V O L U M E 2 2 , N O . 1, J A N U A R Y 1 9 5 0 filled amply; the second purpose leaves much to be desired. The topics treated are qualitative and quantitative spectrochemical analysis, absorption spectra, infrared and Raman spectra, interferometers, and the structure of line spectra. Candler presents the basic principles of each topic in a brief and elementary form, listing some fundamental experiments and a bibliography. The treatments of the topics and subtopics show considerable variation-for example, Candler describes the measurement of wave lengths rather fully, including even the use of Edser-Butler plates, R hile his discussions of light Sources and sensitometry are much too limited to be of practical or educational value. Much of the theory and application is oversimplified and the bibliographies a t the end of each section are incomplete, particularly in so far as developments since 1941 are concerned. The contributions of Sawyer, Duffendack, OMens, Enns, Dieke, Kaiser, and Barnes, to name only a few, are conspicuous by their absence from the text as well as the literature references. These defects limit the usefulness of the book to the first intended purpose of the publishers as mentioned above. Laboratory analysts and practical spectroscopists will find little new information of practical value in thiq hook JICOB CHOLAK Physical Methods of Organic Chemistry. -1. W’eissberger, editor. Part I. 2nd ed. ix 1072 pages. Interscience Publishers, Inc., 215 Fourth dve., Selv Tork 3, ?;. T . , 1949. Price, 512.50.
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This volume is nearly half again as large as the first edition. Three chapters (X-Ray Diffraction, Electron Diffraction, and Refractometry) have been moved forward into a forthcoming Part I1 and four chapters have been added: Temperature Measurement; Temperature Control (both by J. Ll. Sturtevant); Determination of Vapor Pressure iG. W.Thomson); and Determinations with the Ultracentrifuge (J. B. Sichols and E. D. Bailey). Ten of the original chapters have been more or less revised: Melting and Freezing Temperatures (E. L. Skau, H. Rakeham) ; Boiling and Condensation Temperatures (W. Swietoslawski and J. R. Anderson); Density (S. Bauer); Solubility (R. D. Vold and M. J. Vold); Surface and Interfacial Tension (IT. D. Harkins) including a section on the Parachor by G. W. Thomson; Properties of Monolayers and Duplex Films (W. D. Harkins); Calorimetry (J. 11.Sturtevant) : Microscopy ( E . E. Jelley) ; Crystal Form (hl. A. Peacock) ; and Crystallochemical Analysis (J. D. H. Donnay). Three chapters have been rewritten: Viscosity (T. E. hlcGoury and H. Mark); Osmotic Pressure iR. H. Wagner); and Diffusivity (-i. L. Geddes). The treatment of each chapter varies with the scope of the topic covered; some chapters are more theoretical than others;
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thus density requires only t\!o OI tliier pages of theory, whereaa vapor pressure requires nearly forty for adequate treatment. The authors of the various chapters and the editor must be commended both for achieving their stated purpose and for maintaining throughout what is probably an optimum balance between theorl and description. Any chemist, organic or otherwise, who aants to learn a lot about an instrumental technique 01 the theory behind it, or who wants to build good equipment, will find this authoritative invaluable. It is well illustrated and documented, and save t o r one or two minor duplications--e.g., pages 581 and 648-4 is vw 1 uell edited The reviewei’h copy spends little time on the lihrari shelf.
THOMAS R. P. GIBB, JR Manual of Spectroscopy. Theodore A . Cutting. 220 pager. Chemical Publishing Co., Inc., 26 Court St., Brooklyn, 1.Y., 1949. Price, $6.50. This manual, the author says, “has been written to assist tliusr who v h h to analyze ores, minerals, alloys and inorganic chemicals. or wish to teach others to do so.” The contents suggest that aiiy amateur mineralogist, can find $10,000 \vorth of uranium wit11 a $2.50 spectroscope! The history and theory of spectroscopy are presented in 6 scant pages, light sources in 11, spectroscopes in 38, and spectroscopic analysis in 30. The next 85 pages deal with elementary mineralogy and visible spectral lines of 70 elements including such nonspectroscopic material as the discovery, sources, uses, properties. and prices of elements. (The paragraphs on illinium and masurium are obsolete, and the price of xenon is grossly inflated a t 5600 per liter.) The last 38 pages give approximate wave lengths arid intensities of strong linea selected from “M.I.T. Wavelength Tahles.” 1 bibliography of 16 items contains 8 works on mineralogy (from 1907), a manual of clinical therapeutics, and the Smyth Report, hut ignores all spectroscopic publications since 1939. Obviously, this book will not be of use to anyone escept possibly thr tyros for whom it was written.
