HIGHLIGHTS OF T H E SCIENTIFIC A N D T E C H N I C A L ARTICLES IN THIS ISSUE
AC BRIEFS Chromatographic-Solvent Extraction Isolation of Berkelium-249from Highly Radioactive Solutions and Its Determination by Beta Counting High-pressure column chromatography and extraction with thenoyltrifluoroacetone (TTA) along with measurement of the purified 2 "Bk by beta counting are the basic techniques used in this method. L. G . F A R R A R , J . H . C O O P E R , and F. L M O O R E , A n a l y t i c a l Chemistry Division, O a k Ridge N a t i o n a l Laboratory, O a k Ridge, Tenn. 3 7 8 3 0 A n a l . C h e m . 4 0 , 1602 ( 1 9 6 8 )
Thin-Layer Chromatography of Steroidal Pharmaceuticals Chromatographic mobilities of 23 synthetic steroid hormones together with their coloration by three spraying reagents are examined and correlated to the structure of steroids by calculated ARM values for several functional groups. S H O J I H A R A , Division of O r g a n i c Chemistry, Tokyo C o l l e g e of Pharmacy, Ueno-Sakuragi, Taito-ku, Tokyo, and K U N I O MIBE, Tokyo Hospital Printing Bureau, Ministry of Finance, Nishigahara, Kita-ku, Tokyo A n a l . C h e m . 4 0 , 1605 ( 1 9 6 8 )
Gas Chromatographic Characteristics in the Separation of Protium and Deuterium Forms of Trimethylsilyl Sugars The measurement of various factors responsible for peak separation and peak broadening in gas chromatography of protium and deuterium forms of carbohydrates has been investigated. N . C . S A H A and C H A R L E S C . SWEELEY, Department of Biochemisty and Nutrition, G r a d u a t e School of Public H e a l t h , University of Pittsburgh, Pittsburgh, Pa. 15213 A n a l . C h e m . 4 0 , 1628 ( 1 9 6 8 )
Determination of Normal Paraffins in Petroleum Heavy Distillates by Urea Adduction and Gas Chromatography The method consists of a simple, efficient urea adduction step for isolating the normal paraffins, which are then analyzed with good resolution by gas-liquid chromatography. J . R. M A R O U A R T , G . B. D E L L O W , Development C o . , Emeryville, C a l i f .
and E. R. FREITAS, Shell
A n a l . C h e m . 4 0 , 1633 ( 1 9 6 8 )
A Ring-Disk Electrode Study of the Deposition and Stripping of Thin Copper Films at Platinum in Sulfuric Acid
Determination of Reflectance of Pesticide Spots on Thin-Layer Chromatograms Using Fiber Optics A fiber-optic scanning head containing randomly mixed glass fibers is the basic unit of the instrument developed for scanning thin-layer chromatograms by measuring diffuse reflectance.
Monolayer amounts of copper in 0.2M H 2 S0 4 can be deposited and stripped from a rotating platinum ring-disk electrode. Faraday's law is obeyed providing corrections are made for C u ( I ) formed during the experiment.
M O R T O N B E R O Z A and K. R. H I L L , Entomology Research Division, Agricultural Research Service, U . S. Department of A g r i culture, Beltsville, M d . 20705, and KARL H . N O R R I S , Market Q u a l i t y Research Division, Agricultural Research Service, U. S. Department of Agriculture, Beltsville, M d . 20705
G . W . T I N D A L L and STANLEY B R U C K E N S T E I N , Chemistry Department, University of Minnesota, Minneapolis, M i n n . 55455
A n a l . C h e m . 4 0 , 1608 ( 1 9 6 8 )
Detection and Analysis of Unresolved Multiplet Chromatographic Peaks The diagnostic characteristics of the dispersion and displacement differences between experimental and reference peaks are used to demonstrate the detection and determination of up to four components in a single peak. V A C L A V C E J K A , M E R L I N H . DIPERT, S Y L V A N U S A . TYLER and PETER D. K L E I N , Division o f Biological and M e d i c a l Research, Argonne National Laboratory, Argonne, I I I . 60439 A n a l . C h e m . 4 0 , 1614 ( 1 9 6 8 )
Analysis of Ethylene Oxide and Propylene Oxide Adducts of Alkylphenols or Alcohols by Nuclear Magnetic Resonance, Gas—Liquid Chromatography, and Thin Layer Chromatography Procedures The K M R , GLC, and T L C procedures described in this work were developed to determine the composition of EtO a n d / o r PrO adducts of p-alkylphenols or alcohols used as surfactants.
