COMPLEXOMETRIC TITRATIONS
Gerold Schwareenbach, Professor of Chemistry, University of Zurich. Translated by H a r r y Irving, University of Oxford. Interscience Publishers, Inc., New York, 1957. xviii 132 pp. 41 figs. 7 tables. 14.5 X 22 em. $3.75.
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O R ~ I N A L L Ypubli~hed by Ferdinand Enke Verlag, Stuttgart, in 1955 under the title Die ieomplezometrische Titmtion, the German edition of this book received immediate and widespread aacceptanoe, as shown by the fact that the first edition was sold out six months after its first aooear-
lator far any research monograph than the two distinguished scientists who have contributed to this volume. Professor Sehwar~enbach,in 1945, first pointed out the exceptional properties of aminopolycarboxylie acids in forming complexes of simple composition and great stability with a wide variety of metal ions. His later discovery, in 1949, of the first metal ion indicator, andogous to the familiar acidhase indicators for hydrogen ion, laid the foundation for the development of this important new type of titrimetry. Professor Irving is well k n o w for his extensive fundamental work on the structures and stabilities of chelate complexes, especially those involved in precipitation and extraction of metals with organic reagents. An outsthnding feature of this book is the logical and systematic treatment of the equilibria involved in visual titrations, using ethylenediaminetetraacetic acid (EDTA) and to a minor extent nitrilotriacetic acid (NTA) as reagents. The equilibria include (a) formation of the complex between metal ion and reagent, ( 6 ) effect of pH on the reagent, ( c ) the formation of complexes with secondary complexing agents, such as z m o n i a , (d) the formation of complexes between the metal ion and indicator ion, and (e) the effectof pH on the indicator. The effects of pH are Logically considered in terms of competition between hydrogen ions and metal ions for the reagent or indicator anion. Thus the reciprocals of the usual stepwise ionization constants of an acid are recarded as the formation oonstants of the is considered in terms of competition between reagent anion, the indicator, and secondary complexing agents for the metal ion. I t might appear that such an array of equilibria would be most cumbersome to handle. However, with the unifying treatment and the simplifying assumptions VOLUME 35, NO. 5, MAY, 1958
made possible by the fact that the metal ion concentration is generally very low (typically of the order of 10-SM), the titration curve calculations become quite straightforward. This volume cannot be regarded as a. textbook or as a comprehensive book of procedures. Yet it can be highly recommended both for the advanced student and the practicing analyst as a valuable guide to the principles. I t is ehssacteristic of thia rapidly pragressing field that e book must be out of date in certain respects immediately upon publication. Thus, the work of Reilley on the use of the mercury-EDTA complex rts a. source for the coulometric generation of EDTA is mentioned only in the translator's preface, and his use of the mercuryEDTA potentiometric indicator electrode is not mentioned a t all. Likewise, the recent literature contains numerous references to new metal ion indicators. Very few typographical errors were noted, but the quality of the paper is poor. H. A. LAITINEN U N ~ V E ~ ~OPLITL Y LINOI~ Une*w*. I ~ ~ r l r o m
PHYSIC0 CHEMICAL EXPERIMENTS Robert Livingston, Professor of Physical Chemistry, University of Minnesota. Third edition. The Macmillan Co., New 273 ppp. 69 figs. York, 1957. xiv 11 tables. 1 4 X 21 cm. $4.50
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THIS is the third edition of a very useful laboratory manual in physical chemistry. I t was first published in 1939 and revised in 1948. To undertake a critical reevaluation every nine years indicates dertness in a field that is constantly in a state of flux ss regards its emphases. The manual is very well adapted to the first year course in liberal arts colleges where no graduate department of chemistry is a t hand. So often equipment is limited in these institutions. Elaborate experiments require such extensive revision that an instructor is encouraged to write his own procedures. This manual has much to commend i t in that enough variety of experiments is st hand to accommodate any respectable laboratory. Two new experiments have been added, one on the determination of dipole moment and another on the determination of transference numbers by the moving boundary method. The omission of the classic Victor Meyer determination of molecular weight will cause some dismay, but the author makes a good case for its dismissal, even though he retains the equally classic but more simple Dumas determination. There are several eommendsble features.
