AC BRIEFS Multistep Charge Transfers Electrode Polarography
in
H I G H L I G H T S OF 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 THIS ISSUE
Stationary
The theory for single scan and cyclic triangular wave experiments was considered for uncomplicated multistep reversible or irreversible charge transfers. The reduction of Cu(II) in \M ammonium chloride-ammonium hy droxide was used to test the theoretical calculations.
Inhibition of Electrode Reactions by Adsorbed Lead Iodide, Bromide, and Thiocyanate Polarographic and chronopotentiometric techniques were used to study the inhibition of the electroreductions of mercury(II) and bismuth at mercury electrodes by lead absorption from iodide and bromide media.
Depart
DONALD J . GROSS and ROYCE W . MURRAY, Department of Chemistry, University of North Carolina, Chapel H i l l , N. C. 27515
Anal. Chem, 38, 370 (1966)
Anal. Chem. 38, 405 (1966)
DANIEL S. POLCYN and IRVING SHAIN, Chemistry ment, University of Wisconsin, Madison, Wis.
Theory of Stationary Electrode Polarography for a Multistep Charge Transfer with C a t a l y t i c (Cyclic) Regeneration of the Reactant For each of the four cases, the boundary value problem was converted into two integral equations. Theoretical current potential curves were calculated, and the inter action of the two charge transfers with the chemical step was investigated as a function of several parameters. The reduction of the F e ( I I ) complex with triethanalamine in the presence of hydroxylamine w-as studied to test the theory. DANIEL S. POLCYN and IRVING SHAIN, Chemistry ment, University of Wisconsin, Madison, Wis.
Depart
Determination of Emissivities with a Differential Scanning Calorimeter Methods for reducing errors in heats of decomposition or transition caused by cmissivity changes during a de termination and a differential method for determining cmissivity coefficients are presented. R. N. ROGERS and E. D. MORRIS, Jr., University of California, Los Alamos Scientific Laboratory, P. O. Box 1663, Los Alamos, Ν. Μ. Anal. Chem. 38, 410 (1966)
Anal. Chem. 38, 376 (1966)
Continuous Ohmic Polarization Compensator for a Voltammetric Apparatus Utilizing Operational Amplifiers Continuous compensation for the ohmic voltage between reference and working electrodes in an electrochemical cell was achieved by the insertion of an effective resist ance in scries with the cell. DIRK POULI, JAMES R. HUFF, and JAMES C. PEARSON, Re search Division, Allis-Chalmers Manufacturing Co., Milwaukee I, Wis.
On Estimating Activation Energies with a Differential Scanning Calorimeter A method is presented for estimating the activation energy of a decomposition reaction using a small, unweighed sample. R. N. ROGERS and E. D. MORRIS, Jr., University of California, Los Alamos Scientific Laboratory, P. O. Box 1663, Los Alamos, Ν. Μ. Anal. Chem. 38, 412 (1966)
Anal. Chem. 38, 382 (1966)
Comparative Study of the Kinetics of the Benzidine Rearrangement by Four Electrochemical Techniques Four electrochemical techniques were applied to the study of the acid-catalyzed rearrangement of hydrazobenzene. ' D. M. OGLESBY, J . D. J O H N S O N , and CHARLES N. REILLEY, Department of Chemistry, University of North Carolina, Chapel H i l l , N. C.
