AC BRIEFS Highlights of the scientific and technical articles in this issue
Lumometric End Point Detection for Nonaqueous Titrations The end point of nonaqueous titrations is determined by luminescence intensity. At the end point a sharp rise in luminescence occurs which is measured by a sensitive scintillation counter. T h e luminescence may be due to acidity-sensitive side reactions involving auto-oxidation products. MARTIN DIMBAT and G. A . HARLOW, Shell Development Co., Emeryville, Calif. Anal. Chem. 34, 450 (1962)
A New Automatic Spectrophotometric Rate Method for Selective Determination of Glucose in Serum, Plasma, or Blood The glucose content of serum, plasma, and blood samples is rapidly determined by an automatic spectrophotometric rate procedure. T h e method employs the same chemical system as for the potentiometric procedure, b u t the rate of formation of iodine is measured by an automatic spectrophotometric system. H. V. MALMSTADT and S. I. H A D J I I O A N N O U , University of Illinois, Urbana, III. Anal. Chem. 34, 452 (1962)
Specific Enzymatic Determination of Alcohol in Blood by an Automatic Spectrophotometric Reaction Rate Method. An enzymatic-speetrophotometric reaction rate technique is employed for the accurate and rapid determination of et.Hanoi in blood. T h e alcohol is oxidized in the presence of an enzyme and diphosphopyridine nucleotide ( D P N ) , producing the reduced form of the nucleotide, D P N H , which has a characteristic absorbance. Concentration is calculated from the reaction rate value. H. V. MALMSTADT and T. P. H A D J I I O A N N O U , University of Illinois, Urbana, III. Anal. Chem. 34, 455 (1962)
Programmed Temperature Gas Chromatography with Glass Microbeads. Quantitative Analysis of a Homologous Series of Alcohols and Hydrocarbons A 2-meter microbead column coated with Carbowax is suitable for a quantitative analysis of normal alcohols and alkanes and alkenes. A 30-component mixture of these compounds, ranging from C» through Cae is resolved in 30 minutes. The efficiency of this column is compared with various other column substrates. J. G. NIKELLY, Esso Research and Engineering Co., Linden, N. J . Anal. Chem. 34, 472 (1962)
Gas Chromatographic Study of Some Chlorinated Hydrocarbons Paraffin and Apiezon L columns are used for the investigation of the gas chromatographic behavior of eleven chlorinated hydrocarbons. Good qualitative and quantitative results are obtained and specific retention volumes are measured which permits the calculation of partition coefficients, activity coefficients, and excess partial molar heats of solution. PAUL URONE, J . E. SMITH, and R. J . KATNIK, University of Colorado, Boulder, Colo. Anal. Chem. 34, 476 (1962)
Identification of Alcohol Peaks in Gas Chromatography by a Nonaqueous Extraction Technique Gas chromatography is used for the identification of alcohol peaks in a procedure involving a separation technique. The method is based on the nonaqueous extraction of the alcohols from other organic compounds. The sample is dissolved in carbon tetrachloride and the alcohol extracted with propylene glycol. ROBERT SUFFIS and D. E. DEAN, Shulton, Inc., Clifton, N. J . Anal. Chem. 34, 480 (1962)
Liquid Distribution on Gas Chromatographic Support. Relationship to Plate Height A correlation is developed between gas chromatographic performance and the structure of the solid support in packed, capillary, and glass bead columns. Certain conclusions are presented, such as that the uniform film model of capillary columns is physically untenable, and that the liquid around the contact points of glass beads normally controls the plate height. All conclusions are offered in the light of practical implications. J. C. GIDDINGS, University of Utah, Salt Lake City 12, Utah Anal. Chem. 34, 458 (1962)
