AC
BRIEFS Highlights of the scientific and technical articles in this issue
Retention Temperature and Column Efficiency in Programmed Temperature Gas Chromatography
Countercurrent Distribution of High-Boiling Phenols from a Low-Temperature Coal Tar
The relationship between r/F and retention temperature and retention volume is predicted from isothermal chro matographic measurements in programmed temperature gas chromatography. Retention temperature depends on the ratio of heating rate to carrier gas flow rate. Col umn efficiency may be calculated and an equation is established.
Tar acids boiling at 231° to 331° C. from low tem perature bituminous coal tar are fractionated and analyzed by distillation and countercurrent distribution. Of 84 compounds demonstrated, 24 were determined with respect to specific isomers and 36 on structure type. The remainder are unknown tar acids.
H. W . H A B G O O D a n d W . E. HARRIS, University of A l b e r t a , Edmonton Alberta A n a l . Chem. 3 2 , 4 5 0 ( 1 9 6 0 )
CLARENCE KARR, JR., P. A. ESTEP, a n d L. L. HIRST, JR., U. S. D e p a r t ment of Interior, M o r g a n t o w n , W . V a . A n a l . Chem. 3 2 , 4 6 3 ( 1 9 6 0 )
Cocrystallization of Ultramicro Quantities of A l k a line Earth Elements w i t h Potassium Rhodizonate. Determination of Radiobarium in Sea Water
Analysis of Methyl Methacrylate Gas Chromatography
Copolymers
by
Quantitative determination of methyl methacrylate co polymers is obtained by gas chromatographic procedure. The sample is pyrolyzed on hot coils surrounded by the carrier gas. Polymer mixtures and copolymers are distinguished and the determination made with a ± 0 . 5 % precision. J O H N STRASSBURGER, G . M. BRAUER, M A X TRYON, a n d A. F. FORZIATI, N a t i o n a l Bureau o f S t a n d a r d s , Washington 2 5 , D. C. A n a l . Chem. 3 2 , 4 5 4 ( 1 9 6 0 )
Ultramicro quantities of alkaline earth elements separated from solution by cocrystallization with tassium rhodizonate. Radiotracer techniques are ployed to measure the quantitative removal of the ments. Application is made for the separation determination of radiobarium in sea water.
are po em ele and
H. V. WEISS a n d M. G . LAI, U. S. N a v a l Radiological Defense L a b o r a t o r y , San Francisco, Calif. A n a l . Chem. 3 2 , 4 7 5 ( 1 9 6 0 )
Simultaneous Extraction and Spectrophotometric Determination of Cerium with 2-Thenoylfluoroacetone
A systematic investigation on the liquid-liquid extraction behavior is described for cerium-2-thenoyltrifluoroacetone chelate at different pH values. The chelate in ben zene solution affords a quantitative measurement of milli gram amounts of cerium at 450 ττιμ. Certain metal ions, citrate, tartrate, and EDTA interfere. S. M . KHOPKAR a n d A. K. DE, J a d a v p u r University, Calcutta 3 2 , India.
Paper Chromatography of Steroids. A Systematic Approach Using a Generalized RM Function
A systematic approach to steroid paper chromatography makes possible the prediction of the approximate mo bility of a steriod in a selected solvent system. From the steroidal structure the mobility is estimated and a suit able solvent system selected. Pregnane and androstane series of steroids are examined. PETER KABASAKALIAN a n d ALVIN BASCH, Schering Corp., Bloomfield, N.J. A n a l . Chem. 3 2 , 4 5 8 ( 1 9 6 0 )
A n a l . Chem. 3 2 , 4 7 8 ( 1 9 6 0 )
Determination Alloys
of
Zirconium
in
Uranium
Fissium
Two separation procedures are presented for removing zirconium from fissium alloys. Zirconium and other components are precipitated with cupferron and zir conium, then precipitated with ammonium hydroxide. The other procedure consists of ammonium hydroxide precipitation followed by/>-chloromandelic acid precipi tation. Zirconium is spectrophotometrically deter mined. H. B. EVANS, A. M. HROBAR, a n d J. H. PATTERSON, Argonne National L a b o r a t o r y . Lemont, III. A n a l . Chem. 3 2 , 4 8 1 ( 1 9 6 0 )
Liquid Scintillation Compounds Chromatographic Purity of A m i n o Acids.
