AC BRIEFS H i g h l i g h t s f o r t h e s c i e n t i f i c a n d t e c h n i c a l a r t i c l e s in t h i s i s s u e
A d v a n c e s in S t r u c t u r e D e t e r m i n a t i o n Molecular structure determinations are aided by new physical methods and by coupling of the new methods with modern separation techniques. N'MR, E P R , the Mcissbauer effect, x-ray diffraction, microwave and Raman spectrometry, optical rotatory dispersion, circular dichroism, and fhe old technique of microscopy are discussed. F. W . McLAFFERTY, Department of Chemistry, Purdue University, Lafayette, Indiana Anal. Chem. 36, 2386 (1964)
Plasma A r c Solution S p e c t r o c h e m i s t r y . Evaluation and O p t i m i z a t i o n of O p e r a t i n g P a r a m e t e r s Items studied include the open discharge distance and cathode position, helium rate, plasma flow, effective arc resistance, operating current and voltage, response vs. position of view within the open gap, and sample size and intensity as a function of plasma composition. EDWARD H. SIROIS, Major Appliance General Electric Co., Louisville, Ky.
Division
Laboratories,
D e t e r m i n a t i o n of Beta-Olefinic Methyl Groups in Esters of F a t t y A c i d s by N u c l e a r M a g n e t i c Resonance The fact thai the resonance of the terminal methyl protons is shifted slightly downfield by a /3-olefinic bond is used as the basis for a quantitative procedure. Precision has been determined. CURTIS A. GLASS and HERBERT J . DUTTON, Northern Regional Research Laboratory, ARS, USDA, Peoria, III. Anal. Chem. 36, 2401 (1964)
Internal S t a n d a r d X-Ray S p e c t r o g r a p h i c P r o c e d u r e f o r t h e Determination of Calcium, Barium, Zinc, and Lead in H y d r o c a r b o n s The technique described compensates for interelenient effects and achieves good agreement with standard chemical procedures. Procedural modification may also enable lower atomic number determinations. W . E. BURKE, L. S. HINDS, G . E. DEODATO, E. D. SAGER, Jr., and R. E. BORUP, Cities Service Pvesearch and Development Co., Drawer # 2 , Cranbury, N. J . Anal. Chem. 36, 2404 (1964)
Anal. Chem. 36, 2389 (1964)
Determination of Zinc in Biological M a t e r i a l s by Atomic Absorption Spectrophotometry The sample is diluted with metal-free buffer or distilled water and is then aspirated directly into the hydrogen-air flame of the atomic absorption device. Accuracy was determined with NBS samples.
Element C a l i b r a t i o n s b y Plasma J e t Spectrochemistry A single, widely applicable concentration calibration for manganese in acid solutions of different NBS alloy types is demonstrated. Application to systems such as iron, nickel, copper, aluminum, and zinc alloys is illustrated. EDWARD H. SIROIS, General Electric Co., Major Division Laboratories, Louisville, Ky.
Appliance
KEIICHIRO FUWA, PABLO PULIDO, ROBERT McKAY, and BERT L. VALLEE, Biophysics Research Laboratory, Department of Biological Chemistry, Harvard Medical School, and Division of Medical Biology. Department of Medicine, Peter Bent Brigham Hospital, Boston, Mass. Anal. Chem. 36, 2407 (1964)
Anal. Chem. 36, 2394 (1964)
Infrared Examination of C a r b o n - H y d r o g e n S t r e t c h i n g F r e q u e n c y in P y r o c a t e c h o l s , G u a i a c o l s , and Phenols Infrared Emission S p e c t r a of Solid S u r f a c e s The exploratory experiments indicate that emission methods could be applied in special cases for the examination of the surfaces of opaque bulk solids. M. J . D. L O W and H. INOUE, School of Chemistry, Rutgers, The State University, New Brunswick, N. J . Anal. Chem. 36, 2397 (1964)
The infrared spectra in carbon tetrachloride solution were determined in the 2800-3000 cm. -1 region. T h e origin and the frequency variation of several of the vibrations are discussed. WILLIS BECKERING, C . M. FROST, and W . W . FOWKES, Grand Forks Lignite Research Laboratory, Bureau of Mines, U. S. Department of the Interior, P. O . Box 8213 University Station, G r a n d Forks, N . D. Anal. Chem. 36, 2412 (1964)
A n a l y s i s of a Trinuclear A r o m a t i c Petroleum Fraction b y High Resolution M a s s S p e c t r o m e t r y Identifications are achieved by precise mass measurement of the molecular ion. assumntion of a reasonable structure, then measurement of fragment ions to prove or disprove the assumed structure. H. E. LUMPKIN, Research and Development, Humble Oil and Refining Co., Baytown, Texas Anal. Chem. 36, 2399 (1964) Circle No. 78 on Readers' Service Card
C h a r a c t e r i z a t i o n of Alkylphenols b y A c e t y l a t i o n and Proton M a g n e t i c R e s o n a n c e T h e proton absorption of the acetate methyl occurs in a unique region, the sharp methyl resonance has three times t he sensitivity of the hydroxyl group resonance, and the exact position of the methyl resonance permits identification of the ortho and para isomers. L. P. LINDEMAN and S. W . NICKSIC, California Corp., Richmond, Calif.