A n a l . C h e m . 4 0 , 1637 ( 1 9 6 8 )
Determination of Molybdenum by ControlledPotential Coulometry. Application to the Analysis of Molybdenum-TungstenRhenium Alloys The method is based on the reduction of Mo (VI) to Mo(V) at —0.25V vs. SCE in a supporting electrolyte of 0.2M ( N r L J i C O . and 1.3M H 2 S0 4 at pH 2.1. An accuracy and precision of 0.1% is achieved with solution of 0.2 to 10 mg M o / m l . L. P. R I G D O N and J . E. H A R R A R , Chemistry Department, Lawrence Radiation Laboratory, University of C a l i f o r n i a , Livermore Calif. 94550 A n a l . C h e m . 4 0 , 1641 ( 1 9 6 8 )
Electrochemical Equivalents of Benzoic and Oxalic Acid Values of electrochemical equivalents of benzoic and oxalic acid dihydrate reported are 1.265715 ± 0.000036 m g / C and 0.653293 ± 0.000023 m g / C , respectively. The faraday is calculated to be 96,486.7 ± 2.5 C/g-equiv and 96,485.4 ± 3.4 C/g-equiv for benzoic and oxalic acid coulometers, respectively.
Corp.,
G E O R G E M A R I N E N K O and J O H N K. T A Y L O R , Division of A n a l y t i c a l Chemistry, Institute for Materials Research, National Bureau of Standards, Washington, D. C . 20234
A n a l . C h e m . 4 0 , 1620 ( 1 9 6 8 )
A n a l . Chem. 4 0 , 1645 ( 1968)
F. J O H N L U D W I G , Sr., Research Laboratory, 369 Marshall A v e . , St. Louis, M o . 63 119
Petrolite
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AC BRIEFS A Sensitive and Versatile Differential Vapor Pressure Apparatus An accuracy of about 0.25% is obtained at relatively high solute concentrations, >0.01Af, in suitable solvents. I n higher vapor pressure solvents, 1% precision is achieved in solutions as dilute as 1 mM. R. J . F A R M and S T A N L E Y B R U C K E N S T E I N , Department of C h e m istry, University of Minnesota, Minneapolis, M i n n . 55455 A n a l . C h e m . 4 0 , 1651 ( 1 9 6 8 )
Determination of Fluoride in A i r and Stack Gas Samples by Use of an Ion-Specific Electrode Gaseous and particulate fluoride in ambient air are col lected by filtration and chemisorption on membrane fil ters impregnated with sodium formate. As little as 0.25 ppb fluoride in air can be measured with this procedure. L A W R E N C E A . ELFERS and C L I F F O R D E. DECKER, N a t i o n a l C e n t e r for A i r Pollution C o n t r o l , U . S. Department of H e a l t h , Education, and W e l f a r e , Cincinnati, Ohio 45237 A n a l . C h e m . 4 0 , 1658 ( 1 9 6 8 )
Spectrophotometric Analysis of Sulfuric Solutions of Hydrogen Peroxide, Peroxymonosulf uric Acid, and Peroxydisulf uric Acid Effects of concentration, acidity, dissolved oxygen, and cerous ions on the accuracy of the measurements are studied, as well as the variation of the sample composi tions for different sulfuric acid concentrations with time. MARIA
H. MARIANO,
Laboratorio de Fisica e Engenharia N u -
A New Method for Decomposition and Comprehensive Analysis of Silicates by Atomic Absorption Spectrometry A decomposition vessel is described which prevents volatil ization losses by hydrofluoric acid at 110 °C. A fluoboricboric acids system provides a favorable decomposition medium and a suitable salt-free single matrix system. B E D R I C H BERNAS, National A c a d e m y of Sciences, National Aeronautics and Space Administration, G o d d a r d Space Flight Center, G r e e n b s l t , M d . A n a l . Chem. 4 0 , 1682 ( 1 9 6 8 )