The first 51 page8 deal in excellent detail an Measurements, Errors, and Computations. A section on Dimensions and Approximate Computations is north noting. Too often these matters are overlooked in a com'sc m physical chemistry. The sections on Theory of Errors and A p plieation of Error Theory deserve high prai~ise,both for their presentation and for the simple fact that they were included. The section on Evaluation of the Constants of Empirical Equations is, to this reviewer, worthy of special mention. All of this introductory part of the book substantiates the conviction that students should know how to handle data, how to evaluate, and how to determine its degree of rerpectability. Another fine feature of this manual is the inclusion in a separate section, but along with the experiment, an explanation and details of operation of some of the standard pieces of equipment found in a physical chemistry laboratory. Some of these are the Westphal balance, polarimeter, Beckm m n differential thermometer, student's potentiometer, colorimeter, spectrophotometer, even a Sprengel pycnometer. Another helpful feature is that the author is not hesitant in making references to more elaborate sources suih as Weissberger, Kolthoff & Sandell, McDougall, Moore, and Guggenheim & Prue. Many original sources are mentioned in the literature as well as other monographs. This is an excellent laboratory manual. It includes s. fine range of 42 experiments covering all fields of elementary physical chemistry. These are all well set up with a concise theoretical introduction, an itemieed list of apparatus and materials, and successive sections on procedure and computations. 6. J. VELLENGA
Mnsmr*ouv C o m e o ~ NEWCONCORD, O m 0
MISES AU POINT DE CHIMIE ANALYTIQUE PURE ET A P P L I Q U ~ET D'ANALYSE BROMATOLOGIQUE. VOLUME IV Edited by J. A. Goutier, Professor of the Faculty of Pharmacy of Paris. Masson et Cie, Paris, 1956. 212 pp. 21 figs. 16.5 X 2 5 a n . Paper bound, 2400 fr.
TEEfourth volume of these progress reports deals mostly with methods af interest to the biochemists and the food chemists. I t should be interesting to Americans for the reason that one may expect reasonably complete coverage of the French literature and possibly of the liter ature from Latin countries.
J.-E. Courtois (pp.3-33) treats the qualitative identification and quantitative determination of sugars after separation by paper ehromtttography or percolation through columns. Useful micromethods are considered. P. Jaulmes and J. Hamelle (pp.3546) describe methods for the determination of the non-volatile solids in wine. The different methods are critically compared, and the conclusions to be drawn from the findings are discussed. P. Mesnard (pp.57-75) writes on the determination of the hydroxyl group by acetylation. The use of s. mixture of acetic anhydride, phosphoric acid, and dioxane for the acetylation of tertirvy alcohols is recommended. P. Navellier (pp.77-114) presents an investigation concerning the methods of conservation and analysis for s a m ~ l e that s he reasoning applies undergo changes. primarily to the investigation of milk, which is the author's field of specislieation. P. Souchay (pp.115-138) reviews the theory of polawgctphy and applications of the technique in the fields of medicine, toxicology and pharmacy. The very imposing final chapter (pp.139-209 with 265 references to the literature) is written hy R. Truhaut. It deals with a problem of continuously increasing practical importance, the appearance of foreign substances-added intentionally or getting there by mishsp-in food and the biological and analytical aspects of the phenomenon. A. I . BENEDETTI-PICHLER
reference work is of thegreatest value in research. This volume deals with the preparation of amines. The first section (15 pp.) describes reactions used for the direct intrcduction of the amine radioal. The second division (238 pp.) discusses in detail those transformations in which halogens, hydroxyls, carboxyls, nitro, sulfonic acids, and amino radicals may he replaced by the amino group. Part 111(74 pp.) is a treatment of the reactions in which amines are produced by the addition of ammonia or amines to a great variety of unsaturated structures. Section IV (390 pp.) summariees those reactions in which amines are formed by reduction of twenty-two types of nitrogen containing stuetur& with a variety of reducing agents. Division V (66 DD.)is an exoosition of the methods f o r t h i bynthesis of amines through eondensation reactions. Part VI (21 pp.) is a. review of the preparation of amines through organo-metallio compounds. Section VII (1W pp.) is a Critique of the methods of forming amines through rearrangements of the type in whioh groups shift from nitrogen to the aromatic ring or of the Hofman, Curtius, Schmidt, Beckman, Stevens, Sommelet, Chapman, Smiles, and Amedari reactions. The remaining portion of this volume deals with supplementary aspects of *mine chemistry. Chapter VIII (68 pp.) diecusses the formation of amines by the splitting of certain derivatives through hydrolysis, reduction, alcoholysis, dedkyIstion. oxidation. decarboxvlation. ohos-
Q U B E NC~ O L L ~ E
PLU~~N NEW D . YORI
Edited by Eugen Miiller. Fomth edition. Georg Thieme Verlag, 1957. Stuttgart, 1224 pp. 4 figs. 18.5 X 26 cm. lvi $48.70.
