, a n d t h e chemical a n d physical significance of the diagrams considered is assumed a s background o n t h e part of t h e reader. *Itt h e same time even t h e reader with such background may be disturbed if not annoyed by t h e arbitrary definitions of otherwise familiar phase rule terms, despite the mathematical consistency of t h e whole procedure--terms such a s variance, degree of freedom, phase, invariance, a n d pseudo-invariance. T h e second half of t h e book illustrates t h e application of t h e unified set of vectorial equations a n d definitions, using a s examples sets of d a t a from t h e literature pertaining t o ternary, quaternary, and quinary aqueous systems. Most of the d a t a are used directly in units such a s equivalents or moles for 1000 moles of water. T h e procedure is explained through diagrams a n d projections, while t h e actual numerical calculations are done with impressive ease through general vectorial equations. Particularly interesting is a chapter o n “crystallization through isothermal displacement,” a s a parallel t o “isothermal evaporation.” In most treatments of solubility diagrams we customarily place much emphasis on isothermal evaporation not so 11 I ch a s a real or practical process b u t a s a means of explanation a n d instruction. W e consider what can be read from the diag r a m , qualitatively a n d quantitatively, a s water is imagined to be removed (or a d d e d ) , isothermally, a t equilibrium. If we s t a r t with a solution saturated with one salt a n d t o it add some other salt of the system, maintaining isothermal equilibrium, a similar sequence of events m a y be considered. T h e expression “crystallization through isothermal displacement ,’ ’ for the process, indicates t h a t t h e added salt causes a sequence of precipitations a n d transformations, like t h a t caused by evaporation. With his general vectorial a n d graphical methods, t h e author gives a n instructive example of t h e process in t h e fundamental quinary S a , I(, Mg/CI, SO4). He system of the oceanic salts ( H 2 0 treats in detail a n d numerically the sequence of events accompanying the addition of t h e incongruently soluble kainite t o water (saturated alivays with S a C I ) until saturation with kainite in addition is attained.
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Essentially these are numerical problems in material balance, a n d further examples are also given for cyclic (polytherinal) processes of salt separations a n d conversions. .I11 t h a t is treated, however, is a highly restricted situation. T h e calculations appear t o be so simple because only straight lines a n d planes are considered. Solid phases are assumed pure, a n d solid solution is not rnentinned. Solubility surfaces ( a t least for t h e cases in t h e applications) a r e assumed plane. These two restrictions make all crystallization paths straight lines on all projections. Even t h e curves for liquid saturated with t w o or more salts are assumed t o be straight lines. In a sense, t h e n , t h e whole construction is an exercise, applicable only if all these conditions hold, so t h a t we are dealing simply with the problem of the intersections of lines and planes. Also, the only systems considered, even in t h e general introduction, have water a s a n additive component, a n d n o background is given for operation on systerns in which water itself enters into h e t e r o geneous double decomposition. Nevertheless there is value in t h e whole effort. T h e book may hardly be meaningful t o one not familiar with aqueous salt diagrams b u t the specialist interested in their utilization should find it rewarding, both because of the ingenious a n d useful graphical a n d analytical procedures it presents and because of the unificd point of view it demonstrates. There are a few very minor confusions and even one or two numerical slips, b u t t h e general result is not disturbed by these. D E P A R T M E AOT F CHEMISTR~ SEIV YORKUNIVERSITY NEIV Y O R K ,S Y
J O H NE. RICCI
T h e Analytical Chemistry of Indium. By A . I . BUSEV,Professor of Analytical Chemistry, Department of Chemistry, Moscow S t a t e Uni\Tersity Translated from t h e Russian by J . T. GRAVES.The Macinillan Company. 60 Fifth Avenue, New York 11, N. Y. 1963. 22.5 X 14.5 cni. 288 pp. Price, $12.50. This book collects into one volume all of t h e known methods for the detectioti, separation, and determination of indium th:it have been published up t o t h e beginning of 1957’. T h e 1 i O references cover both K u s i a n and Western literature. After a n introduct(iry chapter outlining t h e general analytical behavior of indium, t h e remaining chapters deal with specific methods for iiidium uialysis based upon the use of various reagents or tcchiiiques. ‘l‘lie author has noted t h e advantages and limitations of t h e metli(itls, has included many tables of d a t a t o show t h e reliability of scpar~cticinsand determinations, and has given detailed procedural dircctiiins for methods t h a t have been proved most reliable. Gravitnetrically, indium is determined by weighing a s oxide, after hydrolytic precipitation of t h e li! drous oxide; a s sulfide; as ferrocyanide; :ind its 8-quin(ilin(1late and its substituted derivatives. Xiialytical methods based on halide complexes include solveiit extructioii separaticin\ from Iiydrohalic acid solutions and clironiat~igrapliics e p a ~ i t i ( i n s . Instability constants for many of t h e halide complexes :ire given. T h e slightly soluble comples salt, [Co(SH:g)e][ IiICl6], has been used for gra\.iinetric determination, and its solutioi~for spectropliotometric deterinination of indium. T h e principal titrimetric methods are potenticinietric titration with potassium ferrocyanide and coinplesotnetric titra, tion with E D T X . \-arious l i y d r o x ~ ~ a n t l i r a q u i n o n e striplieiiylmethane dyes, and azo dyes give color reactions with indium, and have been used for detection and spectrnpliotciinetric dctermination of t h e element. Severxl orgxiiic sulfur comp:iunds,
