A C BRIEFS

A C BRIEFS Highlights of Articles in This Issue

Chemical or Solute Vaporization Interferences in Flame Atomic Emission and Absorption Spectrometry. Alkaline Earth Anion Systems

Electrolysis of Organophosphorus Compounds. Study of Mechanism of Reduction of Various Diethyl Aroylphosphonates at a Dropping Mercury Electrode

Depression of alkaline earth emission signals by increasing concentrations of phosphate, sulfate, and borate anions can be eliminated if optimal nebulization and burner systems are used.

This study attempts to correlate the observed half-wave po­ tentials with the Hammett σ-values of various ring substituents.

VELMER A. FASSEL and DONALD A. BECKER, Institute of Atomic Research and Department of Chemistry, Iowa State University, Ames, Iowa 50010

K. DARRELL BERLIN, DAVID S. RULISON, and PAUL ARTHUR, Department of Chemistry, Oklahoma State Uni­ versity, Stillwater, Okla. 74074 Anal. Chem., 41, 1554 (1969)

Anal. Chem., 41, 1522 (1969) Evaluation of Premixed Flames Produced Using a Total Consumption Nebulizer Burner in Atomic Fluorescence Spectrometry The premixed and unpremixed Ν Ϊ 0 / Η 2 flames seem to be the most generally useful hydrogen-based flames for atomic fluorescence spectrometric studies. M. P. BRATZEL, Jr., R. M. DAGNALL, and J. D. WINEFORDNER, Department of Chemistry, University of Florida, Gainesville, Fla. 32601 Anal. Chem., 41, 1527 (1969)

Solid-State Polarographic Instrumentation—A Unique Approach to Versatility A solid-state voltammetry system featuring a digital-logic controlled function generator is described. I t is uncondition­ ally stable and capable of moderately fast time-response. RICHARD BEZMAN and P. S. McKINNEY, Department of Chemistry, Harvard University, Cambridge, Mass. 02138 Anal. Chem., 41, 1560 (1969)

Determination of a Protonation Scheme for Isochlortetracycline Using Nuclear Magnetic Resonance

Pulse Polarographic Study of the Cystine Catalytic Hydrogen Wave

Chemical shift data and potentiometric titrations are used to determine the macro- and mierodissociation constants for isochlortetracycline.

The effects of pH, buffer capacity, ionic strength, and cobalt and ammonia concentrations are studied. Results allow 5 χ 10'° M cystine to be detected in pure solution.

ULRICH W. KESSELRING and LESLIE Z. BENET, College of Pharmacy, Washington State University, Pullman, Wash. 99163 Anal. Chem., 41, 1535 (1969)

D. D. GILBERT, Department of Chemistry, Northern Ari­ zona University, Flagstaff, Ariz. 86001

Utilization of Electron Spin Resonance Spectrometry in Hydrogen-Deuterium Exchange Studies. Exchange Rates and Equilibrium Constants in Some Hydroquinones ESR spectrometry is used to monitor single and multiple H - D exchange in hydroquinones. Advantages and limita­ tions of the technique are discussed. H. C. YAO and H. C. HELLER, Chemistry Department, Sci­ entific Research Staff, Ford Motor Co., Dearborn, Mich.

Anal. Chem., 41, 1567 (1969)

Levelling Effect of Lithium(l) on the Polarographic Reduction of Pyridinium Species in Pyridine. Ion Association and Exchange Equilibria Involved The common Ein observed in this system is due to the for­ mation of a slightly dissociated species between Li (I) and the acid anion. KEIICHI TSUJI and PHILIP J. ELVING, The University of Michigan, Ann Arbor, Mich. Anal. Chem., 41, 1571 (1969)

Anal. Chem., 41, 1540 (1969) Low-Resolution Mass Spectrometric Determination of Aromatic Fractions from Petroleum

New Micro Liquid-Liquid Partition Technique with the Coil Planet Centrifuge

The entire composition of an aromatic sample is accounted for in terms of 12 hydrocarbons, 3 thiopheno types, and 6 unnamed groups.

A fine coiled tube is filled with a two-phase system which is subjected to a planetary motion by a coil planet centrifuge.