WILLIAMF. MEGGERC
laboratory and Workshop Notes In the review of “Laboratory and Workshop Notes,” by liutli Lang [ANAL.CHEM.,21, 1431 (1949)], i t was stated that the Institute of Physics is to receive the royalties on the hook In the case of this and other books, the royalties go to the Renewlent Fund of the Institute of Physics, set up to help physiri\t. and their dependents who find themselves in strained cBir ( n n i stances because of some miqfortune.
Fifth Southwest Regional Meeting HE Fifth Southwest Regional Meeting, sponsored by the
Tthree was Oklahoma Sections of the AMERICANCHEMICAL SOCIETY, held December 8 to 10 in Oklahoma City. Abstracts of the papers presented before the Section on Analytical Chemistry are given below. Colorimetric Determinations of Oxidizing -igents Using the Cadmium Iodide-Linear Starch Reagent. PAULARTHUR, THosr.is E. MOORE,A N D JACK LAVBERT,Oklahoma 4 . and X4. College, Stillwater, Okla. A stable starch-iodide reagent, using cadmium iodide and the linear A (butanol-precipitated) starch fraction isolated by Schoch, has been developed for the quantitative determination of osidizing agents. This reagent is stable indefinitely toward atmospheric ouygen, diffused sunlight, and the growth of microorganisms. The reagent responds to oxidizing agents according to the pH of t h e solution. Weak oxidizing agmts, such as selenious acid, are
reduced only in highly acid solutions, whereas stronger oxidiziiig agents, such as hypochlorite, react even in neutral solution. The blue starch-iodine color produced shows maximum absorption at about 615 mp and obeys Beer’s law closely when absorption i* plotted against concentration of the oxidizing agent. Permanent outside standards for the linear starch-iodine blur color can be prepared by adding a small amount of potassiuni chromate to a solution of nickel hexammine sulfate and making the proper dilutions, always keeping the solutions concentratell with ammonium hydroxide. A colorimetric method of analysis for trace amounts of seleriiurii (as HPSe03)in water has been developed using the cadmium iodide-linear starch reagent. The reagent is also used in a nirthod being developed for the determination of minute concentration. of chlorine in water in the presence of chloramines. Biochemical Oxygen Demand of Some Common Organic Coinpounds Present in Chemiral Wastes. E. R. STROSG,JR.,C. I.
200 SHREWSBURY, AND R. HATFIELD, Southrvest Research Institute, San Antonio, Tex. The 5-day B.O.D. values have been determined a t 20' C. by the dilution method for some of the common water-soluble organic compounds found in chemical wastes. Original data were obtained for such toxic organics as aldehydes, acids, formates, and alcohols. These data are being used to estimate the pollution characteristics of industrial wastes in treatment and disposal problems. In this vork the B.O.D. was determined for a number of compounds which are normally bactericidal. The B.O.D. values were found to increase with increasing dilution to a point where the toxic effect on the bacteria was nil and then the values become consistent. An Improved Method for Determination of Sulfur Dioxide in Beer and Foods. HAROLD E. WEISSLER,San Antonio Brewing .issociation, San Antonio, Tes. The standard method for the determination of sulfur dioxide in beer and food for the past 20 years has been the llonier-Williams method. Despite its inconveniences it has undergone only slight modifications. The method proposed overcomes the objections to the older method without the sacrifice of accuracy. The entire contents of a cold 12-ounce package of beer are introduced into a carbon dioxide gas-filled system similar to that of Thompson and Toy. Thirty milliliters of concentrated hydrochloric acid are added, the solution is slowly heated to boiling, and refluxing is continued for 1 hour, while a steady, slow flow of carbon dioxide is maintained. The sulfur dioxide expelled from the sample is oxidized by iodine contained in the cold receiving flask. After refluxing is completed the excess iodine is removed by boiling and the solut,ion is neutralized with 0.1 N sodium hydroxide. The sulfate. is then titrated with standard barium chloride solution, using tetrahydroxyquinone or potassium rhodizonate as internal indicator in the usual manner. The results are consistently 0.2 to 0.5 p.p.m. higher than those determined by the 3Ionier-Williams method but are in closer agreement' with the gravimetric values than the latter. Bdvantages of the method are: Only one standard solution is required and this is easily obtained, prepared, and preserved. The titration is easily performed without the use of electrometric equipment. Some t,ime is saved.