New Concept in Precision Photometric Analysis Using a Radioisotopic Light Source The theoretical interpretation of the proposed system is based on the unusual properties of a beta-activated radioisotopic light source. The results of a study of five colorimetric systems agree with a simple mathematical model. HARLEY H. ROSS, Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tenn. Anal. Chem. 38, 414 (1966)
Anal. Chem. 38, 385 (1966)
Chronopotentiometric and Chronocoulometric Measurements of Adsorption of Lead and M e r c u r y ( I I ) a t Mercury Electrodes These techniques were used to investigate surface excess values and the nature of adsorptions of mercury elec trodes of lead from iodide, bromide, thiocyanate, and chloride media and of mcrcury(II) from iodide, bromide, thiocyanate, and thiourea media. ROYCE W . MURRAY and DONALD J . GROSS, Department of Chemistry, University of North Carolina, Chapel H i l l , N. C. 2751S
A Critical Study of Carbon-Reduction Techniques for the Determination of Oxygen in Thorium and Yttrium Metals The experimental conditions under which quantitative accuracy can be achieved were studied for carrier-gas fusion, vacuum fusion, and d.c. carbon-arc extraction methods. VELMER A . FASSEL, W A Y N E E. DALLMANN, and C. CLIFTON HILL, Institute for Atomic Research and Development of Chem istry, Iowa State University, Ames, Iowa
Anal. Chem. 38, 392 (1966) Anal. Chem. 38, 421 (1966) VOL. 38, NO. 3, MARCH 1966 ·
11 A
AC BRIEFS Three-Wavelength X-Ray Absorption Edge Method for Determination of Plutonium in Nitrate Media The intensities of the K/3 x-ray for niobium and the K » x-rays for molybdenum and niobium are measured. The method is applicable to plutonium concentrations of 10 to 25 mg. per ml. with a relative standard deviation of approximately 0.6% E. A . H A K K I L A , R. G. H U R L E Y , and G . R. W A T E R B U R Y , Uni versity of California, Los Alamos Scientific Laboratory, Los Alamos, Ν Μ .
Determination of Coal in Formalin-Fixed Pneumoconiotic Lungs. New Method of Tissue Digestion Using Glacial Acetic Acid Formalin-fixed lung tissue is digested by treatment with hot glacial acetic acid containing ammonium acetate followed by formic acid. Reactive bituminous coals and minerals such as kaolin and mica are recovered, while calcifications and iron deposits are removed. I M A N U E L B E R G M A N , Safety in Mines Research Ministry of Power, Sheffield 3, England
Establishment,
A n a l . C h e m . 38, 441
(1966)
A n a l . C h e m . 38, 425 ( 1 9 6 6 )
Dithizone Extraction and X-Ray Spectrographs Determination of Trace Metals in High-Purity Tungsten or Tungsten Trioxide Copper, nickel, and zinc from 0.3 to 20 p.p.m. and lead from 1.0 to 20 p.p.m. were determined to within 0.3 p.p.m. or with a relative standard deviation of 8%. Cobalt was estimated in the 0.1- to 1.0-p.p.m. range. G R A N T L. H U B B A R D and T H O M A S E. G R E E N , C o l l e g e Park M e t a l l u r g y Research Center, Bureau of Mines, U . S. Department o f the Interior, C o l l e g e Park, M d . A n a l . Chem. 38, 428 ( 1 9 6 6 )
Determination of Silver in Minerals and Ores by Neutron Activation Analysis and High Resolution Gamma Spectrometry
Use of High Resolution Mass Spectrometry in the Study of Petroleum Waxes, Microcrystalline Waxes, and Ozokerite The ability of high resolution mass spectrometry to detect nonaliphatic hydrocarbons and heteroatom materials in waxes was demonstrated. Mass measurements, with an accuracy of better than 5 p.p.m., were used to assign t h e most likely ionic formulas to some of the ions observed. W . K. REID, BP Research Centre, The British Ltd., Sunbury-on-Thames, Middlesex, England
Petroleum C o .
A n a l . C h e m . 38, 4 4 5 ( 1 9 6 6 )
Estimation of Solubility of Bismuth Compounds in Liquid Ammonia
The limit of detectability of Ag in minerals rich in Mg was 15 p.p.m. for sample sizes from milligrams to 10 grams.
The solubilities of the triiodide, trichloride, tribromide, nitrate, sulfide, and lactate of bismuth were determined polarographically.
