bluuebunny/crossref_metadata_2025 huggingface dataset:
RADIOCHEMICAL MEASUREMENTS OF ACTIVITY COEFFICIENTS IN MIXED ELECTROLYTES
Authors: Betts R. H. , MacKenzie Agnes N.
Published: May 2006

A method is described for the precise measurement of the activity coefficients of salts in mixed electrolytic solutions. It involves the use of synthetic ion exchange resins and radioactive tracers. The activity coefficients of the chlorides of sodium, potassium, rubidium, and cesium were measured at effectively zero concentration in hydrochloric acid solutions from 0.005 to 1.5 m. The activity coefficient of sodium chloride in solutions of lithium and potassium chlorides was also determined. The results are discussed in terms of both the Harned rule and the Stokes–Robinson theory of activity coefficients.
6,8-Dimethoxy-4-chromanone
Authors: Thorn G. Denis
Published: May 2006

not available
THE REACTION BETWEEN SILVER AND TRIPHENYLMETHYL CHLORIDE
Authors: Perry E. J. , Winkler C. A.
Published: May 2006

Kinetic evidence has been obtained to indicate that, in toluene, the reaction between silver and triphenylmethyl chloride is a tarnishing reaction involving the growth of a silver chloride film on silver. Logarithmic, linear, and parabolic rates were observed, as well as a characteristic, very sudden decrease in reaction rate under certain conditions. The film thicknesses at which most of these phenomena occurred were those predicted by the Cabrera–Mott theory for the oxidation of metals.
MEASUREMENTS OF SELF-DIFFUSION IN AQUEOUS SOLUTIONS OF SODIUM DIHYDROGEN PHOSPHATE
Authors: Burkell J. E. , Spinks J. W. T.
Published: May 2006

Measurements of self-diffusion in aqueous solutions of sodium dihydrogen phosphate have been made using P32 as tracer. The method involves the preparation of two similar solutions differing only in the fact that one is "labelled" by means of the P32 isotope. A capillary cell is filled with the radioactive solution and immersed in a relatively large volume of inactive solution, maintained at a constant temperature. After diffusion has proceeded for a measured length of time, the cell is removed and the radioactivity of the liquid remaining in it measured by counting. The self-diffusion coefficient may be calculated from the length of the capillary cell, the period of diffusion, and the ratio of the final activity to the original activity. The method was checked by repeating some work on the self-diffusion of Na+ in sodium iodide solution. Self-diffusion measurements were made with sodium dihydrogen phosphate solutions of several concentrations between 1.0 and 10−4 molar.
PREPARATION OF KETENE FROM GLACIAL ACETIC ACID. METHYL ACETATE, AND ETHYL ACETATE
Authors: Georgieff K. K.
Published: May 2006

Laboratory studies were carried out to determine whether methyl and ethyl acetates could be pyrolyzed to give yields and conversions to ketene comparable to those obtainable from acetic acid. Acetic acid was pyrolyzed to ketene and water in the presence of 0.33% triethyl phosphate or phosphoric acid catalyst at 680°–760 °C. and 140–160 mm. Hg absolute. Maximum yield obtained was 80.6% and maximum conversion 34.5%. Methyl acetate was cracked to ketene and methanol at 610°–685 °C. and 95–400 mm. absolute, using triethyl phosphate, phosphoric acid, sulphuric acid, dimethyl sulphate, butyl borate, and silica gelboric acid as catalysts. High yields could be obtained only with phosphates in 2–3% concentration. Maximum yield to ketene, including ketene recovered as acetic acid, was 76% (conversion 31–34%). Maximum yield to methanol was 81.3% (conversion 33–34%). Methyl acetate containing 18% methanol was also cracked but results were poorer. Ethyl acetate, in the presence of 0.33% triethyl phosphate, was pyrolyzed to ketene, ethylene, and water at 630°–685 °C. and 140–190 mm. absolute. Maximum yield of ketene, including ketene recovered as acetic acid, was 85.8%. Maximum conversion to ketene was 35.4% and to ketene plus acetic acid 85.7%. Yields to ethylene were nearly quantitative.
ON THE LIQUID–VAPOR COEXISTENCE CURVE OF XENON IN THE REGION OF THE CRITICAL TEMPERATURE
Authors: Weinberger M. A. , Schneider W. G.
Published: May 2006

