A C BRIEFS Highlights of Articles in This Issue
A Kinetic Method for the Determination of Fluoride in the Parts-per-Biilion Range
Gas Chromatographic Estimation of Occluded Solvents in Adhesive Tape by Periodic Introduction Method
Trace amounts of fluoride can be determined very sensi tively by its strong inhibiting action on the catalyst in the zirconium catalyzed reaction between, perborate and iodide.
A new direct method for estimating occluded solvents in coated poljaneric materials has been developed b y means of gas chromatography.
DIETER KLOCKOW, HEINER LUDWIG, and MIGUEL A. GIRAUDO, Chemical Laboratory, University of Freiburg, Freiburg Br., German Federal Republic
MIKIO SUZUKI, Research Department, Nichiban Company, Nerima-ku, Tokyo, Japan, and SHIN TSUGE and TSUGIO TAKEUCHI, Department of Synthetic Chemistry, Faculty of Engineering, Nagoya University, Nagoya, Japan
Anal. Chem., 42, 1682
(1970)
Anal. Chem., 42, 1705 (1970) Determination of Sodium Nitrate in Sodium Nitrite by Selective Ion Electrode Measurement Small amounts of sodium nitrate in sodium nitrite were measured using a nitrate selective ion electrode. Precision (95% confidence) was ± 0 . 0 2 % at the 0.20% nitrate concen tration level. DOUGLAS G. GEHRING, WILLIAM A. DIPPEL, and ROBERT S. BOUCHER, Eastern Laboratory, Explosives Department, E. I. du Pont de Nemours & Company, Gibbstown, N. J. 08027 Anal Chem., 42, 1686 (1970) Rate Measurements of Highly Variable Gas Evolution with a Mass Flowmeter
The automatic a n d continuous recording of the titrant u p take during hydrogénation of olefins using the Brown catalytic hydrogénation technique offers quicker data interpretation and a uniform permanent record. J. J. SZAKASITS, Houston Research Laboratory, Shell Oil Company, P. O. Box 100, Deer Park, Texas 77536 Anal. Chem., 42, 1708
(1970)
Nitrogen Adsorption on Chemically Modified Silica Gels
A mass flowmeter-recorder combination to measure steadystate gas flow is satisfactory for measuring highly variable rates of gas evolution provided necessary corrections are made. Response is rapid and precision high. /SAO MATSUZAKI, ROBERT B. ALEXANDER, and HERMAN A. LIEBHAFSKY, Department of Chemistry, Texas A & M University, College Station, Texas 77843 Anal. Chem., 42, 1690
Automatic Data Recording of Unsaturation by Quantitative Hydrogénation
(1970)
Use of the Molecular Orbital Theory of Charge Transfer Spectra in Searching for Multiple Charge Transfer Bands of the Pi Complexes of 2,3-Dichloro-5,6-Dicyano-p-Benzoquinone M a n y organic π complexes frequently exhibit two charge transfer spectral bands. The Dcwar molecular orbital theory of charge transfer spectra can be used to calculate locations of both the lowest energy and the higher energy bands. GEORGE H. SCHENK and PETER A. FRYER, Department of Chemistry, Wayne State University, Detroit, Mich. 48202
Silica gels modified by attachment of organic groups were studied to determine changes in properties derivable from adsorption isotherms. Site energy distribution profiles showed increased uniformity of surface, and average adsorption energy decreased. JAMES B. SORRELL and ROBERT ROWAN, JR., Mexico State University, Las Cruces, Ν. Μ. Anal. Chem., 42, 1712
New (1970)
Modified Silica Gel Adsorbents in Gas—Solid Ch romatography Chemically modified silica gels, used as adsorbents in gassolid chromatography, showed marked improvements in column efficiency, better resolution, and reduction of tailing. ROBERT ROWAN, JR., and JAMES B. SORRELL, Depart ment of Chemistry, New Mexico State University, Las Cruces, Ν. Μ. 88001 Anal. Chem., 42, 1716 (1970)
Anal. Chem., 42, 1694 (1970) Pyrolysis Gas Chromatographic Determination of Arylsulfonic Acids and Salts
Elutive Displacement of Precipitate Formed d u r i n g Electromigration of Ions The elution phenomenon during electromigration is treated theoretically and examples are given for the way the method can be put in practice.