C. J. ROBINSON, Research and Development Dept, ican Oil Co., Whiting, Ind. 46394, and GLENN L. Laramie Petroleum Research Center, University Laramie, Wyo. 82070 Anal. Chem., 41, 1548

Amer­ COOK, Station, (1969)

YOICH/RO (TO, CHIRO AOKI, and EIICHI KIMURA, De­ partment of Physiology, Osaka City University Medical School, Abeno-ku, Osaka, Japan, and KANICHI NUNOGAKI and YOSHIAKI NUNOGAKI, Sanki Engineering, Ltd., Nagaoka-cho, Kyoto, Japan Anal. Chem., 41, 1579 (1969) VOL. 4 1 , NO. 12, OCTOBER 1969

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9A

AC BRIEFS Gas—Liquid Chromatographic Determination of Solution Properties of Oxygenated Compounds in Water

Column Parameters for Ultra-Low Loaded Glass Bead Columns in Gas Chromatography

Activity coefficients are determined at solute concentrations from infinite dilution to 5.0 mole per cent for low-molecular weight oxygenated organic compounds.

Corning 0201 beads give better column efficiency than Ballotini beads in G L C because of faster mass transfer in both phases, higher permeability, and much lower adsorption, at loads from 0.004 to 0 . 1 % .

DANIEL L. SHAFFER and THOMAS E. DAUBERT, Depart­ ment of Chemical Engineering, The Pennsylvania State University, University Park, Pa. 16802 Anal. Chem., 41, 1585 (1969)

S. J. HAWKES and D. G. NYBERG, Bringham Young Uni­ versity, Provo, Utah Anal. Chem., 41, 1613 (1969)

Computer Assisted Reaction-Rate Analyses Effects of Micropores on Peak Shape and Retention Volume in Gas-Solid Chromatography A high-precision gas ehromatograph is used to changes in retention volume with flow rate.

observe

J. E. OBERHOLTZER and L. B. ROGERS, Department Chemistry, Purdue University, Lafayette, Ind. 47907

of

A small digital computer performs preliminary measure­ ments to optimize measurement conditions. High-reliability data are obtained for wide concentration ranges. GERALD E. JAMES and HARRY L. PARDUE, Department of Chemistry, Purdue University, Lafayette, Ind. 47907 Anal. Chem., 41, 1618 (1969)

Anal. Chem., 41, 1590 (1969)

Radiochemical Determination of Uranium and the Transuranium Elements in Process Solutions and Environmental Samples

Real-Time Sampling Algorithm in an On-line Computer System for Gas Chromatographs An algorithm for gathering equally time-spaced data into a computer from several concurrently operating gas chro­ matographs is presented.

By addition of dilute barium solution dropwise to the sam­ ple solution at its boiling point, precipitation of the elements being carried is increased to 99.995%.

A. W. WESTERBERG, Control Data Corp., 4455 Eastgate Mall, La Jolla, Calif. 92037 Anal. Chem., 41, 1595 (1969)

CLAUDE W. SILL and RODGER L. WILLIAMS, Health Ser­ vices Laboratory, U. S. Atomic Energy Commission, Idaho Falls, Idaho Anal. Chem., 41, 1624 (1969)

Effect of Column to Particle Diameter Ratio on the Dispersion of Unsorbed Solutes in Chromatography

Multielement Neutron Activation Analysis of Rock Using Chemical Group Separations and High Resolution Gamma Spectrometry

The effects of column-to-particle-diameter ratio on disper­ sion of unsorbed solutes are reported and discussed in terms of Gidding's nonequilibrium theory. JOHN H. KNOX and JON F. PARCHER, Department Chemistry, University of Edinburgh, U. K.

of

Anal. Chem., 41, 1599 (1969)

The method is used to determine 45 elements in the three U. S. Geological Survey standard rocks: BCR-1, AGV-1, and G-2. G. H. MORRISON, J. T. GERARD, A. TRAVESI, R. L. CURRIE, S. F. PETERSON, and Ν. Μ. POTTER, Chemistry Department, Cornell University, Ithaca, Ν. Y. 14850 Anal. Chem., 41, 1633 (1969)

Further Studies on the DC Carbon Arc, Gas-Chromatographic Technique for the Determination of Gases in Metal

Analysis of Crude Oil Carboxylic Acids after Conversion to Their Corresponding Hydrocarbons

New observations on several important phenomena related to arc extraction of the oxygen and nitrogen content of metals are presented.

After conversion, identification is achieved by silica gel and gel permeation chromatography combined with UV, IR, and mass spectrometry.