G E R A L D L. S C H R O E D E R and ROBLEY D. E V A N S , Department o f Physics, Massachusetts Institute of Technology, C a m b r i d g e , Mass. 0 2 1 3 9 , and R I C H A R D C . R A G A I N I , Department of Chemistry, Massachusetts Institute of Technology, C a m b r i d g e , Mass. 02139
A N N I E G . SMELLEY, F R A N C I S E. BRANTLEY, and A R T H U R F. FINDEIS, U. S. Bureau of Mines, University, A l a . A n a l . C h e m . 38, 449 ( 1 9 6 6 )
A n a l . Chem. 3 8 , 432 ( 1 9 6 6 )
Ultramicro Spectrophotometry of Calcium in Biologic Fluids
Determination
This method for the determination of calcium in the range of 10^ gram in 5 to 25 mftl. depends on an ultramicro cuvette and chlorophosphonazo I I I . D. S. H O W E L L , J . C . PITA, and J . F. M A R Q U E Z , Department of Medicine, University of M i a m i School of Medicine, M i a m i , Fla. Anal. Chem. 38, 434 (1966)
Spectrophotometric Determination of Gold, Copper, and Cobalt The reaction of formic acid hydrazide with gold, copper, cobalt, and nickel in acid medium to give violet, pink, blue, and violet colors is the basis of a method for the colorimetric determination of gold and the spectrophoto metric determination of copper and cobalt. M . H . H A S H M I , A B D U R R A S H I D , M O H A M M A D U M A R , and F A R O O Q A Z A M , W e s t Regional Laboratories, Pakistan Council o f Scientific and Industrial Research, Lahore, W e s t Pakistan A n a l . Chem. 38, 4 3 9 ( 1 9 6 6 ) -*
See Buyers' Guide for all products/sales offices.
-*
Circle No. 77 on Readers' Service Card
Titrimetric and Equilibrium Studies Using Indicators Related to Nile Blue A Nile Blue A was used as the salt, as the anhydro-base, and as the oxazone. T h e other dyes were used as salts or anhydro-bases having an alkyl, aralkyl, or aryl group a t tached to the 5-amino nitrogen in place of hydrogen. M A R I O N M A C L E A N D A V I S and H A N N A H tional Bureau of Standards, Washington, D. C .
B. HETZER, N a 20234
A n a l . Chem. 38, 451
(1966)
Voltammetric Membrane Electrode Study of the Ion-Exchange Properties of Cellophane Membranes The diffusion properties of hydrogen ion and aquocadmium ion in cellophane, as characterized by their behavior at a voltammetric membrane electrode, were investigated. R I C H A R D C . B O W E R S and R O Y C E W . M U R R A Y , of Chemistry, Northwestern University, Evanston, I I I .
Department
A n a l . C h e m . 38, 461 ( 1 9 6 6 )
VOL. 38, NO. 3, MARCH 1966 ·
13 A
AC BRIEFS Gas Chromatographic Method for Quantitative Determination of Vinyllithium The method involves the use of two complete chromatographic units connnected in series and a single injection to make two quantitative separations requiring different columns and conditions. WILLIAM S. L E O N H A R D T , ROBERT C . C O N R A D W . K A M I E N S K I , Lithium C o r p . Bessemer C i t y , N . C .
MORRISON, of America,
and Inc.,
Syringe Ram for a Rapid-Freeze Sampling Instrument A ram system suitable for driving the syringes of a rapid flow mixing apparatus employs a 1-horsepower d.c. servo motor as a source of mechanical power. R A Y M O N D E. H A N S E N and H E L M U T Enzyme Research, Madison, W i s .