Sulfonic acids, upon pyrolysis, yield sulfur dioxide and the parent hydrocarbon. -Sulfur dioxide and, for some com pounds, the parent hydrocarbon can be measured quanti tatively for a wide range of sample sizes.
JORIS DEMAN, Kliniek voor Radiothérapie en Kerngeneeskunde, Akademisch Ziekenhuis, Gent, Belgium
SIDNEY SIGGIA and LEE R. WHITLOCK, Massachusetts, Amherst, Mass. 01002
Anal. Chem., 42, 1699
(1970)
University
Anal. Chem., 42, 1719
ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
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(1970) ·
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AC Determination of Medazepam ( N o b r i u m ) , Diazepam (Valium) and Their Major Biotransformation Products in Blood and Urine by Electron Capture G a s - L i q u i d Chromatography
Fluorometric Measurement of Aromatic Hydrocarbon Mixtures after the Diels—Alder Reaction of Anthracene
A sensitive and specific electron capture gas chromato graphic assay was developed for the determination of medazepam and diazepam and their major metabolites in blood and urine with a sensitivity limit of 0.02 to 0.04 μg of c o m p o u n d / m l . J. ARTHUR F. DE S/LVA and CARL V. PUGL/Si, Depart ment of Clinical Pharmacology, Hoffman-La Roche Inc., Nutley, N. J. 07110 Anal. Chem., 42, 1725
(1970)
Quantitative Analysis of Triglyceride Mixtures by Mass Spectrometry A rapid and sensitive mass spectrometric m e t h o d has been developed for determining the molecular weight distribu tion of triglyceride mixtures. Triglyceride composition and structure are thereby deduced. RONALD A. HITES, Northern tory, Peoria, III. 61604
Regional
Research
Anal. Chem., 42, 1736
BRIEFS
Labora (1970)
Diffusion Coefficients of Ferri- and Ferrocyanide Sons in Aqueous Media, Using Twin-Electrode Thin-Layer Electrochemistry A critical evaluation of this steady-state amperometriccoulometric m e t h o d is m a d e . D-values found for ferri- and ferrocyanide in LOOM KC1 are 0.726(±0.011) χ 10' 5 and 0.667(±0.014) χ 10~5 cmVsec., respectively, with essentially identical values in 0.10M" KC1. S. J. KONOPKA and BRUCE MCDUFFIE, Department of Chemistry, State University of New York at Binghamton, Binghamton, Ν. Y. 13901 Anal. Chem., 42, 1741 (1970)
T h e Diels-Alder adduct of maleic anhydride and anthracene is not fluorescent (although it is phosphorescent). This per mits the fluorometric measurement of some aromatic hydro carbons. GEORGE H. SCHENK and DONALD R. W/RZ, Department of Chemistry, Wayne State University, Detroit, Mich. 48202 Anal. Chem., 42, 1754
(1970)
Gas—Liquid Chromatographic Determination of Chlorpheniramine in Blood Plasma Flame ionization detectors have adequate sensitivity when coupled with selective and efficient extraction methods, modern column technology and a semi-programmed mode of operation. EDWARD TOWNLEY, ISIDORO PEREZ, and PETER KABASAKALIAN, Research and Development Division, Schering Corp., Bloomfield, N. J. 07003 Anal. Chem., 42, 1759
(1970)
Diffusion Controlled Polarographic Catalytic Hydrogen (Brdicka) Currents in Systems Containing C o b a l t ( l l ) , Cysteine-Like Compounds, and Alkaline Buffers Catalytic Brdicka currents obtained with cysteine-like com pounds become diffusion controlled when the molar ratio of the sulfhydryl compounds to cobalt(II) attains a certain value which is close to 1. /. M. KOLTHOFF, School of Chemistry, University of Minne sota, Minneapolis, Minn. 55455, and P. MADER, Depart ment of Biophysics and Plant Physiology, University of Agriculture, Prague 6, Czechoslovakia Anal. Chem., 42, 1762
(1970)
Trace Analysis of Pesticides Using Cholinesterase f r o m Human Serum, Rat Liver, Electric Eel, Bean Leaf Beetle, and White Fringe Beetle