X Field Kit for the Approximate Chemicsl Analysis of Oil Field Kat,ers. MARYANN DUGGAN AND 4 . V. ~ I E T L E Magnolia R, Petroleum Co., Dallas, Tes. The construction, equipment, reagents, and method of operating a portable water analysis kit are described. The kit was designed with a view toward economy as well as versatility and simplicity of operation. The pH value of the water is found colorimetrically or by use of a pH meter. Total dissolved solids in the wat,er are found by either density or conductivity measurements. Calcium, magnesium, barium, chloride, sulfate, and sulfide are determined by turbidimetric tests. Turbidimetric standards are furnished in the kit. Ferrous and ferric iron are determined colorimetrically. The method for determining total alkalinity, carbonate, bicarbonate, free carbon dioxide, and hydroxide incorporates the use of two pH measurements and t'he carbonate equilibrium slide rule of Hirsch. The results obtained with the kit compare well with results obtained using standard water analysis methods for a number of i%-at,er samples of various types. Economic evaluation indicates that use of the kit can obviate many of the usual delays and expenses of laboratory analyses. Initial cost of outfitting this kit is low compared to market prices of available wat'er-testing kits. The tests possible with the kit are adequate for purposes of corrosion control, water repressuring programs in oil fields, identification of oil field brines, boiler water treatment diagnosis, and inhibition of scale formation. Radiochemical Separation of Tungsten, Rhenium, and Osmium. G. S. BRICKAM, S. E. TCRSER, AXD L.0. AIORGAN, University of Texas, Austin, Tex. S n ion exchange method for the separation of tracer quantities of rhenium and osmium from larger amounts of tungsten has been developed in order to facilitate the t'arget chemistry of tungsten. In this method, the hydroxide, or free base, form of the anion exchange resin Amberlite IR-4 is used in a chromatographic column. Sample solutions probably contain the elements in the form of tungstate, perrhenate, and perosmate anions at €1 6 to 8. The rate of adsorption of tungstate at this pI3 is relative6 slow, so that if a rapid rate of flow is maintained in the column the tungsten may be recovered quantitatively from the aqueous eluate. Rhenium may then be removed from the column by hydrolysis
ANALYTICAL CHEMISTRY with ammonium hydroxide. Osmium remains on the rolumn in a reduced form. At high tungstate concentrations, or a t a pH lower than 6, appreciable amounts may be retained on the column. In this case, the hydrolytic elution may be controlled, by adjustment of the ammonium hvdroside concentration, to give selective elution of tungsten and rhenium, the tungsten being removed more readily. Some Errors Involved in the Use of Radioactive Tracers a t Very Low Concentrations. L. 0. MORGAX, University of Texas, Austin, Tex. The effect of adsorption of ionic or molecular species from solution is often overlooked as a source of error in radiochemical experiments, especially when one or more of the components is present at extremely low concentrations. In experiments in this laboratory by D. lIarshall, S . Hackerman, and L. Morgan, other\$-iseundetectable amounts of sulfur 35 were found to adsorb preferentially on chromium surfaces from active chloride solutions. This gave rise to erroneous interpretations until the situ ttion m s recognized. In connection with another problem, the ndsorption of perrhenate ions on the glass vialls of the transfer svstem was found to increase to a large extent the apparent width of the elution band of rhenium tracer from a chromatographic column. Others have noted the anomalous behavior of radiocolloids. In experiments with zirconium 95 tracer, considerable difficulty c m be encountered unless adequate precautions are taken to minimize the detection of the daughter columbium 95 Fshich iJ present in very low- concentration and which has a marked tendency to colloid or subcolloidal polymer forniation in most media. Determination of Calcium and Magnesium Ions in R a t e r Using the High Frequency Titrimeter. FRED W. JEXSEN, G. 11. WATSON,AXD L. GUTIERREZ-VELA, Texas A. & M. College, College Station, Tex. The standard soap method for the determination of total hardness in waters is not too accurate. Instead of utilizing the formation of a permanent foam as an indication of the end point, the use of the high frequency titrimeter was introduced. Soap solutions were standardized by titration with hydrochloric acid in the titrimeter not only more rapidly but with greater accuracv and reproducibility than by the standard method. The interesting form of the titration curve suggests possible uses of the titrimeter in other fields. The determination of calcium by soap solution gave reproducible results which checked the stoichiometric