Arginine
The R/ values for 29 amino acids are obtained after single, double, and triple development in one or two dimensions with their solvent systems. The chromatographic meth ods are applied to determine the purity of amino acids with special reference given to arginine. M . S. D U N N a n d E. A. MURPHY, Unversity o f C a l f o r n i a , Los Angeles, Calif. A n a l . Chem. 3 2 , 4 6 1 ( 1 9 6 0 )
Counting of Tritiated
Organic
An evaluation study is conducted for some of the variables in liquid scintillation counting techniques. Variables including optimum sample volume, ratio of internal standard to sample, and counting rate are investigated. A routine procedure for measurng radioactivity of tri tiated organic compounds is outlined. M . L. W H I S M A N , B. H. ECCLESTON, a n d F. E. ARMSTRONG, U. S. Department of Interior, Bartlesville, O k l a . A n a l . Chem. 3 2 , 4 8 4 (1 9 6 0 )
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BRIEFS Infrared Absorption Frequencies of the ferf-Butoxy Group Separation of Rhodium from Powder
Iridium
by
Copper
Copper powder is used as a selective precipitant for rhodium in the separation of rhodium from iridium in l.OJV hydrochloric acid solution. The metal and copper are separated by cation exchange procedure in forms convenient for gravimetric or colorimetric determinations. G . G . TERTIPIS a n d F. E. BEAMISH, University of Toronto, Toronto, Ontario, Canada A n a l . Chem. 3 2 , 4 8 6 ( 1 9 6 0 )
N e w Fire Assay for Osmium and Ruthenium
A new fire assay procedure used for determining platinum and palladium is applied to determine osmium and ruthenium. Losses to slags or pot wells are insignificant and platinum does not interfere in the determination. The procedure is applied to assay concentrates from natural ore. J. M. K A V A N A G H and F. E. BEAMISH, University of Toronto, Toronto, Ontario, Canada A n a l . Chem. 3 2 , 4 9 0 ( 1 9 6 0 )
Infrared absorption spectra of 17 tert-hutoxy compounds are obtained and used to determine the regions of absorption for the tert-butoxy group. The absorption bands lie within the 720 to 1200 cm.- 1 region. Molecular structure influences the absorption bands exhibited by the various compounds. H. A. ORY, Monsanto Chemical Co., Texas City, Tex. A n a l . Chem. 3 2 , 5 0 9 ( 1 9 6 0 )
Spectrophotometric Study of N,N'-Bis(3-dimethylaminopropyl)dithio-oxamide as a Reagent for Palladium
Palladium(II) is spectrophotometrically determined by a procedure employing JV,N'-bis(3-dimethylaminopropyl)dithio-oxamide as the complexing reagent. With an excess of reagent the reaction proceeds in hydrochloric acid solution to give a stable complex with an absorption maximum at 427 πΐμ. W . D. JACOBS, University of G e o r g i a , Athens, G a . A n a l . Chem. 3 2 , 5 1 2 ( 1 9 6 0 )
Spectrophotometric Determination of Rhodium w i t h N,N'-Bis(3-dimethylaminopropyl)dithio-oxamide
A spectrophotometric method is devised for determining rhodium(III) using 7V,7V'-bis(3-dimethylaminopropyl)dithio-oxamide as the complexing reagent. The sample and reagent are heated in strong hydrochloric acid solution and the yellow complex formed has absorbance peaks at 3 50 πιμ and 420 πΐμ. Platinum metals interfere. Separation of Bismuth from Lead with (Ethylenedinitrilo)tetraacetic A c i d . Application to Radiochemistry