Method and Apparatus for Determining Helium Content of Gas Mixtures A m e t h o d and apparatus are presented for determining the helium content of gaseous mixtures. T w e n t y or more analyses with a standard deviation of ± 0 . 0 4 % can be made in eight hours. DAVID E. EMERSON and RICHARD L. KAPLAN, Division of Helium, Bureau of Mines, U. S. Department of the Interior, Amarillo, Texas 79106 Anal. Chem., 42, 1746 (1970)
In this present study, the inhibitory effects of 14 different pesticides including organophosphorus compounds, carba mates, and chlorinated hydrocarbons on cholinesterase from human serum is reported. M. H. SADAR, S. S. KUAN, and G. G. GUILBAULT, Depart ment of Chemistry, Louisiana State University in New Orleans, New Orleans, La. 70122 Anal. Chem., 42, 1770
Use of Selective Ion Exchange Paper in X-Ray Spectrography and Neutron Activation. Application to the Determination of Gold
(1970)
Effect of Matrix Material on Laser-Induced Elemental Spectral Emission
A new collection procedure provides a simple means of preconcentrating trace elements from large samples. T h e determination of gold in the ppm and ppb ranges is given as an example. THOMAS E. GREEN, STEPHEN L. LAW, and WILLIAM J. CAMPBELL, U. S. Department of the Interior, Bureau of Mines, College Park Metallurgy Research Center, College Park, Md. 20740 Anal. Chem., 42, 1749 (1970)
The magnitude of suppression of spectral emission of silver and magnesium b y organic and inorganic material with laser microprobe sampling and excitation was studied. KENNETH W. MARICH, PETER W. CARR, WILLIAM J. TREYTL, and DAVID GLICK, Division of Histochemistry, Department of Pathology, Stanford University School of Medicine, Stanford, Calif. 94305 Anal. Chem., 42, 1775
ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
(1970) 11A
AC An Electrode for Determination of Amino Acids An electrode for the determination of amino acids is described which is made with immobilized L-amino acid-oxidase. T h e electrode detects S H j * ions formed in the enzyme catalyzed oxidation of the amino acid. G. G. GU1LBAULT and E. HRABANKOVA, Department of Chemistry, Louis/ana State University in New Orleans, New Orleans, La. 70122 Anal. Chem., 42, 1779 (1970)
Gas—Liquid Chromatographic Study of Selected Derivatives of 2-lmidazolidinone
AUSTIN L. BULLOCK and STANLEY P. ROWLAND, Southern Regional Research Laboratory, P. O. Box 19687, New Orleans, La. 70119 Anal. Chem., 42, 1783 (1970)
Separations of Enantiomeric Derivatives of Amines and Amino Acids by Adsorption Chromatography Chromatographically active and inactive solid, forms of the ureide of L-valine isopropyl ester are described as well as the behavior below the melting point of two other opticallyactive stationary phases. of Chem-
Anal. Chem., 42, 1786
(1970)
Described is the use of a polyalkylene amine ion exchange resin in mixed solvents to effect separation of aromatic sulfonates. T h e separation of phenol sulfonates, amino-sulfonates, and diphenyl sulfonates is described. RUDOLPH H. STEHL, Analytical Laboratories, Chemical Company, Midland, Mich. 48640
The Dow
Anal. Chem., 42, 1802
(1970)
Determination of the Number and the Nature of the End Groups of Poly(Vinyl Chloride) Optimum conditions of complete reaction of P V C and model compounds with lithium aluminum hydride have been established. One unsaturated end group, 1-chlorovinyl, seems to be present in each P V C molecule. MARC CARREGA, CLAUDE BONNEBAT, and GEORGES ZEDNIK, Péchiney-Saint Gobain, Centre de Recherches de la Croix-de-Berny, 182, Avenue Aristide Briand, 92 Antony, France Anal. Chem., 42, 1807 (1970) Spectrophotometric Submïcrodetemiination of Nitrites after Double Extraction of the Azo Compound Produced An extraction followed b y a retrograde extraction with different p H ranges is proposed in order to improve the optim u m concentration range for a classical method for spectrophotometric determination of nitrite. G. R. MACCHI and B. S. CESCON, Osservatorio Geofisico Sperimentale, Viale Romolo Gessi, 4 Trieste, Italy Anal. Chem., 42, 1809