Research
Anal. Chem. 36, 2414 (1964) VOL. 36, NO. 13, DECEMBER 1964 · 9 A
BRIEFS Differential C o n t r o l l e d - P o t e n t i a l C o u l o m e t r y . A p p l i c a t i o n t o D e t e r m i n a t i o n of Chromium A now technique combines controlled-potential coulometry and differential methods to determine electroactive materials in the sub-millimolar concentration range. T h e advantages over direct controlled-potential coulometry are illustrated. G. A. RECHNITZ and K. SRINIVASAN, Department of Chemistry, University of Pennsylvania, Philadelphia, Pa.
Sodium Borohydride Reduction and P o l a r o g r a p h i c D e t e r m i n a t i o n of Tin Sn(IV) can be determined in the presence of C I , As(V), A s ( I I I ) , B i ( I I I ) , C u ( I I ) , P b ( I I ) , and Zn(II) by prcreducing Sn(IV) to Sn(II) with borohydride, then determining Sn(II) via its cathodic polarographic wave. DENNIS H. EVANS, Department of Chemistry, Harvard sity, C a m b r i d g e , Mass.
Univer-
Anal. Chem. 36, 2435 (1964)
Anal. Chem. 36, 2417 (1964)
Teflon Dropping M e r c u r y E l e c t r o d e f o r P o l a r o g r a p h y in Hydrofluoric A c i d and O t h e r G l a s s - C o r r o d i n g M e d i a . Evaluation with T h a l l i u m ( l ) ±? Thallium R e a c t i o n The results indicate that polarograms obtained with Teflon dropping mercury electrodes have the same meaning as those taken with glass dropping mercury electrodes and can be analyzed in the same way. HELEN P. RAAEN, Analytical Chemistry National Laboratory, Oalc Ridge, Tenn.
A u t o m a t i c Ion Exclusion—Partition C h r o m a t o g r a p h y of A c i d s Acids are separated on a column of a sulfonic acid ionexchange resin using only water as the eluent. The effluent is titrated automatically and the volume of titrant required is recorded as a function of time. G. A. H A R L O W and D. H. MORMAN, Shell Development Co., Emeryville, Calif. Anal. Chem. 36, 2438 (1964)
Division, Oak Ridge
Anal. Chem. 36, 2420 (1964)
S e p a r a t i o n and Identification of Phenols in A u t o m o b i l e Exhaust by P a p e r and G a s Liquid Chromatography C y c l i c S t a t i o n a r y E l e c t r o d e V o l t a m m e t r y of Some Aliphatic Amines The variation of peak current with sweep rate and concentration follows the relationship expected for irreversible reactions. Data are presented t o illustrate the precision obtainable in quantitative analysis. CHARLES K. MANN, Department of Chemistry, Florida University, Tallahassee, Fla. 32306
State
Anal. Chem. 36, 2424 (1964)
V o l t a m m e t r i c Behavior of t h e S y s t e m N i t r o s o benzene-Phenylhydroxylamine a t the Graphite Electrode The couple studied behaves reversibly a t the stationary pyrolytic graphite electrode in 50% ethanolic buffer solution. T h e use of graphite allows the system t o be studied at p H as low as 1.6. LAURA C H U A N G , ILANA FRIED, and PHILIP J . ELVING, The University of Michigan, Ann Arbor, Mich. Anal. Chem. 36, 2426 (1964)