A new method is employed for separating lead from bismuth, whatever their respective concentrations. The procedure avoids the use of calcium to dissociate the bismuth-EDTA complex. The method is useful in radiochemical problems and can be completed in 15 minutes. F. W . LIMA and ALCIDIO ABRAO, Instituto d e Energia A t ô m i c a , Sâo Paulo, Brazil A n a l . Chem. 3 2 , 4 9 2 ( 1 9 6 0 )
W . D. JACOBS, University of G e o r g i a , Athens, G a . A n a l . Chem. 3 2 , 5 1 4 ( 1 9 6 0 )
Potassium Pyrosulfate Fusion Technique. Deter mination of Copper in Mattes and Slags by X - R a y Spectroscopy
A rapid and accurate x-ray spectrographic method is devised for determining copper in mattes and slags. A potassium pyrosulfate fusion technique is used and the fusion is ground and briquetted to give a uniform surface exposure. The method compares favorably wtih chem ical analysis. T. J. CULLEN, United States Metals Refining Co., C a r t e r e t , N. J. A n a l . Chem. 3 2 , 5 1 6 ( 1 9 6 0 )
Analysis of Explosives Using Infrared Spectroscopy
Infrared spectrograms of 68 common high explosive compounds, additives, and related compounds are compiled and examined. The data facilitates the infrared structural investigation of unknown ingredients. Infrared spectroscopy affords accuracy and specificity in analysis of simple or multicomponent high explosives. FRANK PRISTERA, MICHAEL HALIK, ALEXANDER CASTELLI, a n d WALTER FREDERICKS, Picatinny Arsenal, Dover, N. J. A n a l . Chem. 3 2 , 4 9 5 ( 1 9 6 0 )
A Quantitative Method for the Differential Deter mination of Hydroxylamine and Beta-Aspartyl Hydroxamate in Mixtures
A spectrophotometric method is devised for the differ ential quantitative determination of hydroxylamine and (3-aspartyl-hydroxamate in mixtures. The procedure is based on the fact that hydroxylamine gives a color reaction by Blom's method atpH 2.3 and 3.7, and the hydroxamate reacts only at pH 3.7. The method is applicable to biological oxidation systems. J. YASHPHE, Y. S. HALPERN, a n d N A T H A N G R O S S O W I C Z , The H e b r e w University, Jerusalem, Israel A n a l . Chem. 3 2 , 5 1 8 ( 1 9 6 0 )
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ι=ι>»**^ Adsorption of the Elements from Hydrofluoric Acid by Anion Exchange
Hydrofluoric acid is used as an elutant for some 50 ele ments from a strongly basic anion exchange resin. Spectrographic analysis data were obtained for effluents of 1Λ1 to 24Λ1 concentration of acid. The procedure suggests a wide range in analytical application. J. P. FARIS, Argonne N a t i o n a l L a b o r a t o r y , Lemont, 111. A n a l . Chem. 3 2 , 5 2 0 ( 1 9 6 0 )
Determination of Boron in Borohydrides and Organo boron Compounds by Oxidation with Trifluoroperoxyacetic Acid
A titrimetric method is used to determine boron in boro hydrides and organoboron compounds. Boric acid is produced by oxidation with trifluoroperoxyacetic acid and converted to mannitoboric acid which is titrated with sodium hydroxide. R. D. STRAHM a n d M. F. H A W T H O R N E , Rohm & Haas Co., Huntsville, Ala. Anal. Chem. 3 2 , 5 3 0 ( 1 9 6 0 )
Automatic Apparatus for Determination of Nitrogen Adsorption and Desorption Isotherms Square-Wave Polarography of Plutonium
A square-wave polarographic procedure is used to deter mine small amounts of plutonium in hydrochloric and nitric acids. Concentrations below 10- 6 mole per liter are analyzed using a stationary platinum electrode. Sen sitivity of this procedure is higher than the conventional method.