Determination of Dissolved Gases in Aqueous Solutions by Gas Chromatography Dissolved gases in concentrations as low as 0.3 p.p.m. in 1-2 milliliter samples of liquid are determined by gas chromatography. In a specially designed sample chamber, the dissolved gases are stripped from solution by a carrier gas and introduced directly into a conventional gas chromatograph for analysis. J . W . SWINNERTON, V. J . LINNENBOM, and C. H. CHEEK, U. S. Naval Research Laboratory, Washington D. C. Anal. Chem. 34, 483 (1962)
Gas Chromatographic Analysis of Aromatic Hydrocarbons a t Atmospheric Concentrations Using Flame Ionization Detection The hydrogen flame ionization detector is used in the gas chromatographic analysis of Ce to Cio aromatic hydrocarbons in automobile exhaust. Sensitivity is great enough to permit analysis of dilute exhaust and S3'nthctic "smogs." Photochemical reaction due to solar radiation reduces the hydrocarbon concentration in air. A. P. ALTSHULLER and C. A . CLEMONS, Robert A . Taft Sanitary Engineering Center, Cincinnati 26, Ohio Anal. Chem. 34, 466 (1962)
Determination of Boron-Hydrogen Bonding by Chemically Active Gas Chromatography A quantitative gas chromatographic procedure is developed for determining the total boron-hydrogen bonding in chloroboranes and boron hydrides. Hydrogen is produced in a wet 5A Molecular Sieve column and separated on a dry column of the same material. P. F. PUTNAM and H. W . MYERS, Stauffer-Aeroiet Laboratories, Nimbus, Calif. Anal. Chem. 34 486 (1962) VOL. 34, NO. 4, APRIL 1962
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BRIEFS Determination of the Relative Polarity of Sur face Active Agents by Gas-Liquid Chromatog raphy
A Comparison of Methods for Spot Test Detec tion and Spectrophotometric Determination of Glyoxal
A gas-liquid chromatographic technique permits the rapid estimation of relative polarity of surface active agents. The method is based on a comparison of the retention times of methanol and τι-hydrocarbons when the surface active agent is used as the liquid phase.
Certain spot test and spectrophotometric procedures are compared for their selectivity and sensitivity in the de tection of glyoxal. T h e 2-aminobenzenethiol and the 1,2dianilinoethane methods are the most selective, while the 4-nitrophenylhydrazine procedure is the most sensi tive. This latter method has certain interference problems.
V. R. H U E B N E R , Armour and C o . , Chicago, I I I . A n a l . C h e m . 34, 488 (1962)
Volatility Effects in the Paper Chromatography of the Lower Fatty Acids A study indicates the volatility effects due to temperature and humidity on the radioactive intensity of C"-tagged sodium salts of lower fatty acids on paper chromatograms. Losses in radioactivity are attributed to the hydrolysis of the salts and the volatility of the free acid formed. A . A . M O L L O Y and Θ . N . K O W K A B A N Y , versity of A m e r i c a , W a s h i n g t o n , D. C .
The Catholic
Uni
A n a l . C h e m . 34, 491 ( 1 9 6 2 )
Integral Chronoamperometry Manual Apparatus
with
a
Simple
Integral chronoamperometric measurements at stationary solid micro electrodes are made with a simple manual apparatus. T h e advantage of this apparatus lies in its use for the determination of concentration of species which require some type of solid electrode for their meas urement. T h e precision of this apparatus is equivalent to that of the manual polarograph.