BEINERT,
Institute for
A n a l . C h e m . 38, 4 8 4 ( 1 9 6 6 )
A n a l . C h e m . 38, 4 6 6 ( 1 9 6 6 )
Studies on the Mechanism of Separation of Diastereoisomeric Esters by Gas-Liquid Chromatography. Effect of Bulk Dissymmetry and Distance between Optical Centers The differences of the diastereoisomeric esters of acetylatrd lactic acid were measured in terms of relative volatility. From this, the free energy differences in gas-liquid partition equilibria were determined. HERBERT C . ROSE, K A R G E R , Department Boston, Mass. 021 15
Scientific
Communication
Analysis of Hydrazine-Ammonia
Mixtures
BRUCE E. K N O X and E D W A R D T. M c H A L E , The Department of Fuel Science, The Pennsylvania State University, University P a r i , Pa. Anal. Chem. 38, 487
ROBERT L. STERN, and BARRY L. of Chemistry, Northeastern University,
(1966)
Anal. Chem. 38, 469 (1966)
Analysis of Alkylene Oxide Polymers by Nuclear Magnetic Resonance Spectrometry and by Gas-Liquid Chromatography Analysis of the polyether sample for oxyethylene/oxypropylene ratio by nuclear magnetic resonance epectrometry and a method involving splitting the polyether with H B r followed by chromatographic analysis of the products are described. A L A N M A T H I A S and N O R M A N M E L L O R , Imperial C h e m i c a l Industries L t d . (Dyestuffs Division), Hexagon House, Blackley, Manchester 9, England
Correspondence Evidence on the Nature of Eddy Diffusion in Gas Chromatography from Inert (Nonsorbing) Column Data A . K L I N K E N B E R G , Bataafse Internationale Petroleum, Maatschappii N . V. (Royal Dutch/Shell G r o u p ) , The H a g u e , The Netherlands A n a l . C h e m . 38, 4 8 9 ( 1 9 6 6 )
A n a l . C h e m . 38, 4 7 2 ( 1 9 6 6 }
The Nature of Eddy Diffusion Separation of Cis- Trans-Cobalt ( I I I ) Amine Complexes by Thin Layer Chromatography
J . C A L V I N G I D D I N G S , Department of Utah, Salt Lake C i t y , Utah
of
Chemistry,
University
Anal. Chem. 38, 490 (1966)
Separation, achieved using Silica Gel H and an acidic niethanol-dimcthyl sulfoxide solvent, appears to be based on ion exchange equilibria. L E O N A R D F. D R U D I N G and ROBERT B. H A G E L , D e p a r t m e n t of Chemistry, Rutgers, The State University, Newark, N . J . 07102 A n a l . C h e m . 38, 4 7 8 ( 1 9 6 6 )
The Nature of Eddy Diffusion in Gas Chromatography A . K L I N K E N B E R G , Bataafse Internationale Petroleum, Maatschappij N.V., (Royal D u t c h / S h e l l G r o u p ) , The H a g u e , The Netherlands
Tritiated Alumina as a Reagent for SelfLabeling Chromatographic Analyses The radiochemical visualization and separation of a mixture of three ketostcroids on a chromatographic column of tritiated alumina, prepared by exchange of the surface hydroxyl groups with tritiated water, is used to illustrate that it is a suitable reagent for the self-labeling chromatographic analysis of appropriate classes of molecules.
A n a l . C h e m . 38, 4 9 !
(1966)
Solvent Enhancement of Emission Lines for Plasma Arc Determination of Vanadium in Petroleum Fractions
PETER D. K L E I N and E R I C H . E R E N R I C H , Division of Biological and M e d i c a l Research, Argonne National Laboratory, A r g o n n e ,
R A Y M O N D J . H E E M S T R A and N O R M A N G . FOSTER, Bartlesville Petroleum Research Center, Bureau of Mines, U . S. Department of the Interior, Bartlesville, O k l a . 74004
A n a l . C h e m . 38, 4 8 0 ( 1 9 6 6 )
A n a l . C h e m . 38, 492 ( 1 9 6 6 )
VOL. 3 8 , N O . 3, MARCH
1966
·
15
A
AC
BRIEFS
Extraction and Spectrophotometric Determination of Thorium with 8-Çuinolinol
Causes of Carbon Dioxide Loss from Sodium Carbonate a t 400° C.