end point better than the standard method. Magnesium was determined by titration with sodium hydroxide in ethanol, again the accuracy was better than by the standard method. Mixtures of calcium and magnesium present difficulties which have not yet been overcome. A High Frequency Oscillator Utilizing the Heterodyne Principle to hleasure Frequency Change Induced by Diverse Chemical Systems, PHILIPW. WEST AKD T. S. BURKHALTER, Louisiana State University, Baton Rouge, La. An instrument which has unusual potential utility in the field of chemical analysis consists essentially of two high frequency oscillators (one a reference and the other a working oscillator) and a detector svstem for measuring the frequency difference between the two oscillators. ADDlication of the instrument to chemical analysis is based upon-the principle that the frequency of an osciliator changes with a change of composition of the core material of the tank circuit coil. In this instrument the tank circuit coil form is hollow and the core material is changed by placing a small glass cell, filled with any desired chemical system, within the hollow coil form. The frequency change, caused by inserting a chemical system into the tank circuit coil of the working oscillator, is measured by comparing the frequency of the working oscillator with that of the reference o d l a t o r before and after insertion of the chemical system. The magnitude of the frequency change is a function of the composition of the chemical system inserted. Stability of oscillation, essential for this tvpe of operation, has been checked and found satisfactory. A pieliminary investigation of sensitivity and possible application has been made The instrument has been used to make conductometric titrations, to analyze binary organic mixtures, to detect very small changes in concentration of dilute ionic aqueous systems, and to distinguish between isomers of short-chain saturated alcohols. The following data illustrate the instrument's sensitivity to change in composition: Distilled water caused a frequency change of 4725 cycles, while 0.001 'V hydrochloric acid caused a change of 5977 cycles; isopropyl alcohol caused a change of 4025 cycles, while n-propyl
20 1
V O L U M E 2 2 , NO. 1, J A N U A R Y 1 9 5 0 alcohol caused a change of 4170 cycles. The instrument is sensitive to a frequency change of about 10 cycles. Determination of Solubilities with the Beckman Du Spectrometer. RIADISON L. MARSHALL, Texas State College for Women, Denton, Tex. Solubility data in the literature are extensive and frequently of a high degree of accuracy. However, the widespread usefulness of such data justifies the extension of solubility studies. Ultraviolet absorption measurements provide a novel method for the determination of the solubility of certain organic compounds in water. Data were supplied for the solubility of benzene and for toluene i n water. Comparisons with the literature values were made. Three conditions must be met for applicability of the method: The solute must exhibit absorption in the mr,asurable range, whereas the solvent must be optically clear; the solute must be only slightly soluble; and absorption must obey closely the Beer-Lambert law. Fortunat,ely, the third condition is likely to be met if the second is fulfilled. Possible ext,ension of the method to systems involving aldehydes, ketones, and other classes of organic compounds was proposed.
conibiiiinq the useful features of several exist,ing methods for type anal sis of nonolefinic oils and by making various adaptations, to lerive a scheme of analysis which is believed to be fairly general for polyolefinic oils. This scheme was illustrated in connection with the analysis of a typical polyolefinic, polycyclic drying resin marketed under the trade name Panapol 2-C. The oil is selectively hydrogenated in order to saturate only the olefinic linkages, aft,er which it is completely hydrogenated to saturate the residual aromatic bonds. The average number of rings per molecule and the average size of t'he rings are computed on the completely saturat'ed oil, making use of type formulas and molecular volumes. The true unsaturation is derived from the increase in hydrogen content on selective hydrogenation, whereas the aromaticity is computed from the difference in hydrogen content between the selectively and totally hydrogenated oil. Final results show the percentages of naphthenic, aromatic, and alkyl carbon atoms, as well as the distribution of olefinic double bonds, along the entire boiling range of the oil. The analysis is supplemented by a study of ultraviolet and infrared spectra. In common xith any analytical procedure, certain assumptions are nece.;iary. These were pointed out and the limits of uncertainty were defined. The method is also applicable t o oils containing conjugated olefinic and/or alkyne linkages.