E U G E N E S A W I C K I , T. R. H A U S E R , and R O N A L D W I L S O N , Robert A . Taft Sanitary Engineering Center, Cincinnati 26, Ohio A n a l . C h e m . 34, 505 ( 1 9 6 2 )
Polarography of Diethyldithiocarbamate, a Ti trant with the Rotated Dropping Mercury Indi cator Electrode A study is made of the polarographic behavior of diethyl dithiocarbamate and its use as a reagent for amperometric titrations. Results show that the rotated dropping mer cury electrode may be used as an indicator electrode for amperometric titrations of metal ions with diethyldithio carbamate used as reagent. W A L T E R STRICKS and S. K. C H A K R A V A R T I , M a r q u e t t e Uni versity, Milwaukee 3, W i s . A n a l . C h e m . 34, 508 ( 1 9 6 2 )
A New Polarographic Method for the Microdetermination of Chloropicrin in Air
A . L. BEILBY and A . L. BUDD, Pomona C o l l e g e , C l a r e m o n t , C a l i f . A n a l . C h e m . 34, 493 ( 1 9 6 2 )
Determination of Aluminum in Thorium Com pounds by Linear-Sweep Oscillographic Polarography Trace amounts of aluminum in thorium compounds are determined by oscillographic polarography. No separa tion of thorium is necessary, b u t heavy metal impurities are removed by rapid mercury-cathode electrolysis. Alu minum is complexed with an azo dye prior to being polarographed. Iron, nickel, lead, and vanadium interfere. T. M . F L O R E N C E , Australian A t o m i c Energy Commission Re search Establishment, Lucas Heights, N.S.W., Australia A n a l . C h e m . 34, 4 9 6 ( 1 9 6 2 )
Controlled-Potential Antimony
Coulometric
Titration
of
Controlled-potential coulometric titration procedures are developed for determining antimony in its two oxidation states. Antimony (III) is coulometrically reduced to Sb (Hg) as a mercury cathode in a 0AM acetic acid-lM hydrochloric acid electrolyte. Antimony(V) is reduced to ( I I I ) and subsequently to Sb(Hg) in a 0AM acetic acid-6M hydrochloric acid electrolyte.
A direct and rapid polarographic procedure is used for determining trace amounts of chloropicrin in air. The polarographic system employs a dropping mercury elec trode and a silver-silver chloride reference electrode. Air samples from fumigated grain, flour, and soil are analyzed. The presence of acrylonitrile causes serious interference. BEN BERCK and J O H N S O L O M O N , C a n a d a Department Agriculture Research Station, W i n n i p e g , Manitoba
of
A n a l . C h e m . 34, 514 ( 1 9 6 2 )
Determination of 2-lsovaleryl-l,3-indandione with 2,4-Dinitrophenylhydrazine. Rodenticide Analysis A sensitive and specific spectrophotometric method is described for determining the rodenticide, 2-isovalery 1-1,3indandione. T h e 2,4-dinitrophenylhydrazine of this ro denticide reacts with potassium cyanide and produces a colored complex with a strong absorbancc at 540 ταμ. Microgram amounts of the rodenticide are estimated by a spot test using the same reaction. C . M . M E N Z I E , V. A . A D O M A I T I S , and W . L. R E I C H E L , U . S. Fish and W i l d l i f e Service, Laurel, M d . A n a l . C h e m . 34, 516 ( 1 9 6 2 )
L B. D U N L A P and W . D. SHULTS, O a k Ridge N a t i o n a l Labora tory, Oalt Ridge, Tenn. A n a l . C h e m . 34, 4 9 9 ( 1 9 6 2 )
Ultra
Determination of Rare Earths in Fission Products by Ion Exchange a t Room Temperature
A single method is developed for calibrating a fluorescence spectrometer to give corrected fluorescence emission spectra in the ultraviolet region. Corrected emission spectra and relative fluorescence efficiencies are given for anthracene, naphthalene, phenol, and benzene.
A radiochemical method is described for the determination of rare earth elements in fission products. The rare earths are separated on a certain resin exchange column using a-hydroxylisobutyrate as the eluent. T h e activity is determined with a gamma scintillation counter and chem ical yield determined by titration with E D T A .