The liquid–vapor coexistence curves of very pure xenon have been determined in bombs of vertical lengths 1.2 cm. and 19 cm. The longer bomb yielded a flat-topped coexistence curve, the shorter a more rounded curve. The classical van der Waals theory is capable of explaining a large portion of the flat top if effects of gravity are taken into account. Details of the theoretical variation of the width of the flat top with vertical bomb lengths are given. The critical data obtained for xenon are ρc = 1.105 gm./cc., Tc = 16.590 ±.001 °C. The danger of contamination of gases in the critical region on contact with gasket or packing materials is stressed.
NORMAL AND CROSS-LINKED POLYSTYRENE: I.HUGGINS' k′ AS A MEASURE OF NONLINEARITY
Authors: Manson J. A. , Cragg L. H.
Published: May 2006

Polystyrene polymerized in emulsion at 55 °C. to near-complete conversion has been subjected to careful primary, secondary, and tertiary fractionation. For representative samples and fractions thereof, the intrinsic viscosity [η] and the slope constants β and k′ have been determined at 25 °C. in butanone and benzene. For intrinsic viscosities in benzene ranging from 2.10 to 8.37, the equation log [η] (in benzene) = 0.31 + 1.23 log [η] (in butanone) holds. In butanone the value of k′ is 0.40 ± 0.01, changing from 0.39 for the lower fractions ([η] in butanone <2.00) to 0.41 for the highest fractions; in benzene, the better solvent, the corresponding values of k′ are 0.02 units lower.Samples of cross-linked polystyrene were prepared by copolymerizing styrene with small proportions of divinylbenzene. Values of k′ determined for the soluble cross-linked species, both unfractionated and fractionated, varied (in butanone) all the way from the normal 0.40 to 1.14, depending on the proportion of divinylbenzene used.It is concluded that k′ is a sensitive indicator of nonlinearity in polymer molecules, and that in polystyrene as normally prepared in emulsion systems the molecules are essentially linear.
THE PAPILIONACEOUS ALKALOIDS: XVII. THE SYNTHESIS OF STRUCTURAL ISOMERS OF SPARTEINE
Authors: Leete Edward , Marion Léo
Published: May 2006

A structural isomer of sparteine, Ψ-sparteine, has been synthesized from 2,2′-dipyridylmethane which was condensed via its lithium salt with β-bromomethylmalonic ester, followed by fission of the ether link. The product of the condensation, αα-di(2-pyridyl)-γγ-dicarbethoxy-propane, was reduced catalytically to the corresponding dipiperidyl compound which on heating in vacuo readily lost ethanol, giving rise to two isomeric dilactams. Each dilactam was reducible to a different isomer of sparteine. Just like sparteine, Ψ-sparteine can exist in three stereoisomeric forms, two of which, however, are internally compensated and therefore not resolvable.
ELECTROPHORETIC HOMOGENEITY OF POLYSACCHARIDES IN MOLAR ALKALI
Authors: Colvin J. Ross , Cook W. H. , Adams G. A.
Published: May 2006

The usefulness of electrophoretic patterns of polysaccharides in molar alkali as a general criterion of the purity of these substances has been studied. No clear separation of the components of a hemicellulose, of wheat starch, or of potato starch could be demonstrated. Similarly, mixtures of wheat starch and inulin, pectin and sodium alginate, laminarin and sodium alginate, inulin and wheat starch plus sodium alginate could not be resolved in 1 M potassium hydroxide. Nonetheless, mixtures of laminarin and sodium alginate separated rapidly at pH 6.8 and 10.4. Contrary to previous reports, it is shown that the electrophoretic technique cannot be used with confidence as a general criterion of the purity of polysaccharides in molar alkali. However, it may be applicable for the characterization and fractionation of a limited class of polysaccharides which are soluble close to neutrality.
STUDIES OF RDX AND RELATED COMPOUNDS: VII RELATION BETWEEN RDX AND HMX PRODUCTION IN THE BACHMANN REACTION
Authors: Epstein S. , Winkler C. A.
Published: May 2006