Gas Analysis by Modulated Molecular Beam Mass Spectrometry The system has been tested by analyzing natural oxygen gas for various isotopic combinations. The 1.5-ppm 1 7 0 1 8 0 isotope was measured with a relative error of 5%· T h e ultimate sensitivity of the technique is approximately 0.1 ppm. D. R. O L A N D E R and W . W . W A D D E L , Inorganic Materials Re search Division, Lawrence Radiation Laboratory, and Department of Nuclear Engineering, C o l l e g e of Engineering, University of California, Berkeley, C a l i f . A n a l . C h e m . 4 0 , 1687 (1968)
Chelation Studies by Conformational Analysis. Proton Magnetic Resonance of df-Propylenediaminetetraacetic Acid The formation of weak 1:1 K + , Rb + , and (CH 3 ) 4 N + chelates of P D T A is established for the first time, and their forma tion constants at 100 °C have been determined to be 1.3, 0.14, 0.12, respectively. J A M E S L. S U D M E I E R and A L A N J . SEN2EL, Department Chemistry, University of California, Los Angeles, C a l i f . 90024
of
cleares, Sacavem, Portugal A n a l . C h e m . 4 0 , 1662 ( 1 9 6 8 )
A Precision Photometer Using Milliwatt Light Sources and Photon Counting Presented is a study on the use of a low-power tungsten bulb or hollow cathode tube with a photomultiplier pulse detection system to count single photoelectron events over several orders of magnitude of radiant power. E D W A R D H . PIEPMEIER, D O N A L D E. B R A U N , and R O X I E R. R H O D E S , Department of Chemistry, O r e g o n State University, Corvallis, O r e . 97331 A n a l . C h e m . 4 0 , 1667 ( 1 9 6 8 )
An Adjustable-Waveform High-Voltage Spark Source for Optical Emission Spectrometry A high-voltage spark source is described that is capable of producing high-current discharges ranging from fully oscillatory a t frequencies in the submegacycle range to fully unidirectional in the conventional overdamped mode. J . P. W A L T E R S , Department of Chemistry, University of W i s c o n sin, Madison, W i s . 53706 A n a l . C h e m . 4 0 , 1672 ( 1 9 6 8 )
A n a l . C h e m . 4 0 , 1693 11968)
Electron Spin Resonance in American Coals Reported are the spin center concentrations, spectral linewidths, and g values for a coalification series consisting of samples of peat and lignitic, subbituminous, bituminous, and anthracitic coals, all of which were mined in the United States. H . L. RETCOFSKY, J . M . STARK, and R. A . FRIEDEL, U . S. De partment o f the Interior, Bureau of Mines, Pittsburgh C o a l Re search Center, Pittsburgh, Pa. 15213 A n a l . C h e m . 4 0 , 1699 ( 1 9 6 8 )
Fluorometric Determination of Acrolein and Related Compounds with m-Aminophenol A fast and simple procedure to 5determine concentrations of acrolein as low as 5 Χ 10" ^mole/ml is described. The fluorescent compound from acrolein has been identi fied as 7-h3'droxyquinoline by the excitation and fluo rescence spectra. R. A . A L A R C O N , The Children's Cancer Research Foundation, and The Department of Pathology, H a r v a r d M e d i c a l School, Boston, Mass. 021 15 A n a l . Chem. 4 0 , 1704 ( 1 9 6 8 )
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AC BRIEFS Synergic Extraction of Gallium with Thenoyltrifluoroacetone and Tetraphenylarsonium Chloride The maximum synergism is observed in the p H region of 2.4 to 2.6 with 0.05M T T A and 5 χ 10~2Μ tetraphenyl arsonium chloride. At p H 2.4, the distribution ratio with the combined reagents is 80 times greater than that with T T A alone. M D . SYEDUR R A H A M A N and H . L. F I N S T O N , Department of Chemistry, Brooklyn C o l l e g e of the C i t y University of New York, Brooklyn, Ν . Υ . Ι12Ι0 A n a l . C h e m . 4 0 , 1709 ( 1 9 6 8 )