ROYCE K. W/NGE and VELMER A. FASSEL, Institute for Atomic Research and Department of Chemistry, Iowa State University, Ames, Iowa 50010

WOLFGANG K. SEIFERT, RICHARD M. TEETER, W. GLENN HOWELLS, and MANFRED J. R. CANTOW, Chevron Re­ search Co., Richmond, Calif. 94802

Anal. Chem., 41, 1606 (1969)

Anal. Chem., 41, 1638 (1969) VOL. 4 1 , NO. 12, OCTOBER 1969

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11 A

AC BRIEFS Spectrophotometry Determination of Urea and Ammonia in Natural Waters with Hypochlorite and Phenol The lower limit of detection of both urea and ammonia analyses is 0.2 χ 10"° gram atoms nitrogen per liter in seawater of 35%„ salinity. ROBERT TEMPLE EMMET, Naval Ship Research and De­ velopment Laboratory, Annapolis, Md. 21402 Anal. Chem., 41, 1648 (1969)

Electron Acceptor Complexes for Chromogenic Detection and Mass Spectrometric Identification of Phenol and Aniline Derivatives, Related Fungicides, and Metabolites Electron acceptors are used to detect microgram amounts of aromatic amino and hydroxy compounds on thin layer plates. OTTO HUTZINGER, Atlantic Regional Lab., National Re­ search Council of Canada, Halifax, Nova Scotia, Canada Anal. Chem., 41, 1662 (1969)

Notes

Analysis of Human Hair by Spark Source Mass Spectrometry

Spectrophotometric Determination of Uranium(VI) with 2-(2-Pyridylazo)-5-diethyIaminophenol

Up to 27 elements are determined in human hair. Sample preparation and matrices are studied along with comparison data from different samples.

The complex formed has a molar absorptivity of 7.61 X 104 at 564 nm in 40% acetone and p H 8.2. The P A D A P method is also highly selective towards U ( V I ) . T. M. FLORENCE, D. A. JOHNSON, and YVONNE J. FARRAR, Analytical Chemistry Section, Australian Atomic Energy Commission, Lucas Heights, N.S.W., Australia Anal. Chem., 41, 1652 (1969)

Gas-Chromatographic Separation and Quantitative Determination of Arene Tricarbonylchromium Complexes Included in the study are benzene-, fluorobenzene-, methylbenzoate-, toluene-, mesitylene-, durene-, and hexamethylbenzene-tricarbonylchromium. HANS VEENING, NANCY J. GRAVER, DAVID B. CLARK, and BENNETT R. WILLEFORD, Department of Chemistry, Bucknell University, Lewisburg, Pa. 17837

J. P. YURACHEK, G. G. CLEMENA, and W. W. HARRISON, Department of Chemistry, University of Virginia, Char­ lottesville, Va. 22901 Anal. Chem., 41, 1666 (1969)

Oxidation-Reduction and Acid—Base Indicator Properties of Some Substituted Derivatives of Dicyanobis(l,10-Phenanthroline)lron(ll) Formal redox potentials and indicator properties of seven substituted derivatives are presented. The complexes are suitable indicators for both types of titrations. ALFRED A. SCHILT and JONATHON BACON, Department of Chemistry, Northern Illinois University, DeKalb, III. 60115 Anal. Chem., 41, 1669 (1969)

Anal. Chem., 41, 1655 (1969)

New Liquid-Liquid Extraction Method for the Separation of Cerium(IV) from Berkelium(IV) and Other Elements The method is based on the preferential extraction of Ce (IV) from dilute nitric acid solution containing bromate ion with a quaternary ammonium nitrate dissolved in xylene. FLETCHER L. MOORE, Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tenn.

Column Esterification in the Gas Chromatography of the Desalkyl Metabolites of Methyl Parathion and Methyl Paraoxon The gas chromatography of the desmethyl metabolites is possible by on-column esterification with injection of methanolic-HCl solutions of these metabolites. P. S. JAGLAN, R. B. MARCH, and F. A. GUNTHER, Depart­ ment of Entomology, University of California, Riverside, Calif. 92502 Anal. Chem., 41, 1671 (1969)

Anal. Chem., 41, 1658 (1969)

Determination of Organic Isocyanates and Isothiocyanates in Dimethylformamide

Determination of Vanadium by Controlled-Potential Coulometry

Dimethylformamide is used as the solvent and n-butylamine as the reagent to quantitatively determine aliphatics after reaction at room temperature for 10 minutes.

Milligram amounts of vanadium, as either V ( I V ) or V ( V ) , are determined by this method with an accuracy and pre­ cision of 0 . 1 % .