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ANTISTHENES,overcome by a lasting and painfull illness, cried out in his agony, "Who will releane me from my pains?" Whereupon his friend Diogenes, approached the hedside with drawn dagger. "Ah, you rascal, I said who will release me from my pains, not my life." Although this attitude may he condemned by Stoics, dolorous organic chemists sympathiee with Antisthenes. Repeated failures of inadequate synthetic methods may so torture chemists that many would think of giving over this life and becoming engineers or lawyers. However, for some of the paim of synthetic organic chemistry, "Die Methoden der Organischen Chcmie" will he a puissant antidote. This series is the most exhaustive source of informrttion an synthetic methods available to chemists. Unlike Beilstein, this work does not describe individual compounds, but on tlor contrary ronr;idrre urncrnl mrthmlz of ~ y n t ! w ~of i i enrim CIBFT?and illusrraf,~rhrre rrsrrions with srlcct~rl examples. I t is for thin reason that this 268
zation, from aeides and p oxc-amines, eta. Section X (21 pp.) is a oonsideration of the preparation of amines from other amines through retention of the amine structure by protective reactions for that group. Chapter X I (8 pp.) deals with the problems of separating mixtures of primary, seoondery, and tertiary amines by physioal and chemical techniques. The'last section, Pert XI1 (5 pp.), is a summary of the properties of ammonia and methods for handling i t in the laboratory. Some idea of the comprehensive nature of this work may begained from the knowledge that the author index contains about 11,000 entries and the compound index lists over 6000 substances. This work is a. signifioant contribution to the literature of organic chemistry. It should grace the shplves of every resesrch lahorstory. GEORGE HOLMES RICHTER
T m Rme 1 ~ a . r r . m ~ ~ Housron, T E X * ~
DANGEROUS PROPERTIES OF INDUSTRIAL MATERIALS
N. Irving Sax, Nuclear Development Corp. of America, White Plains, New York. Reinhold Publishing Carp., New York, 1957. v 1467 pp. 18.5 X 26.5 em. $22.50.
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READERSinterested in safety practices involving the use and handling of hazard-
ous chemicals and/or materials where radiation is involved are probably familiar with Sax's "Handbook of Dangerous Material" published in 1951. This work is successor to that earlier volume. The neotians and their authors are as follows: Toxicology by Leonard J. Goldwater; Ventilation Control. Personnel Protection
Fire ~ r o t e i t i o nand ~ t o r a g e h d~ a n d l i n ~ of Hazardous Materials by N. Irving Sax; Reactor Safeguards by Joseph J. Fitzgerald; and Allergic Disease in Industry hy Milton S. Dunn, M.D. I n addition there is a 1060 page section listing nearly 9000 chemicals. For each there is a. desoription,formula, list of physical constants and a discussion of toxicity, fire hazard, storage and handling. In many eases other more specialized topics are considered. For example tricresyl phosphate, known in commerce as T C P and used as a gasoline additive, was responsible for poisoning of 15,000 people in 1930. Of those, 10 died. An alooholio beverage known as Jamaica ginger or "Jake" had been adulterated with 2% of the T C P and was responsible for the poisoning. There is a oomprehonsive ~ectiondealing with shipping regulations and the final section of 19 pages is an Index to Synonyms. This reviewer is favorably impressed with the comprehensive nature of the volume and the lucid presentation of most sections. The sections Radiation Hazards and Reactor Safeguards are excellent and should he of great value to college science departments which have programs in radioisotopes and use of reactors. This volume is recommended as a reference in academic laboratories an well as for "those involved in the manufrtcture, use, hsndling, storing or shipping of hazardous materials." M o n r ~ w nS
WILLIAM B. COOK ~ m Comeoe e
Boaer*~.MONTAR*
INDUSTRIAL CHEMICALS
W. L. Foith, Air Pollution Foundation, San Marino, California; DonoldB. Keyes, Arthur D. Little, Inc., New York; Ronold L. Clmrk, Collier Carbon and Chemical Corp., Brea, California. Second edition. John Wiley & Sons, Inc., New York, 1957. ix 844 pp. 16 X 24 cm. $16.
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ONEhundred and forty industrial chemare icals from acetaldehyde to ~ i n oxide c discussed in this second edition. The plan followed is quite similar to that used in the first edition [reviewed in J . Chem. Educ. 28, 58 (1957)) for 106 chemicals. Each chemical iis discussed separately: name, formula, principal manufacturing processes with equations, materials required and flawsheets, use pattern and price for the lest 20 years, properties, commercial grades, containers and shipping regulations, economic aspects, and finally a list of manufacturers and plant sites. All of the 106 chemicals discussed in the (Continued on page A%%) JOURNAL OF CHEMICAL EDUCATION