Spectrofluorometer violet Region
C . A . PARKER, A d m i r a l t y Poole, Dorset, England
Calibration
in the
M a t e r i a l s Laboratory, H o l t o n
Heath,
A n a l . C h e m . 34, 502 ( 1 9 6 2 )
KURT W O L F S B E R G , University o f C a l i f o r n i a , Los Alamos, Ν . Μ . A n a l . C h e m . 34, 518 ( 1 9 6 2 )
VOL. 34, NO. 4, APRIL 1962 • 11 A
BRIEFS Analytical Extraction of Neptunium Using Triiso-octylamine and Thenoyltriftuoroacetone
Further Elucidation of Hydrocarbon Types in Olefinic Gasoline by Mass Spectrometry
Neptunium is quantitatively extracted from plutonium, amerieium, curium, uranium, thorium, and fission products with tri-iso-oetylamine-xylene solution. This organic ex tract is scrubbed with nitric acid, then t h e neptunium is stripped from the solution into dilute hydrochloric acid, and finally extracted into thenoyltrifluoroacetone-xylene solution for analysis.
The mass spectrometric analysis of gasoline is extended to include the determination of a molecular weight dis tribution for alkylbenzenes, alkylindans, and alkylnaphthalenes. New calibration data and calculation procedures are given for various gasoline components. Using a dig ital computer, an analysis requires three and a half manhours.
R. A. SCHNEIDER, General Electric Co., Richland, Wash. Anal. Chem. 34, 522 (1962)
Study of the Titanium-N-Benzoyl-N-phenylhydroxylamine Complex Under controlled conditions the reagent, N-benzoyl-Nphenylhydroxylamine is found to be specific for the de termination of microgram quantities of titanium. T h e complex forms in an acidified alcohol solution and indi cates maximum absorbance at 340, 370, and 400 ιαμ. Iron, vanadium, and molybdenum are the principle sources of interference. J . E. S C H W A R B E R G A i r Force Base, O h i o
and R. W .
MOSHIER,
Wright-Patterson
A n a l . C h e m . 34, 525 ( 1 9 6 2 )
D. M . G . L A W R E Y and J . F. P A U L S O N , Sun O i l C o . , Marcus Hook, Pa. A n a l C h e m . 3 4 , 538 ( 1 9 6 2 )
Spectrophotometric Titration of phatic Amines
Primary
Ali
A direct spectrophotometric titration procedure determines primary aliphatic amines in the presence of secondary and tertiary amines and other basic substances. T h e amine solution is dissolved in an acetic acid and dioxane mixture and titrated with 2-ethylhexanol. The end point is meas ured by the absorbance of the excess aldehyde at 305 τημ. Y . G . L I U and C . A . R E Y N O L D S , University of Kansas, Lawrence, Kan. A n a l . C h e m . 34, 542 ( 1 9 6 2 )
of
Evaluation of an Automatic Nitrogen Analyzer for Tractable and Refractory Compounds
A spectrophotometric method determines microgram amounts of technetium and is based on the formation of the red technetium(V)-thiocyanate complex. This com plex is extracted from solution with butyl acetate and its absorbance measured at 585 ταμ. Uranium does not inter fere.
The Coleman automatic nitrogen analyzer is used for the rapid and accurate determination of tractable and re fractory compounds. T h e refractory sample must be oxidized by fusion with vanadium pentoxide in a platinum sleeve. T h e platinum sleeve acts as a catalyst and pro tects the quartz combustion tube at the same time.
Rapid Spectrophotometric Determination Technetium in Uranium Materials
O . H . H O W A R D and C . W . WEBER, Union C a r b i d e Nuclear C o . , Oalc Ridge, Tenn. A n a l . C h e m . 34, 5 3 0 ( 1 9 6 2 )
P. D. S T E R N G L A N Z and H E I N Z Institute, Birmingham, A l a .
KOLLIG,
Southern
Research
A n a l . C h e m . 34, 544 ( 1 9 6 2 ]
Use of 1,3-Dimethylvioluric Acid in Spectro photometric Titrations of Alkali and Alkaline Earth Salts
Use of Differential Reaction Rates to Analyze Mixtures of Organic Materials Containing the Same Functional Group. Application to Mix tures of Amines
Alkali and alkaline earth metals are determined by a spectrophotometric titration procedure. T h e aqueous sample solution is titrated with 1,3-dimethylvioluric acid which forms a colored chelate with the metals. The maximum absorbance of the complex is measured at 538 ιημ. T h e titrant is not specific for any of the metals in volved.