P o l a r o g r a p h i c and A d s o r p t i o n S t u d i e s of Dimethyldodecylamine Oxide
Phenols have been determined in automobile exhaust, gases by gas liquid chromatography and by paper chromatography using the Crump procedure. T h e results of analyses of several samples are presented. ETHEL D. BARBER, EUGENE SAWICKI, and SYLVESTER P. McPHERSON, Laboratory of Engineering and Physical Sciences, Division of Air Pollution, Robert A. Taft Sanitary Engineering Center, Public Health Service, U. S. Department of Health, Education, and Welfare, Cincinnati, Ohio Anal. Chen. 36, 2442 (1964)
G a s C h r o m a t o g r a p h i c and I s o t o p e Dilution A n a l y s i s of Isomers Formed on Mononitration of Benzoic A c i d A combination of the isotope dilution method with preparative-scale gas chromatography is used in which the gas chromatography fractions are collected and assayed for activity. BIANCA ALIPRANDI, FULVIO C A C A C E , and G I O V A N N A CIRANN1, Centro Nazionale di Chimica délie radiazioini e Radioelementi del C.N.R., Istituto di Chimica Farmaceutica e Tossicologica dell' Universita di Roma, Italy Anal. Chem. 36, 2445 (1964)
Thin Layer C h r o m a t o g r a p h i c A n a l y s i s of Simple Alkyl Phenols
The polarographic wave for dimethyldodecylamine oxide (DDAO) in buffered acid media is irreversible, and the Ei/2 varies nonlinearlv with p H and bulk concentration of DDAO.
Mixtures of 20 simple alkyl phenols coupled as ;;-nilrophenylazo dyes have been separated by using a two dimensional chromatographic technique with thin layers of silica gel impregnated with alkali.
L. M. CHAMBERS, Proctor & G a m b l e Co., Ivorydale Technical Center, Cincinnati, Ohio 45217
G. B. CRUMP, Central Laboratories, Shell Research Ltd., Whitehall Lane, Egham, Surrey, England
Anal. Chem. 36, 2431 (1964)
Anal. Chem. 36, 2447 (1964) VOL. 36, NO. 13, DECEMBER 1964 · 1 1 A
BRIEFS Extraction and S p e c t r o p h o t o m e t r i c Determination of G o l d T h e method is based on the extraction of the bromoaurate-trioctylphosphine oxide complex into chloroform followed by an in situ absorbance measurement. The precision is better than 1% standard deviation. W A Y N E B. H O L B R O O K a n d J A M E S E. REIN, Phillips C o . , A t o m i c Energy D i v i s i o n , I d a h o Falls, I d a h o
Petroleum
Trialkyland Hexaalkylphosphorothioic Tria m i d e s a s E x t r a c t a n t s for Metal Ions. Selec t i v e Extraction of Mercury ( I I ) , Silver ( I ) , and Copper(l) The metal ion concentration, type of organic solvent, and substituent group of the trialkyl phosphorothioic triamides are significant variables studied. Structures are postulated for the complex species formed between the extract ant and the metal ions.
Anal. Chem. 36, 2451 (1964) T H O M A S H. HANDLEY, Analytical Chemistry R i d g e N a t i o n a l L a b o r a t o r y , O a k R i d g e , Tenn.