JOE A. VINSON, Chemistry Department, State College, Shippensburg, Pa. 17257

L. P. RIGDOM and J. E. HARRAR, Chemistry Department, Lawrence Radiation Laboratory, University of California, Livermore, Calif. 94550 Anal. Chem., 41, 1673 (1969)

Shippensburg

Anal. Chem., 41, 1661 (1969)

VOL. 41, NO. 12, OCTOBER 1969 • 13 A

AC BRIEFS Direct D e t e r m i n a t i o n of Oxygen in Coal

The method is based on sample pyrolysis at 1050 °C, cata­ lytic conversion of all oxygen into CO, determination of the volume of evolved gas, and measurement of the concentra­ tion of CO by gas chromatography. B. S. IGNASIAK, B. N. NANDI, and D. S. MONTGOMERY, Department of Energy, Mines, and Resources, Fuels Re­ search Centre, Ottawa, Canada Anal. Chem., 41, 1676 Poly-M-phenoxylene.

(1969)

A N e w Liquid Phase

The polar gas-chromatographic stationary phase reported is usable in the range from 125 °C to in excess of 400 °C. Physical properties are characterized and possible applica­ tions are presented. J . H. BEESON and R. E. PECSAR, Varian Mitchell Dr., Walnut Creek, Calif. 94598

Aerograph,

2700

Anal. Chem., 41, 1678

(1969)

Determination of Gold in Natural Waters at the Parts per Billion Level by Chelation and Atomic Absorption Spectrometry The method uses a polyschiff base in a column which spe­ cifically chelates gold. Concentrated metal is eluted from the chelate and determined by atomic absorption. ALBERT ZLATK1S, WILHELM BRUEN1NG, and ERNST BAYER, Department of Chemistry, University of Houston, Houston, Texas Anal. Chem., 41, 1692 (1969) Activity Measurements in Concentrated Sodium Chloride-Potassium Chloride Electrolytes Using Cation-Sensitive Glass Electrodes The mean activity coefficient of NaCl in mixed electrolyte is measured and agreement with isopiestic data is found. Electrode selectivity for sodium ions is retained at high ionic strengths. RIMA HUSTON and JAMES N. BUTLER, Tyco Laborato­ ries, Inc., Waltham, Mass. 02154 Anal. Chem., 41, 1695 (1969)

Reactions of S o m e Low-Spin Nickel Chelates with Heterocyclic Nitrogen Bases

Determination of 2,3-Dialkylaziridines by Direct Titration with Hydrogen Iodide

Equilibrium formation constants of some mono- and bidentate nitrogen bases with nickel chelates of dithizones, 8-mercaptoquinolinate have been measured. KUMAR S. MATH and HENRY Chemistry, University of Arizona,

FREISER, Department Tucson, Ariz. 85721

Anal. Chem.,

41, 1682

of

(1969)

G a s - C h r o m a t o g r a p h i c D e t e r m i n a t i o n of C , t o C 7 Monocarboxylic Acids and Lactic Acid by Pyrolysis of t h e Tetrabutyl A m m o n i u m Salts

In the 0.02 to 0.2 mg of aoid/ml range, the precision error is 5 % or less. The conversion appears linear in the range 0.2-6 ,ug of lactic acid. J . W. SCHWARZE and MARION N. GILMOUR, Department of Bacteriology, Eastman Dental Center, Rochester, Ν. Υ. 14603 Anal. Chem., 41, 1686 (1969)

Internal aliphatic aziridines, unsubstituted on nitrogen, are treated with acetic anhydride and titrated with H I formed in situ from 0.02ÏV perchloric acid and tetrabutyl ammonium iodide. GERHARD MAERKER, E. T. HAEBERER, L. M. GREGORY, and T. A. FOGLIA, Eastern Utilization Research & Development D/v., Philadelphia, Pa. 19118 Anal. Chem., 41, 1698 (1969) Gas-Liquid Chromatographic Determination of Oligogalacturonic Acids The precision of the method as determined for digalacturonic acid methyl ester is 1.8% and the relative error, 1.6%. The method is used to analyze an enzyme digest mixture. WYNN R. RAYMOND and CHARLES W. NAGEL, Food Sciences Program, Dept. of Horticulture, Washington State University, Pullman, Wash. 99163 Anal. Chem., 41, 1700 (1969)

Atomic Absorption D e t e r m i n a t i o n of T r a c e Elements in C a l c i u m Sulfate M i n e r a l s U s i n g a n Organic Enrichment Technique

Automatic Titration of Calcium with EDTA Using a Calcium-Selective Electrode

I n the proposed method, the sample solution containing Cd as a collector, is treated with three organic reagents, and the p H is adjusted to 5.9.

The method uses a commercial automatic titrator and a calcium selective electrode for precise titrations of Ca with E D T A . A relative precision of ± 0.05% is achieved.