A differential reaction rate analysis technique is used for determining mixtures of primary, secondary, and tertian' amines, and mixtures of aliphatic and aromatic amines, as well as mixtures of homologous primary or secondary amines. The method involves the reaction between amines and isothiocyanate to form thiourea.
M. E. T A Y L O R and R. J . R O B I N S O N , University of Washing ton, Seattle, W a s h . A n a l . C h e m . 34, 533 ( 1 9 6 2 )
J . G . H A N N A and S I D N E Y S I G G I A , C o r p . , N e w H a v e n 4, C o n n .
Spectrophotometric Determination of Vanadium with 2,6-Pyridinedicarboxylic Acid
Calculation of Intrinsic Viscosities by the BakerPhilippoff Equation
Vanadium in the presence of diverse ions is determined by reactions with 2,6-pyridinedicarboxylic acid and hydro gen peroxide. T h e colored complex formed with a maxi mum absorbance at 430 χημ is specific for vanadium. Hydrofluoric acid is used to block the interference of iron and titanium.
A short-cut graphical method is used for calculating the constant a in the Baker-Philippoff equation for intrinsic viscosity. The constant is estimated by locating the ob served viscosity data on a specially prepared graph for the corresponding concentration. The technique is ap plicable for any polymer-solvent system.
G . A . PEARSE, Jr., LeMoyne C o l l e g e , Syracuse 3, Ν . Υ . A n a l . C h e m . 3 4 , 536 ( 1 9 6 2 )
O l i n Mathieson
Chemical
A n a l . C h e m . 34, 547 ( 1 9 6 2 )
L. B. G E N U N G and I. L. G A G E , Eastman Kodak C o . , Rochester, N. Y. A n a l . C h e m . 3 4 , 549 ( 1 9 6 2 )
VOL. 34, NO. 4, APRIL 1962
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BRIEFS Evaluation of Methods for the Determination of Mercuric Chloride on Carbon An isotope-dilution method and an x-ray fluorescence method are found most reliable for the determination of mercury on carbon inpregnated with mercuric chloride and cerous chloride. Methods other than these two give low, erratic results due t o t h e formation of the mercuric chloride-cerous chloride complex. R. L. MAUTE, R. H. BENSON, J . D. STROUD, NEIL HODGSON, and D. R. BEASECKER, Monsanto Chemical Co., Texas City, Tex. Anal. Chem. 34, S53 (1962)
The Determination of Antimony Oven Technique
by the
Ring
A ring oven technique is modified for the determination of micro amounts of antimony in air samples. T h e method utilizes solvent extraction of the formed antimony tetraiodide complex which forms a colored complex in reac tion with phosphomolybdic acid. No serious interfer ence is encountered. P. W . W E S T and A . J . LLACER, Louisiana State University, Baton Rouge, La. A n a l . C h e m . 34, 555 ( 1 9 6 2 )
Estimation of Beryllium with Eriochrome Cyanine R Using the Ring Oven Technique A rapid microdetermination of solutions of air containing beryllium uses Eriochrome Cyanine R as reagent in a ring oven technique. Sodium nitrilotriacetate is used as a masking agent, enhancing the selectivity of Eriochrome Cyanine Κ for beryllium. Interference is encountered from magnesium, thorium, chromium, and aluminum. P. W . W E S T and P. R. M O H I L N E R , Baton Rouge, La,
Louisiana State
University,
A n a l . C h e m . 34, 558 ( 1 9 6 2 )
Determination of Iodine in Mineral Premixes A titrimetric procedure is used for determining iodine in mineral premixes for livestock feeds. The sample is di gested and the iodine liberated upon the addition of formic acid. The iodine is distilled off and collected in a sodium hypochlorite solution. I t is then titrated with sodium thiosulfate. PERRY KING, E. S. BRETZ, and T. J. KNE1P. Mallinclcrodt Chem ical Works, St. Louis 7, Mo. Anal. Chem. 34, 565 (1962)
An Extractant for Microamounts of Anionic Sur f a c t a n t Bound to Large Amounts of Protein, with Subsequent Spectrophotometric Determination An extractant solution is prepared which will separate microamounts of anionic surfactants from combination with large amounts of protein. The extractant solution is composed of magnesium sulfate-sodium hydroxide and acetone. T h e extracted surfactants are determined by a spectrophotometric method. EDITH G O U L D , Harvard Medical General Hospital, Boston, Mass.