An apparatus is designed which automatically adds or removes constant volumes of nitrogen from an absorbent sample system. In studies of pore size distribution of small-pore materials the apparatus affords a saving of time and recorded data on pressure-volume characteris tics of the system. E. V. BALLOU a n d O . K. D O O L E N , G u l f Research & Development Co. Pittsburgh, Pa. A n a l . Chem. 3 2 , 5 3 2 ( 1 9 6 0 )
KARL K O Y A M A , G e n e r a l Electric Co., Richland, W a s h . A n a l . Chem. 3 2 , 5 2 3 ( 1 9 6 0 )
Convenient pH-Stat Assembly
Coulometric Titrations with Electrolytically Generated Sulfhydryl Compounds. Applications of Thioglycollic Acid
A constant current coulometric procedure employs the sulfhydryl group as reagent, generated from mercuric thioglycollic acid. A mercury pM electrode is used for endpoint detection. The sulfhydryl group forms a com plex with metals such as copper, gold, mercury, and ferricyanide making their coulometric determination feasible with this procedure. BARRY MILLER a n d D. N. HUME, Massachusetts Institute o f Technology, C a m b r i d g e 3 9 , Mass. A n a l . Chem. 3 2 , 5 2 4 ( 1 9 6 0 )
The construction and operation details are given for a pH-stat assembly. The instrument displays high ac curacy and stability with convenience in operation. It permits a 50 to 1 change in rate of addition of reagent without necessary adjustment. K. I. W O O D , C. S. I. R. O . W o o l Research Laboratories, Parkville, N. 2 , (Melbourne), V i c t o r i a , Australia A n a l . Chem. 3 2 , 5 3 7 ( 1 9 6 0 )
Determination of Free Fatty Acids in Fat
Free fatty acids are separated from unsaponified fat by absorption on a strong anion base exchange resin. The fat is eluted with petroleum ether, and the fatty acids are converted on the column to their methyl ester with methanol-hydrochloric acid solution. The fatty acid concentration is determined by gas chromatography. IRWIN HORNSTEIN, J. A. ALFORD, L. E. ELLIOTT, a n d P. F. C R O W E , U. S. D e p a r t m e n t of Agriculture, Beltsville, M d . A n a l . Chem. 3 2 , 5 4 0 ( 1 9 6 0 )
Determination of Small Stoichiometric Deviations in O x i d e Monocrystals
A modified Bunsen method permits the measurement of stoichiometric deviations in oxide monocrystals down to 1 milliatom of oxygen per molecule sample. The method is applied to the analysis of oxygen surplus in monocrystals of manganese oxide, cobalt oxide, and nickel oxide. H. B. SACHSE, Keystone C a r b o n Co., St. M a r y s , Pa. A n a l . Chem. 3 2 , 5 2 9 ( 1 9 6 0 )
Colorimetric Determination of Traces of Acids in Dimethyl Terephthalate
A rapid spectrophotometry method is developed for determining the acid number of dimethyl terephthalate. The ester is dissolved in a selected solvent and reacted with the potassium salt of bromothymol blue. The de crease in the intensity of the blue color is proportional to the acid concentration. A. L. HENSLEY, S t a n d a r d O i l Co. (Indiana), W h i t i n g , Ind. A n a l . Chem. 3 2 , 5 4 2 ( 1 9 6 0 )
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BRIEFS The Analytical Chemistry of Organometallics. Quantitative Determination of Organoalkalies
Characterization of A l k y l Halides
A new titrimetric method is employed to determine organoalkali compounds. The sample is added slowly to a standardized diethylether-iodine solution. The ex cess iodine is then titrated with aqueous thiosulfate solu tion. The method indicates better accuracy than current procedure. A. F. CLIFFORD a n d R. R. OLSEN, Purdue University, L a f a y e t t e , Ind.