K A T S U M I G O T O , D. S. RUSSELL, and S. S. B E R M A N , Division of A p p l i e d Chemistry, N a t i o n a l Research Council, O t t a w a 2 , Ontario, Canada
D U M A S A . O T T E R S O N , Lewis Research Center, N a t i o n a l A e r o nautics and Space Administration, C l e v e l a n d , O h i o
A n a l . C h e m . 3 8 , 493
A n a l . C h e m . 3 8 , 506
(1966)
(1966)
Indirect Determination of Hypochlorite and Hypobromite by Thallium
High Resolution Mass Spectra of Compounds Separated by Capillary Columns. Use of a Plate Scan Technique DIETER H E N N E B E R G , Max-Planck-lnstitut fur Kohlenfroschung, M'ulheim-Ruhr, W e s t G e r m a n y A n a l . C h e m . 3 8 , 495 ( 1 9 6 6 )
M . H . H A S H M I , A B D U L R A S H I D , A . A . A Y A Z , and N . A . C H U G H T A I , W e s t Regional Laboratories, P.C.S.I.R., Lahore, W e s t Pakistan A n a l . C h e m . 3 8 , 507 ( 1 9 6 6 )
Separation of Uranium by Combined Ion Exchange-Solvent Extraction
Infrared Study of New Sulfonylurea Derivatives and Sulfonamides
JOHANN K O R K I S C H , and S. S. A H L U W A L I A , Analytical Institute, University of Vienna, IX, Wahringerstrasse 3 8 , Vienna, Austria
M . F. A B D E L - W A H A B , S. A . E L - K I N A W Y , N . A . F A R I D , and A M I N A M . E L - S H I N N A W Y , M i d d l e Eastern Regional Radioisotope C e n t r e for A r a b Countries, Doklci Drug Research and Control Centre G . O . P . C . A . , G i z a , C a i r o , U.A.R.
A n a l . C h e m . 3 8 , 497
(1966) A n a l . C h e m . 3 8 , 508
Rapid and Precise Determination of Carbon Dioxide from Carbonate-Containing Samples Using Modified Dynamic Sorption Apparatus J O S E P H U S T H O M A S , Jr., and G R A Y M . S t a t e G e o l o g i c a l Survey, N a t i o n a l Resources I I I . 61803
H I E F T J E , Illinois Building, U r b a n a ,
A n a l . Chem. 38, 500
(1966)
Fructose-Resorcinol-Hydroehloric Acid Test for Detection and Determination of Acetaldehyde G . P. A R S E N A U L T and W . Y A P H E , A t l a n t i c Regional Laboratory, N a t i o n a l Research Council of C a n a d a , H a l i f a x , N . S., C a n a d a
Improved Extraction Method for Isolation of Trivalent Actinide-Lanthanide Elements from Nitrate Solutions F. L. M O O R E , A n a l y t i c a l Chemistry tional Laboratory, O a k Ridge, Tenn.
Division, O a k
Ridge
A n a l . C h e m . 3 8 , 510
Electronic
A n a l . C h e m . 3 8 , 504
(1966)
W . W . W H I T E , C o m m e r c i a l Receiving Tube and Semiconductor Division, Radio C o r p o r a t i o n of A m e r i c a , Harrison, N . J . 0 7 0 2 9 (1966)
(1966)
Conductometrie Method for the Determination of Carbon on the Surface of Nickel Strip I. S. SOLET, Radio Corporation of A m e r i c a , ponents and Devices, Somerville, N . J . 0 8 8 7 6
Na-
Gravimetric Determination of Germanium in Germanium-Rich Alloys
A n a l . C h e m . 3 8 , 512 A n a l . C h e m . 38, 503
(1966)
Com-
(1966)
Rapid Preparation of Fatty Acid Esters from Lipids for Gas Chromatographic Analysis L. D. M E T C A L F E , A . A . S C H M I T Z , and J . R. PELKA, Research Laboratory, Armour Industrial Chemical Co., McCook, III. 60529 A n a l . C h e m . 3 8 , 514
(1966)
Spectrophotometric Method for the Determination of Natural Rubber Hydrocarbon
Thermometric Titration of Cetylpyridinium Chloride
P R A N A B K. S E N G U P T A and P R E M A M O Y G H O S H , Department of A p p l i e d Chemistry, University C o l l e g e of Science and Technology, C a l c u t t a - 9 , India
N O R M A N D. W E I N E R and A L V I N FELMEISTER, Department of Pharmaceutics, C o l l e g e of Pharmacy, Columbia University, N e w York, N . Y . I0023
A n a l . C h e m . 3 8 , 505
(1966) A n a l . C h e m . 3 8 , 515
V O L . 3 8 , N O . 3, MARCH
1966
·
(1966)
17
A
AC BRIEFS Simultaneous Polarographic Estimation of Major Constituents in Lead-Tin and LeadTin-Indium Alloys D. E. SELLERS and D. J. ROTH, Mound Laboratory, Monsanto Research Corp., Miamisburg, Ohio. Anal. Chem. 38, 516 (1966)
Separation of Alkaline Earth Elements by Anion Exchange WILLIAM E. BENNETT and DEAN O. SKOVLIN, Department of Chemistry, University of Iowa, Iowa City, Iowa Anal. Chem. 38, 518 (1966)
Determination of Sodium. Arsenic, Copper, and Gallium in Tin Oxide by Neutron Activation H. E. RAUSCHER, Research & Development Corning Glass Works, Corning, Ν. Υ.