Division,
Anal. C h e m . 36, 2467
R e a c t i o n s in C o n c e n t r a t e d Lithium C h l o r i d e Solution. Determination of Free A c i d and Hydrolyzable Cation This method involves potcntiometric titration with base in 10M LiCl medium without using any complexing agent. Continued titration past the free acid end point gives a second break which shows the equivalents of hydrolyzable cations. H I S A S H I K U B O T A a n d D. A . C O S T A N Z O , A n a l y t i c a l C h e m i s t r y D i v i s i o n , Oalc R i d g e N a t i o n a l L a b o r a t o r y , O a k R i d g e , Tenn. Anal. C h e m . 36, 2 4 5 4
(1964)
Simultaneous C o l o r i m e t r i c l o d a t e and Bromate
Oak
(1964)
Determination
of
An equimolar mixture of isonicotinic acid hydrazide and 2,3,5-triphenyltetrazolium chloride in dilute HC1 gives a pink color with iodate at room temperature and with bro mate only on heating. This forms the basis for the method described. M. H . H A S H M I , HAMID A H M A D , ABDUR RASHID, and F A R O O Q A Z A M , W e s t R e g i o n a l L a b o r a t o r i e s , Pakistan C o u n c i l of S c i e n t i f i c a n d Industrial R e s e a r c h , Lahore, W e s t Pakistan Anal. Chem. 36, 2471 (1964)
C o r r e c t i o n of Quenching in Liquid Scintillation Counting of H o m o g e n e o u s S a m p l e s Containing Both C a r b o n - 1 4 and Tritium by Extrapolation Method A method is described in which the sample containing both C " and H 3 is counted at two different concentrations and from the observed counts in the two channels, quench ing in the sample is corrected by the extrapolation method. C . T. P E N G , R a d i o a c t i v i t y R e s e a r c h C e n t e r a n d S c h o o l of Phar m a c y , U n i v e r s i t y of C a l i f o r n i a , S a n F r a n c i s c o , C a l i f . Anal. Chem. 36, 2456
C o n v e n i e n t Anion Exchange Resin of Magnesium-EDTA C h e l a t e f o r Titrations
of
Preparation Substitution
Chemistry,
Determination
Franklin
and
of
Vanadium
in
Vanadate ion is assayed by acidifying the sample and pouring it through a column containing radioactive metal lic silver. The silver ions are released into the solution where their concentration may be measured by Geiger or scintillation counting. A R T H U R S. GILLESPIE, Jr., a n d H A R O L D G . RICHTER, T r i a n g l e Institute, Box 4 9 0 , Durham, N . C . 2 7 7 0 2
(1964)
No standard solutions or critical adjustment steps are necessary for the preparation, and the chelate can be added directly to the solution to be titrated in the form of resin beads, or t h e chelate can first be eluted with 0.50M NaC10 4 . EUGENE D. OLSEN, Department Marshall C o l l e g e , Lancaster, Pa.
Radio R e l e a s e Water
Research
Anal. Chem. 36, 2473
Titration of A r o m a t i c aqueous Solvents
Sulfinic
Acids
(1964)
in
Non
Acid-base titrations of sulfinic acids and mixtures of sul finic and sulfonic acids with quaternary ammonium titrants in nonaqueous solvents are possible Tn general, the rela tive standard deviation is within Τ 0.25% and the relative error within =F 0.4%. D A V I D L. WETZEL a n d C L I F T O N E. M E L O A N , D e p a r t m e n t of C h e m i s t r y , Kansas S t a t e U n i v e r s i t y , M a n h a t t a n , Kan. Anal. Chem. 36, 2 4 7 4 (1964)
Anal. Chem. 36, 2461 (1964)
An A u t o m a t i c S p e c t r o p h o t o m e t r i c Method the Specific Enzymatic Determination G a l a c t o s e in W h o l e Blood and Plasma
Ion Exchange Determination of Uranium in Ferrous A l l o y s Microgram and milligram quantities of uranium are separated from large quantities of iron, aluminum, alka line earth metals, lanthanides, and many other elements using strongly basic anion exchanger Dowex 1, X 8. J O H A N N K O R K I S C H a n d ISIDOR H A Z A N , A n a l y t i c a l U n i v e r s i t y of V i e n n a , IX. W a h r i n g e r s t r a s s e 3 8 , A u s t r i a
Institute,
for of
The method is based on the catalysis by galactose oxidase of the oxidation of galactose. Hydrogen peroxide pro duced by the enzymatic reaction oxidizes o-dianisidine in the presence of peroxidase to a species which absorbs at 440 ιημ. C H R I S T O P H E R S. F R I N G S and H A R R Y L. P A R D U E , of C h e m i s t r y , Purdue U n i v e r s i t y , L a f a y e t t e , Ind.
Anal. Chem. 36, 2 4 6 4 ( 1964)
Department
Anal. Chem. 36, 2477 (1964)
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B R I E F S
No. ^jlh Determination of C a r b o x y l i c Acid Hydrazides by Titration of the A c i d i c Hydrazones Formed with 2,4-Dichlorobenzaldehyde
ADVANCES IN
The method involves reacting the hydrazide with 2,4dichlorobenzaldehyde to form the hydrazone, which is subsequently titrated as an acid in pyridine with tetrabutylammonium hydroxide.