Separation and Characterization of Methylethylnaphthalene Isomers by Chromatographic and Spectrometric Methods Thirteen of the fourteen possible methylethylnaphthalene isomers were characterized in the synthetic mixtures using instrumental methods of analysis. T h e sterically hindered l-methyl-8-ethylnaphthalene was not found. J. M. DUSWALT and T. J. MAYER, Sun Oil Company, Marcus Hook, Pa. 19061 Anal. Chem., 42, 1789 (1970)
Chemiluminescent Measurement of Atmospheric Ozone. Response Characteristics and Operating Variables T h e chemiluminescent reaction of ozone with a dye compound adsorbed on silica gel has previously been used to monitor ozone concentration in the upper atmosphere. J. A. HODGESON, K. J. KROST, A. E. O'KEEFFE, and R. K. STEVENS, U. S. Department of Health, Education, and Welfare, Public Health Service, Consumer Protection and Environmental Health Service, National Air Pollution Control Administration, Division of Chemistry and Physics, 3820 Merton Drive, Raleigh, N. C. 27609 Ana!. Chem., 42, 1795
Separation and Détermination of Aromatic Sulfonates by Ion Exchange Column Chromatography
Notes
T h e effect of p H on reactions occurring in aqueous solutions of methoxymethyl methyl imidazolidinone was investigated by G L C . Low p H increases the rate of conversion to the final product, methylenebis-l-[3-methyl-2-imidazoIidinone)].
J. A. CORBIN and L. B. ROGERS, Department istry, Purdue University, Lafayette, Ind. 47907
BRIEFS
(1970)
(1970)
Combination of Gas Chromatography and Chemical Ionization Mass Spectrometry A Bendix T O F mass spectrometer has been combined with a gas chromatograph to give a G C - M S system in which the carrier gas of the chromatograph also serves as the chemical ionization reactant gas. DONALD M. SCHOENGOLD and BURNABY MUNSON, Department of Chemistry, University of Delaware, Newark, Del. 19711 Anal. Chem., 42, 1811 (1970) Determination of Blood Ammonia by Derivative Spectrometry Total blood ammonia was determined by liberating ammonia gas from an alkalinized supernatant sample in a closed cell and measuring the ammonia partial pressure using a second derivative spectrometer. ROBERT N. HAGER, JR., DAVID R. CLARKSON, and JOHN SAVORY, Department of Aerospace Engineering, University of Florida, Gainesville, Fla. Anal. Chem., 42, 1813
ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
(1970) « i3 A
AC Analysis of /3,/j'-Bis-(Chlorocyclohexyl) Sulfides Mixtures of bis-(chlorocyclohexyl) rnonosulfide and polysulfides (ïan be analyzed rapidly b y I R spectrophotometry. Analysis for rnonosulfide b y titration of hydrolyzed chlorine and semi-quantitative analysis of mixtures by thin-layer chromatography are described. DUNCAN A. MACKILLOP, Dunlop Research Center, Sheridan Park, Ontario, Canada Anal. Chem., 42, 1815 (1970)
BRIEFS
Determination of Fluoride in Silicate Rocks without Separation of Aluminum Using a Specific Ion Electrode A technique for potential measurement of fluoride in solu tions containing 0.02 to 0.4 ppm F is described. Aluminum interference is controlled with O.lAi sodium citrate. BLANCHE L. INGRAM, U. S. Geological Survey, Washing ton, D. C. Anal. Chem., 42, 1825 (1970)
Simple, Rapid, Gravimetric Method for the Estimation of Phenylphosphine and Pentaphenylcyclopentaphosphine
Gas Chromatographic and Related Properties pf the Alkaline Earth Chelates with 2,2,6,6-Tetramethyl-3,5-Heptahedione
Dilute solutions of phenylphosphine and pentaphenylcyclopentaphosphine quantitatively reduce tellurium tetrachloride to the metal and provide a rapid, convenient method for the analysis pf these air sensitive compounds.