Laboratories,
Anal. Chem. 38, 519 (1966)
Use of the Computer to Calculate Thermo dynamic Constants from Thermogravimetric Curves J . M. SCHEMPF, F. E. FREEBERG, D. J . ROYER, and F. M. ANGELONI, The Pennsylvania State University, Department of Chemistry, University Park, Pa. Anal. Chem. 38,520 (1966)
Refined Calculation for Determination of Nitrogen in Nitrocellulose by Infrared Spectrometry ALBERT CLARKSON and C. M. ROBERTSON, Master General of the Ordnance Inspectorates, Chemical Inspectorate, Woolwich, London S.E. 18, England Anal. Chem. 38, 522 (1966)
Aids for Analytical Chemists Powder-Polyethylene Film Technique for Spectral Measurements KARL J. S C H W I N G , Department of Chemistry, Upsala College, East Orange, N. J., and LEOPOLD MAY, Department of Chem istry, The Catholic University of America, Washington, D. C. 20017 Anal. Chem. 38, 523 (1966)
Servo-Controlled Zero Intercept Correction and Calibration of Analytical Data HARRY L. PARDUE and DAVID K. MEANS, Chemistry Depart ment, Purdue University, Lafayette, Ind.
AMINO ACIDS AND SERUM PROTEINS ADVANCES IN CHEMISTRY SERIES 44 Perhaps more individuals are concerned with amino acid and protein research than any other area of bio chemistry, not only from the standpoint of nutrition and nutritional and physiological effects, but the growing evidence of a possible link to the genetic code. AMINO ACIDS AND SERUM PROTEINS is based on the Richard J. Block Memorial Symposium, organized by the Division of Biological Chemistry of the American Chemical Society. The 10 papers by 20 contributors reflect work at the frontier of today's research activity in amino acids and protein chemistry. In the opening paper Julius Schultz discusses the nature and origin of serum proteins and suggests that undifferentiated proteins may be continuous systems rather than discrete molecular species. Other papers on biosynthesis examine the role of the liver in the biosynthesis of plasma proteins, aminoacyl transfer in ribosomes, and the role of phosphates in the urea cycle. A paper by Nobel Laureate Vincent du Vigneaud reports the fate of cystathionine in a human cystinuric. 154 Pages, cloth bound $5.50 postpaid in U. S. and Canada; 20 cents foreign and PUAS
plus
Anal. Chem. 38, 526 (1966)
Quantitative Gas Chromatographic Sampler for Static Gaseous Reaction Systems ERIC R. ALLEN, Laboratory of Atmospheric Sci ences, National Center for Atmospheric Research, Boulder, Colo. 80302
Order from: Special Issues Sales/American Chemical Society 1155 Sixteenth St., N. W./Washington, D. C. 20036
Anal. Chem. 38, 527 (1966) VOL. 38, NO. 3, MARCH 1966 ·
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