A method is developed for characterizing alkyl halides through their reaction with methyl fluorene-9-carboxylic acid. Alkylation succeeds with chlorides, bromides, and iodides. The size of the alkyl group is determined by hydrolysis of the product to alkylfluorene-9-carboxylic acid and measuring the equivalent weight P. M. G . B A V I N , The University, Hull, East Yorkshire, England A n a l . Chem. 3 2 , 5 5 4 ( 1 9 6 0 )
A n a l . Chem. 3 2 , 5 4 4 ( 1 9 6 0 )
Modified Method for Hydroxyproline Determination
A spectrophotometric method is used to determine microamounts of hydroxyproline in tissue hydrolysates. The sample is reacted with />-dimethylaminobenzaldehyde in propyl alcohol and the absorbance measured at 500 and 560 π\μ. Rubeanic Acid Human Serum
for
Determination
of
Copper
in
Trace amounts of copper in biological tissues and enzyme preparations are determined spectrophotometrically with rubeanic acid. Extraction is unnecessary and the rubeanic acid-copper complex is developed in aqueous solution. Iron interference is eliminated by complexation with malonic acid. D. S. M c C A N N , PATRICIA BURCAR, and A. J. BOYLE, W a y n e State University, Detroit, Mich. A n a l . Chem. 3 2 , 5 4 7 ( 1 9 6 0 )
FERENC HUTTERER and E. J. SINGER, The Mount Sinai Hospital, N e w York 2 9 , N.Y. A n a l . Chem. 3 2 , 5 5 6 ( 1 9 6 0 )
Determination of Microgram Quantities of Sulfate in Organic Linkages
The sulfate content of mucopolysaccharides is deter mined by a turbidimetric procedure using a wet digestion with chloric acid. The method is suitable for determin ing over 20 samples simultaneously with sulfur contents from 10 to 300 gamma. GERALDINE ZDYBEK, D. S. M c C A N N a n d A. J. BOYLE, W a y n e State University, Detroit 2, Mich. A n a l . Chem. 3 2 , 5 5 8 ( 1 9 6 0 )
Potassium Cobaltinitrite as a Precipitation Form for Cobalt Using Radiocobalt Tracer
The rate of precipitation of cobalt with potassium nitrite is investigated to determine quantitative conditions. Radiocobalt tracers are used in examining the variables in the procedure. A method is recommended which gives quantitative precipitation in 2 hours. DARNELL SALYER and T. R. SWEET, The O h i o State University, Columbus 10, Ohio A n a l . Chem. 3 2 , 5 4 8 ( 1 9 6 0 )
Fluorometric Microdetermination of Human Serum Albumin
The albumin content of human serum is determined by fluorometric procedure. The albumin in alkaline solu tion is reacted with vasoflavine and the fluorescence measured against a quinine standard. The method com pares favorably with established procedures for serum albumin. J. J. BETHEIL, Yeshiva University, N e w York 6 1 , Ν. Υ. A n a l . Chem. 3 2 , 5 6 0 ( 1 9 6 0 )
Design and Use of a Refined Microelectrophoresis Unit Characterization of A l k y l Halides by Use of Ethylenethiourea
A qualitative procedure is used to identify alkyl halides from the derivatives formed with ethylenethiourea. The alkyl halides studied form solid derivatives with ethyl enethiourea and are identified by melting point analysis. R. N. BOYD a n d M O R T O N M E A D O W , York 3, Ν. Υ.
An improved precise microelectrophoresis apparatus is described which simultaneously analyzes eight 0.01 to 0.1 microliter samples. A high degree of reproducibility is obtained through accurate positioning of precisely cut, multistrip papers. Ink dye, blood serum protein, and ferritin solutions are analyzed.
New
B. W . G R U N B A U M , University of C a l i f o r n i a , San Francisco, Calif., a n d P. L. KIRK, University of C a l i f o r n i a , Berkely, Calif.
A n a l . Chem. 3 2 , 5 5 1 ( 1 9 6 0 )
A n a l . Chem. 3 2 , 5 6 4 ( 1 9 6 0 )
New
York
University,
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