2,2',6,6-Tetramethyl-3,5-heptanedionato chelates of calcium and strontium have considerably different gas chromato graphic retention times. In spite of these differences, it was possible to separate mixtures of the metal chelates.
M. J. GALLAGHER and I. D. JENKINS, Department of Organic Chemistry, University of New South Wales, Kensington, N.S.W., 2033, Australia Anal. Chem., 42, 1817 (1970)
J. E. SCHWARBERG, R- E. SIEVERS, and R. W. MOSHIER, Contribution from the Chemistry Research Laboratory, Aerospace Research Laboratories, ARC, Wright-Patterson Air Force Base, Ohio 45433 Anal. Chem., 42, 1828 (1970)
Enhanced Stability of Sulfur Dioxide in Solution The stability of SO a in solutions of tctracbloromercuratc is enhanced by the addition of ethylenediamine tetraacetate. The decay rate is 1% per day and is independent of the concentration of SO2 because it follows a first order reaction. F. P. SCARINGELLI, L. ELFERS, D. NORRIS, and S. H0CHHE/SER, Division of Chemistry and Physics, National Air Pollution Control Administration, Environmental Health Service, Public Health Service, U. S. Department of Health, Education, and Welfare, Cincinnati, Ohio 45226 Anal. Chem., 42, 1818
(1970)
Détermination of Trace Elements In Glass by Activation Analysis Using Hydrated Antimony Pentoxide for Sodium Removal Methods are described for the determination b y neutron activation analysis of ppm and ppb levels of some trace elements in glass containing 10% sodium. THOMAS E. GILLS, WILLIAM F. MARLOW, and BARBARA A. THOMPSON, Analytical Chemistry Division, National Bureau of Standards, Washington, D. C. 20234 Anal. Chem-, 42, 1831 (1970)
Spark Source Mass Spectrometric Survey Analysis of Air Pollution Particulates A survey for trace elements in air pollution particulates may be carried out with detection limits in the nanogram per cubic meter range, and precision estimated at ± 3 0 % standard deviation. R. BROWN and P. G. T. VOSSEN, Consultant Laboratory, ΑΕΙ Scientific Apparatus Ltd., Manchester, England Anal. Chem., 42, 1820
(1970)
Cadmium(H)/Cadmium(Mercury) Exchange and Double Layer Structure The application of two different criteria, that the ΐίτι and Ci. remain constant and t h a t the correct behavior of the Warburg impedance for solving the model of the electrode interphase be used, yield differing results. An alternative model of the electrode interphase is proposed. NOEL A. HAMPSON, Department of Chemistry, Lough borough University of Technology, Loughborough, Leices tershire, England and DAVID LARKIN, Department of Chemistry, The University of Texas at Austin, Austin, Texas 78712 Anal. Chem., 42, 1823 (1970)
Determination of Tin in Copper-Base Alloys by Mossbauer Spectrometry The Mossbauer spectrometric method was applied to the determination of tin in NBS S R M copper-base alloys. The absorption intensity of SnO z was measured vs. ,8-Sn as an internal standard absorber. P. A. PELLA and J. R. DEV0E, Institute for Materials Research, National Bureau of Standards, Washington, D. Ç. 20234 Anal. Chem., 42, 1833 (1970)
Analysis of Butyllithium and Butylsodium in the Presence of Alkoxides The effect of various alkoxides of lithium, sodium, and potassium in the determination of the activity of BuLi and B u N a compounds was studied· R. R. TURNER, A. G. ALTENAU, and T. C. CHENG, The Firestone Tire and Rubber Company, Central Research Laboratories, Akron, Ohio 44317 Anal. Chem., 42, 1835
ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
(1970) .