The reactions to form RDX and HMX in Bachmann-type mixtures are comparable in respect of optimum nitric acid concentrations and in the fact that optimal amounts of acetic anhydride and ammonium nitrate are necessary for maximum yields of either explosive. The activation energies for formation of RDX and HMX were also found to be comparable, at 15 ± 1 kcal. per mole. However, withholding ammonium nitrate from the reaction mixture was found to have a more deleterious effect on RDX production than on HMX production. A mechanism is proposed which attempts in a general way to represent the relation between RDX and HMX production in the type of reaction mixtures used.
PITHECOLOBINE, THE ALKALOID OF PITHECOLOBIUMSAMAN BENTH. I
Authors: Wiesner K. , MacDonald D. M. , Valenta Z. , Armstrong R.
Published: May 2006

Pithecolobine, C22H46N4O2, has a lactam group, one primary and two secondary amino groups, and a hydroxyl group. Lithium aluminum hydride converts it into a monocyclic saturated compound, desoxypithecolobine, C22H48N4. Hofmann degradation of this compound gives tetramethylputrescine, trimethyl amine, a doubly unsaturated base C16H31N with a terminal methylene group, and a base C16H34N2. Heating with selenium yields a hydrocarbon, C12;H24–26, with a sequence of six or more CH2 groups. A crystalline oxygen-free compound with two nitrogens (m.p.94 °C.) is also obtained, the ultraviolet spectrum of which is almost identical with aminopyridine.
TEMPERATURE INDEPENDENT FACTORS OF HYDROGEN ABSTRACTION REACTIONS IN THE GAS PHASE
Authors: Bywater S. , Roberts R.
Published: May 2006

Temperature independent factors for a series of hydrogen abstraction reactions in the gas phase have been calculated using the absolute reaction rate theory of Eyring and co-workers. The calculated values have been compared with experimental values wherever possible. Reasonable agreement is obtained. The factors producing variations have been examined and the sources of error in this type of calculation are discussed.
BINDING OF ANIONS BY DENATURED PROTEINS
Authors: Colvin J. Ross
Published: May 2006

The adsorption by soluble and insoluble heat-denatured lysozyme of eight anionic dyes, including methyl orange, has been determined at several temperatures and pH values. In addition, the adsorption of methyl orange by both the soluble and insoluble forms of seven other heat-denatured proteins has been determined as a function of temperature and pH. The isotherms, which are normal, reproducible, reversible, and independent of protein concentration confirm the notion of a sheath of strongly orientated water molecules about small positive proteins. They also demonstrate directly the importance of −ΔF of hydration in protein interaction studies. pH dependence of adsorption of methyl orange and other anions to denatured proteins is normal but −ΔH of adsorption per mole of anion bound is greater than for the corresponding native form.These results discredit the current concept of unique specific binding sites on a protein for weak interactions of the type studied.
ON THE OXIDATION OF 1, 1, 1-TRICHLORO-2,2-BIS- (p-TOLYL) -ETHANE
Authors: Perron Yvon
Published: May 2006

The condensation of benzene with chloral hydrate in the presence of concentrated sulphuric acid gave rise to 1,1,1-trichloro-2,2-bis-(p-tolyl)-ethane. The oxidation of this condensation product with potassium dichromate in dilute sulphuric acid at the boiling temperature yielded 1,1-dichloro-2,2-bis-(p-carboxyphenyl)-ethylene, the structure of which was shown by its oxidative degradation to 4,4′-dicarboxybenzophenone. When the oxidation of the same condensation product was carried out in the cold, with the aid of chromium trioxide in glacial acetic acid and acetic anhydride, 1,1,1-trichloro-2,2-bis-(p-carboxyphenyl)-ethane was obtained in a good yield. This last compound was converted to the dichloroethylenic-dicarboxylic acid upon refluxing with a methanolic solution of sodium hydroxide. The corresponding amide derivatives of both the dichloro and trichlorodicarboxylic acids were also prepared.
HYDROXYLATION AND EPOXIDATION OF RAPESEED OIL DERIVATIVES WITH SUBSEQUENT PYROLYSIS AND AMMONOLYSIS
Authors: Mageli O. L. , Patteson E. W. , Spencer E. Y.
Published: May 2006