School
at
Massachusetts
A n a l . C h e m . 34, 567 ( 1 9 6 2 )
Spectrophotometric Determination of Micro gram Quantities of Manganese in Uranium and Aluminum with 8-Hydroxyquinaldine A spectrophotomeric method is devised for the deter mination of microgram amounts of manganese in uranium and aluminum metals. T h e manganese is complexed with 8-hydroxyquinaldine and extracted with chloroform. The absorbance of the extract is measured at 395 ταμ. In uranium analysis the uranium is previously extracted with tributyl phosphate. KENJI M O T O J I M A , H I R O S H I H A S H I T A N I , and T S U Y O S H I I M A H A S H I , Japan A t o m i c Energy Research Institute, Ibarakiken, Japan A n a l . C h e m . 3 4 , 571 ( 1 9 6 2 )
Olefin Isomerization in Adsorptive Sampling on Activated Carbon
Removal of Sulfur Fumes by Lead Dioxide in the Combustion Method for Carbon in Iron and Steel
Three unsaturated hydrocarbons are studied for their olefin isomerization in adsorption and desorption with activated carbon. Of the three, 1-hexene indicated no isomerization. Therefore, gasoline hydrocarbons may be sampled on carbon and recovered for analysis without serious structural rearrangement.
Lead dioxide is used for the removal of sulfur dioxide in the combustion method for determining carbon in iron and steel procedures. The lead dioxide is deposited as a film on quartz sand grains to reduce the retention time of carbon dioxide during the analysis.
A M O S TURK, J . I. M O R R O W , C o l l e g e , New York 3 1 , Ν . Υ.
and Β. Ε. K A P L A N , The C i t y A n a l . Chem. 34, 561 ( 1 9 6 2 )
Analysis of 4,4'-lsopropylidenediphenol by Iso tope Dilution An isotope dilution technique is used for the determination of 4,4'-isopropylidenediphenol. The procedure requires only a fraction of a gram of sample for analysis and is applicable to high purity grade samples as well as crude in-process materials. L. H . G R I F F I N , Shell Chemical C o . , Deer Park, Tex. A n a l . C h e m . 34, 564 ( 1 9 6 2 )
W . M . PETERSON, The A . H . Putnam C o . , Rock Island, I I I . A n a l . C h e m . 34, 575 ( 1 9 6 2 )
Determination of Hydrogen in Calcium by Vac uum Fusion A vacuum fusion technique using a tin bath at 670° C. quantitatively extracts hydrogen from calcium samples. The technique permits the rapid, accurate determination of hydrogen in calcium at concentrations from 200 p.p.m. of hydrogen to almost pure calcium hydride. D. T. PETERSON, Iowa State University, Ames, Iowa, and V. G . FATTORE, Sicedïson S.p.A., Centro Studi e Ricerche, Bol late, M i l a n , Italy A n a l . C h e m . 34, 579 (1962)
VOL. 34, NO. 4, APRIL 1962
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