15 A
AC Complex Formation in Lead Oxalate Solutions A solubility technique was used to characterize the com plexes formed in lead oxalate solutions. Ionic strength and temperature effects arc presented. T h e presence of two mononuclear species of lead oxalate is established. LEON N. KLATT, Department Georgia, Athens, Ga. 30601
of Chemistry,
University
Anal. Chem., 42, 1837
of
(1970)
BRIEFS
Microdetermination of Molybednum by Anodic Stripping at Constant Current Using the Hanging Mercury Drop Electrode The stripping method used for analyzing dilute M o ( V I ) solutions gives a relative precision of ±1.7%' for \0~lM solutions and ± 5 % for 5 χ IQ~°M solutions. PHILIPPE LAGRANGE, and JEAN-PAUL SCHWING, Insti tut de Chimie, 1 rue Blaise Pascal, 67—Strasbourg, France Anal. Chem., 42, 1844
(1970)
High Resolution Field Ionization Mass Spectrometry of the Condensable Phase of Cigarette Smioke Field ionization is used to enhance the molecular ion in tensities of the components of cigarette smoke condensate. The elemental composition of 56 ions in the field ionization mass spectra of this complex mixture is reported. J. B. FOREHAND and W. F. KUHN, Philip Morris, Inc., P. O. Box 3D, Richmond, Va. 23206 Anal. Chem., 42, 1839 (1970)
Correspondence Quaternary Oxide Systems as Hosts for X-Ray Excited Optical Fluorescence Detection of Rare Earths in Nuclear Materials at the Part per Giga (Part per 10 s ) Level ARTHUR P. D'SILVA, EDWARD L. DEKALB, and VELMER A. FASSEL, Institute for Atomic Research and Department of Chemistry, Iowa State University, Ames, Iowa 50010
Carbowax as Dispersant in Counting and Sizing of Small Alumina Particles Using a Coulter Counter
Anal. Chem., 42, 1846
Carbowax-1500 is found to be the best of a series of dis persants used in sizing alumina with a Coulter Counter. T h e relative standard deviation of the measurements is improved by a factor of two in comparison to the best of the other dispersants used (Triton X-100).
(1970)
Aids for Analytical Chemists
ELMER C. LUPTON, JR. and PATRICIA A. SHELBY, Air Force Rocket Propulsion Laboratory, Edwards, Calif. 93523 Anal. Chem., 42, 1841
(1970)
Simplified Laser Degradation Inlet System for Gas Chromatography WILLIAM T. RISTAU and NICHOLAS E. VANDERBORGH, Department of Chemistry, The University of New Mexico, Albuquerque, Ν. Μ. 87106
Rapid Method of Determining First-Order Rate Constants from Experimental Data
Anal. Chem., 42, 1848
A new graphical method of determining first-order rate constants is presented. The method utilizes a maximum in stead of a slope in the rate constant calculation; rate con stant error estimates are easily obtainable. RICHARD O. VIALE, Department of Biochemistry, School of Medicine, University of Pennsylvania, Philadelphia, Pa. 19104 Anal. Chem., 42, 1843 (1970)
(1970)
Rapid Acid-Hydrogen Peroxide Decomposition and Solubilization of Copper Phthalocyanines for Analysis DANIEL KRUH, Imperial Color and Chemical Department, Hercules Incorporated, Glens Falls, Ν. Y. 12801 Anal. Chem., 42, 1849
ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
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