Theoretical Evaluation of Entropy Titration Method for Calorimetric Determination of Equilibrium Constants in Aqueous Solution Optimum experimental conditions for the determination of equilibrium constants by the entropy titration method are defined based on measured heat values, titrant con centration, and solution concentration variables. J A M E S J . C H R I S T E N S E N , D O N A L D P. W R A T H A L L , J O H N O . O S C A R S O N , and REED M . IZATT, Departments of Chemical En gineering and Chemistry, Brigham Young University, Prove Utah 84601 A n a l . C h e m . 4 0 , 1713 (1968)
Determination of Linear 1-Chloroalkanes in Mixtures of Linear and Nonlinear (C 12 —Ci 6 ) Chloroalkanes by Reaction Kinetics The chloroalkane mixture is reacted at steam bath tem peratures with a large excess of piperidine in 9:1 N,AT'dimethylformamide-water solvent until the linear 1chloroalkane is 9 9 + % reacted (120 min). D O N A L D E. J O R D A N , Continental O i l C o . , Ponca C i t y , O k l a . A n a l . C h e m . 4 0 , 1717 ( 1 9 6 8 )
Spectrophotometric Method for Estimating Alkyl Ester Hydrolysis The difference in molar absorptivities between alkyl esters and alkyl acids is the basis for determining the concentra tions required for estimating the velocity constant of an ester and its acid at any interval during hydrolysis. R. S. R O Y , Science C o l l e g e , Mosul University, Mosul, Iraq A n a l . C h e m . 4 0 , 1724 ( 1 9 6 8 )
Spectrophotometric Method for Studying the Kinetics of Saponification of Alkyl Esters The saponification of ethyl acetate by sodium hydroxide is reported. The average velocity constant estimated for a 0.03M, 3:1 mixture at 20 °C is 0.68 Χ 10"1 m o l e ' sec"1. R. S. R O Y and H . N . A L - J A L L O , Faculty of Science, University of Mosul, Mosul, Iraq A n a l . C h e m . 4 0 , 1725 ( 1 9 6 8 )
Rapid Electrophoretic Separation of Rhenium(lll), Rhenium(IV), and Rhenium(VII) A rapid method for the study of nuclear transformations in rhenium systems is described which does not result in coprecipitation and is effective for small amounts of sub stance. J U A N F. FACETTI and M A R C E L I N A VELEZ d e S A N T I A G O , Puerto Rico Nuclear Center, Mayaguez, P. R. 00708 A n a l . C h e m . 4 0 , 1726 ( 1 9 6 8 )
Notes Chromatographic Separation and Colorimetric Determination of Polyoxyethylene Glycols in High Condensation Products of Ethylene Oxide with Fatty Alcohols and Alkylphenols Described is the application of reversed phase partition chromatography in determining P E G involved in polyoxyethylene-type, nonionic surfactants especially in high condensates. K A Z U O K O N I S H I and S H I N I C H I R O Y A M A G U C H I , Industrial Research Laboratories, Kao Soap C o . , Ltd., 1334 Minatoyakushubata, Wakayama-shi, Japan A n a l . C h e m . 4 0 , 1720 ( 1 9 6 8 )
Problems in Gas Chromatographic Determination of Methionine, Methionine Sulfoxide, and Methionine Sulfone Evidence is presented that under a number of conditions, methionine sulfoxide is converted to an iV-acylmethionine methyl ester and is chromatographed as such.
Separation and Gas Chromatographic Determination of Normal Hydrocarbons in Tobacco Leaves The method described minimizes the possibilities of isomerization, rearrangements, condensations of other nonhydrocarbon compounds present during the separation and identification of the hydrocarbon fraction. R O Y L. J O H N S T O N and L O U I S A . J O N E S , Department of C h e m istry, North Carolina State University, Raleigh, N . C . 27607 A n a l . C h e m . 4 9 , 1728 ( 1 9 6 8 )
Determination of Lithium by Potentiometric Titration with Fluoride This method uses quantitative precipitation of L i F in alcohol as the basis for a potentiometric titration with a lanthanum fluoride membrane electrode as the indicator electrode.