CHEMISTRY SERIES
ALBERT A. LATOUR, EDWARD J . KUCHAR. and SIDNEY SIGGIA, Olin Research Center, Olin Mathieson Chemical Corp., New Haven 4, Conn. Anal. Chem. 36, 2479 (1964)
Falling Ball Viscometry. P r e c i s e Measurements
An
Instrument
in the
BORAX
for
The instrument uses electronic timing and small steel balls and is sensitive enough to measure fall times of ViH-inch stainless steel balls with a precision similar to I hat obtained in capillary viscometry. W . K. LIM, H. W . J O H N S O N , Jr., P. C. WILHELMSEN, and F. H. STROSS, Shell Development Co., Emeryville, Calif. Anal. Chem. 36, 2482 ( 1964)
Structure and Behavior of O r g a n i c A n a l y t i c a l R e a g e n t s . Formation C o n s t a n t s of Transition Metal C o m p l e x e s of 2-Hydroxypyridine-l-Oxide and 2 - M e r c a p t o p y r i d i n e - l - O x i d e The acid dissociation constants and the chelate formation constants of the two compounds with M n ( I I ) , C o ( I I ) , K i ( I I ) , C u ( I I ) , and Zn(II) were determined potentiometrically and spoctrophotometrically. PENG-JOUNG SUN, QUINTUS FERNANDO, and HENRY FREISER, Department of Chemistry, University of Arizona, Tucson, Ariz. Anal. Chem. 36, 2485 (1964)
Q u a n t i t a t i v e Conversion of M o l y b d a t e t o M o ( V ) by t h e Stannous Chloride-Perchlorate Reaction and S p e c t r o p h o t o m e t r i c Determination of Tricaprylylmethylammonium O x y t e t r a t h i o c y a n a t o molybdate(V) Removal of excess stannous ion by excess perchlorate previous to thiocyanate addition and development of the characteristic orange-red color of oxypentathiocyanatomolvbdatc(V), assures stable absorbance of this complex in (he aqueous phase up to one hour and in the quaternary-chloroform extract up to 24 hours. A. M. WILSON, Department of Chemistry, Emory University, Atlanta, G a . 30322, O . K. McFARLAND, Department of Chemistry, W a y n e State University, Detroit 2, Mich. Anal. Chem. 36, 2488 ( 1964)
4-Methoxy-a-Naphthol a s a S p e c t r o p h o t o m e t r i c R e a g e n t S u b s t r a t e for Measuring Peroxidatic Activity With the described procedure, 0.010 to 0.700 unit/ml of peroxidase, 0.00550 to 0.220, and 0.000330 to 0.00666 unit/ ml. of glucose oxidase and xanthine oxidase were assayed with standard deviations of 1.9, 1.8, and 1.6, respectively. GEORGE G . GUILBAULT and DAVID N. KRAMER, Detection Research Branch, Defensive Research Division Directorate of Defensive Systems, CRDL, Edgewood Arsenal, Md.
TO BORANES With preface by PROFESSOR THOMAS WARTIK Pennsylvania State University This is a collection of 27 p a p e r s given at two ACS symposia (1958 and 1959) on t h e production of boron hydrides from borax, and on the chemistry of the boranes. Five papers are included on t h e fundamental chemistry of boron, and one on t h e history of this e l e m e n t and its c o m p o u n d s . Among t h e applications of boron and t h e boranes discussed in this definitive monograph are t h o s e to nuclear reactors, "exotic" jet engine and rocket fuels, and semiconductors. Boron is, b e c a u s e of its electronic structure, an extremely versatile elem e n t and forms a great variety of c o m p o u n d s of potential but unrealized usefulness. Boron chemistry is one of t h e new frontiers in organo-inorganic chemistry. Therefore, this volu m e is of interest and importance to c h e m i s t s in any of t h e fundamental fields, a s well a s to specialists in t h e theory of valency, crystal structure, metallo-carbon c o m p o u n d s , t h e chemistry of explosion, and t h e history of chemistry. 244 pages.
Paper bound.
Price:
$5.00
Order from: Special Issues Sales, American Chemical Society 1155 Sixteenth Street, N. W., Washington 6, D. C.
Anal. Chem. 36, 2494 ( 1964) -Circle No. 117 on Readers' Service Card
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