JOHN W. HUSLER and EDGAR F. CRUFT, University of New Mexico, Department of Geology, Albuquerque, N.M. 87106 Anal. Chem., 41, 1688 (1969)

STANFORD L. TACKETT, Indiana University of Pennsylvania, Indiana, Pa. 15701 Anal. Chem., 41, 1703 (1969)

2-[(2-Hydroxy-5-nitrophenyl)azo]-4,5-diphenylimidazole Monoacetic Acid as a n Analytical Reagent

The crystalline reagent described is used as a metallochromic indicator in E D T A titrations and for the spectro­ photometry determination of cobalt and copper. L. E. MATTISON, J. M. METAXAS, and C. S. O'DELL, De­ partment of Chemistry, King College, Bristol, Tenn. 37620 Anal. Chem., 41, 1690

(1969)

Rapid Mass Spectrometric Determination of Chromium as Chromium(lll) Hexafluoroacetylacetonate Samples are oxidized with perchloric acid in a sealed tube, and then simultaneously reduced and complexed with hexafluoroacetylacetone to give the volatile chromium chelate. JAMES L. BOOKER and T. L. ISENHOUR, Department of Chemistry, University of Washington, Seattle, Wash. 98105, and R. E. SIEVERS, Aerospace Research Laboratories, ARC, Wright Patterson Air Force Base, Ohio 45433 Anal. Chem., 41, 1705 (1969) VOL. 4 1 , NO. 12, OCTOBER 1969 • 15 A

Circle No. 60 on Readers' Service Card

A C BRIEFS Aids for Analytical Chemists Gas Purification and Pressure Control System for Inert Atmosphere Boxes I. DWAINE EUBANKS and FLOYD J. ABBOTT, Department of Chemistry, Oklahoma State University, Stillwater, Okla. 74074 Anal. Chem., 41, 1708 (1969)

Klett

...

Photometers Klett Summerson

Photoelectric Glass Cell Colorimeter

Titrimetric Determination of Acid Gases in Alkali Hydroxides and Amines RALPH H. WEILAND and OLEV TRASS, Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto 5, Canada Anal. Chem., 41, 1709 (1969) No. 900-3

Determination of Carbon Dioxide in Aqueous Solutions under Pressure PAUL B. STEWART, PREM K. MUNJAL, and FRANK QUIR­ ING, Sea Water Conversion Lab. and Department of Mechanical Engineering, University of California, Berkeley, Calif. 94720 Anal. Chem., 41, 1710 (1969)

The Klett Fluorimeter

Gas-Sampling Technique for Arsenic Determination by Atomic Absorption Spectrophotometry WALTER HOLAK, Food and Drug Administration, Third Ave., Brooklyn, Ν. Y. 11232

850

Anal. Chem., 41, 1712 (1969) Motor-Speed Control for Rotating Disk Electrode Systems J. D. E. Mc/NTYRE and W. F. PECK, Bell Telephone Lab­ oratories, Inc., Murray Hill, N. J. Anal. Chem., 41, 1713 (1969) No. 2070

Procedure for Determination of Lead-210 and Total Lead in Biological Samples J. C. LANGFORD, Battelle Memorial Northwest Lab., Richland, Wash. 99352

Institute,

Pacific

Anal. Chem., 41, 1716 (1969)

Designed for the rapid and accurate determina­ tion of thiamin, riboflavin, and other substances which fluoresce, in solution. The sensitivity and stability are such that it has been found particularly useful in determining very small amounts of these substances.

Nonextinguishing Flame Photometric Detector Burner and Housing for Gas Chromatography Η. Α. ΜΟΥΕ, Pesticide Research Laboratory, Department of Food Science, University of Florida, Gainesville, Fia. Anal. Chem., 41, 1717 (1969)

New Rapid Method for Average Particle Size Measurement FRED 0. CARTAN and GEORGE J. CURTIS, Idaho Nuclear Corp., Idaho Falls, Idaho 83401 Anal. Chem., 41, 1719 (1969)

KLETT SCIENTIFIC PRODUCTS PHOTOELECTRIC COLORIMETERS · BIO-COLORIMETERS COLORIMETER-NEPHELOMETERS · COLONY MARKER • KLETT REAGENTS · GLASS CELLS

Klett

Manufacturing Co., Inc.

179 EAST 87TH STREET, NEW YORK, Ν. Υ. Circle No. 41 on Readers' Service Card VOL. 4 1 , NO. 1 2 , OCTOBER 1 9 6 9 • 17 A