Quantitative Ultraviolet .4nalysis of Two Aromatic Hydrocarbon Isomer Systems. JOHN .4.PERRY, Monsanto Cheniical Co., Texas Division, Texas City, Tex. Quantitative analvtical methods based on ultraviolet absorption spectrophotometry have been set up for the xvlenes and ethylbenzene, and for the diethylbenzenes and sec-butylbenzene. n-Heptme purified by silica gel filtration is used throughout as the solvent. Extinction coefficients are established in a two-step procedure. I n the first step, the relative magnitudes of the coefficients are determined merely by introducing an unweighed sample of the pure hydrocarbon into the absorption cell and observing the optical densities a t the various selected wave lengths. In the second step, the optical densities observed from synthetics are used to establish the relative magnitudes of the sets of coefficients. This is done by successive solutions of the matrix formed from the coefficients and the observed densities, xyith indicated adjustment>sof the sets of coefficients between the solutions. Apparent deviations from Beer's law seem to be the chief limitation of accuracy and precision of the method. Excellent accuracy (0.2% relative) is available for the middle concentration ranges, and only fair accuracy (5 to 10%) for the extreme concentration ranges. The high accuracy and precision are the result of deriving the values of the constants directly from the experimental conditions; t'he diminution of accuracy and precision is believed to be the result of uncorrected apparent deviations from Beer's law. The approach described permits rapid development or revision of multicomponent normalized analyses; the speed is achieved by the eliminat,ion of most of the experimental work in the determination of extinction coefficients. Polarographic Determination of Zinc in Oils. J. T. WILEY, J. E. DELONEY, AND R. L. WINSTEAD, Texas Co., Port Arthur, Tex. The ever-increasing use of various types of additives by the oil industry has made it desirable to have a rapid and accurate means of controlling the amount of additive present in the oil, and also to assure a homogeneous mixture. This can be controlled by the determination of zinc, where it is one of the metals present in the additive being used. The polarographic method gives accurate and reproducible results and is much faster than the usual gravimetric or electroplating methods. Zinc has been determined accurately in concrntration from 0 to 0.10% by weight, and the method should be applicable to much larger concentrations. Barium, phosphorus, or calcium, other metals which are sometimes present along with the zinc in additives, do not interfere. The method consists of carefully ashing the oil to remove the organic matter, dissolving the ash in concentrated hydrochloric acid, adding gelatin as a maximum suppressor, making up to a known volume, and determining the polarogram. The percentage of zinc is then calculated from the step height obtained versus known standard samples where zinc oxide is used. Determination of Molecular Structures in Polyolefinic Hydrocarbon oils. SnfoN MIRONAND R. J. LEE, Pan-American Refining Corp., Texas City, Tex. The thorough characterization of molecular types present in the complex high-boiling olefinic oils derived by thermal or catalytic treatment of petroleum fractions is not possible by the use of any one scheme present in the literature. It was found possible, by
Fifth Annual Microchemical Symposium H E Fifth Annual Microchemical Symposium, organized under Tthe auspices of the Metropolitan Rlicrochemical Society to stimulate interest in the field of microchemistry and to promote more widespread use of microchemical techniques, will be held in New York, N. Y., February 24 and 25. There is no registration fee, and the public is cordially invited to attend. ilt 6:OO p.if. on Friday, February 24, the symposium will open with a dinner a t the Hotel Alden, 225 Central Park West. Technical sessions will be a t the American Museum of Natural History. Friday Evening
8:OO Welcome. OLGAR. FRY,Presiding, BELLALITTXAX, Chairman, Metropolitan Microchemical Society. Introduction. OLGAR . FRY,Symposium Chairman. 8: 15 Rapid Analyses by Means of Emission Spectroscopy HAROLD HUGHES. 9 : 15 Microscopy, Textiles, and Dyes. GEORGEL. ROYER. Saturday Alorning
JAMES S. WIBERLEY,Presiding 10 :00 Separation and Identification Techniques in Organic iinalysis. SIDNEY SIGGIA. 11:oo Identification of Resinous Plastics. T. G. ROCHOW. 12: 15 Luncheon, Hotel Alden Saturday Afternoon JOHSA. MEINS, Presiding 2:oo Developments in Techniques and Uses of Spot Test Methods of Analysis. PHILIPW.WEST. 3:OO Problems in Agricultural Microchemistry. C. 0. WILLIT.,
Dinner and luncheon reservations should be made by February
16 x i t h Mrs. Olga R. Fry, E. I. du Pont de Nemours & Company, Inc., A4rlington,S.J.
L.S.U. Analytical Symposium H E third annual Louisiana State University Symposium on T M o d e r n Methods of Analytical Chemistry will be held on the campus a t Baton Rouge, January 30 to February 2, 1950. Registration will begin 12londay morning in the Coates Chemical