STEVEN R. T A N N E N B A U M , W I L L I A M G . T H I L L Y , and PHILLIP ISSENBERG, Department of Nutrition and Food Science, Massa chusetts Institute of Technology, C a m b r i d g e , Mass. 02139
ELIZABETH W . B A U M A N N , Savannah River Laboratory, E. I. du Pont de Nemours and C o . , Aiken, S. C . 2 9 8 0 I
A n a l . CheWi. 4 0 , 1723 ( 1 9 6 8 )
A n a l . C h e m . 4 0 , 1731 ( 1 9 6 8 )
-Circle No. 99 on Readers' Service Card
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AC Improvements in Preparation and Operation of Electrodeless Discharge Lamps as High Intensity Sources in Atomic Fluorescence Flame Spectrometry Increases of intensity and stability of lamps of some ele ments result if the lamps containing metal iodides also contain excess metal. Many lamps produce more intense atomic fluorescence when operated in an evacuated jacket on the "A" antenna or when operated in a rectangular cavity. K. E. Z A C H A , M . P. BRATZEL, Jr., J . D. W I N E F O R D N E R , and J . M . M A N S F I E L D , Jr., Department of Chemistry, University of Florida, Gainesville, Fia. 3 2 6 0 I A n a l . C h e m . 40, 1733 ( 1 9 6 8 )
Apparatus and Materials for Hyperpressure Gas Chromatography of Nonvolatile Compounds A hyperpressure gas chromatograph is described as de veloped from studies on an analytical or preparative method for nonvolatile organic, organometallic, and in organic compounds. N I C H O L A S M . K A R A Y A N N I S , A L S O P H H . C O R W I N , EARL W . BAKER, ERNST KLESPER, and J O S E P H A . W A L T E R , Depart ment of Chemistry, The Johns Hopkins University, Baltimore, M d . A n a l . C h e m . 4 0 , 1736 ( 1 9 6 8 )
BRIEFS
Correspondence Reaction Kinetics as a Diagnostic Tool for the Gas Chromatographic Column STANLEY H . L A N G E R , J O A N N E Y. Y U R C H A K , and C H R I S T O PHER M . S H A U G H N E S S Y , Department of Chemical Engineering, University of Wisconsin, Madison, W i s . 53706 A n a l . Chem. 4 0 , 1747 (1968)
Spectrophotometry Determination of Pyrrolizidine Alkaloids—Some Improvements A . R. M A T T O C K S , Toxicology Research Unit, M e d i c a l Research Council Laboratories, Woodmansterne Road, Carshalton, Surrey, England A n a l . Chem. 4 0 , 1749 ( 1 9 6 8 )
Aids for Analytical Chemists Rolling-Ball Viscometer for Measuring Viscosity of Fluids at High Pressures and Moderate Temperatures E. M . STANLEY and R. C . BATTEN, N a v a l Development Center, Annapolis, M d . 21402
Ship Research
and
A n a l . Chem. 4 0 , 1751 ( 1 9 6 8 )
Quantitative Analysis with the Aid of Calculated X-Ray Powder Patterns The ratios of integrated intensities of diffraction lines of a mixture, measured on an arbitrary scale, and the corresponding absolute intensities of the calculated pat terns are proportional, after absorption corrections, to the quantities of components present. I. C Y R U S J A H A N B A G L O O , Materials Research Laboratory, The Pennsylvania State University, University Park, Pa. 16802, and T I B O R Z O L T A I , Department of G e o l o g y and Geophysics, Uni versity of Minnesota, Minneapolis, M i n n .
Rapid Determination of Organic Nitrogen with a Coulometric Detector I. J . O I T A , Research and Development Dept., American O i l C o . , W h i t i n g , Ind. 46394 A n a l . Chem. 4 0 , 1753 ( 1 9 6 8 )
Use of Powder Covered Surface to Enhance Sensitivity in Detection of Aerosols via Internal Reflection Spectrometry
A n a l . C h e m . 4 0 , 1739 ( 1 9 6 8 ) N. J. HARRICK, 10510
Philips
Laboratories,
Briarcliff
Manor,
Ν.
Υ.
A n a l . C h e m . 4 0 , 1755 ( 1 9 6 8 )
Determination of Acyl-Thiolesters by Gas-Liquid Chromatography of Their Sodium Borohydride Reduction Products Because NaBHt does not reduce normal esters (O-acyl esters) its reduction of thiolesters, along with separation and quantitation of the alcohols by GLC, allows the spe cific and sensitive determination of thiolesters.
A Sensitive Low Volume Conductivity Detector for Liquid Chromatography ROBERT L. PECSOK and D E N N I S L S A U N D E R S , Department of Chemistry, University of California, Los Angeles, C a l i f . 90024 A n a l . Chem. 40, 1756 ( 1 9 6 8 )
E D W A R D J . B A R R O N and LARRY A . M O O N E Y , Virginia Mason Research Center, Seattle, W a s h . 98 101 A n a l . C h e m . 40, 1742 ( 1 9 6 8 )
Heat-Sealed Polyethylene Sample Containers for Neutron Activation Analysis W . D. E H M A N N and D. M . M c K O W N , Department of Chemistry, University of Kentucky, Lexington, Ky. 40506
Determination of Trace Nitrogen in Organic Materials by a Microcombustion Technique Nitrogen contents of 0.0005-1.00% as nitro, amide, nitrile, amine, and heterocyclic (nicotinic acid) compounds were determined. Errors averaged ± 1 0 % of the amount of nitrogen added. J . P. W I N E B U R G , Eastern Laboratory, Explosives Department, E. I. du Pont de Nemours & Company, Gibbstown, N . J . A n a l . C h e m . 4 0 , 1744 ( 1 9 6 8 ) •