A method was developed to follow the hydroxylation of rapeseed oil and erucic acid derivatives with peracetic acid. Peracetic acid prepared insitu was found to be equally as effective as the preformed acid in hydroxylation of methyl erucate. Among the compounds synthesized were ethyl 13,14-dihydroxybehenate, methyl 13,14-oxidoerucate, ethyl 13,14-diacetoxybehenate, and methyl 13,14(14,13)-hydroxyacetoxybehenate which were subsequently pyrolyzed at approximately 300 °C with p-toluenesulphonic acid as catalyst. The first compound yielded mainly the corresponding ketone with a small amount of the oxido derivative, the chief product of the second compound was also the ketone with some unsaturated material, the third compound yielded 43% of the diene, while the last one yielded 60%. Ammonolysis of the oxido compound or the bromohydrin to yield the corresponding aminohydroxy derivative under pressure with liquid ammonia and ammonium bromide was unsuccessful. A new compound oxidoerucamide, m.p.101.5°, was synthesized.
FREE RADICALS BY MASS SPECTROMETRY: III. RADICALS IN THE THERMAL DECOMPOSITION OF SOME BENZENE DERIVATIVES
Authors: Ingold K. U. , Lossing F. P.
Published: May 2006

The following benzene derivatives have been pyrolyzed in a free radical mass spectrometer: benzene, toluene, benzaldehyde, anisole, diphenyl, phenyl ether, and benzyl ether. The products and intermediates were analyzed, particular attention being paid to the formation (and stability) of any aromatic free radicals found. The phenyl, benzyl, phenoxy, and benzoyl radicals, as well as atomic carbon, were detected. The first two could be obtained abundantly and are fairly stable below 1150°. The oxygenated radicals were much less abundant and appeared to be less stable.
THE ULTRAVIOLET ABSORPTION SPECTRA OF NITROGUANIDINE DERIVATIVES
Authors: McKay A. F. , Sandorfy C.
Published: May 2006

The ultraviolet absorption spectra of the ammonia and amine addition products of 1-nitro-2-nitramino-2-imidazoline verify the linear structure A for these compounds. Also the ethanol addition product is considered on the basis of [Formula: see text]its absorption spectrum to be N-β-nitraminoethyl-N-nitro-o-ethylisourea. The relative effects of the nitramino and nitroguanidine chromophores on the absorption spectra of several nitroguanidine derivatives are discussed.
THE ESSENTIAL OIL OF ABIES BALSAMEA (L.) MILL.
Authors: Shaw A. C.
Published: May 2006

Foliage of Abies balsamea yielded 0.591% of an essential oil comprised of l-β-pinene, l-bornyl acetate, d-Δ3-carene, l-limonene, l-α-pinene, l-camphene, myrcene, santene, tricyclene, l-camphor, l-borneol, d-canadene, bisabolene, terpinolene, and a compound related to S-guiaiazulene.
AN ELECTRON-MICROGRAPH STUDY OF OXIDE FILMS ON ELECTROPOLISHED SURFACES OF IRON
Authors: Caule E. J. , Cohen M.
Published: May 2006

An electron micrographic study has been made of iron surfaces subjected to electropolishing. It has been found that although electropolishing produces a relatively smooth surface, the iron is covered with a film. The strengthening of this film by oxidation and its disruption by reduction with hydrogen have been followed. The film is assumed to be oxide and its thickness has been estimated to be approximately 100 Angstrom units. The effect of reduction of the film on surface area and thus on initial oxidation rates of the reduced specimen has been considered.
THE ALKALOIDS OF LYCOPODIUM SPECIES: XII. RELATIONSHIP BETWEEN SOME OF THE MINOR ALKALOIDS AND LYCOPODINE
Authors: Douglas Bryce , Lewis D. G. , Marion Léo
Published: May 2006

Reduction of the carbonyl group of lycopodine with lithium aluminum hydride gives rise to dihydrolycopodine which contains a secondary alcoholic group. The new base can be dehydrated to form anhydrodihydrolycopodine and this is identical with alkaloid L14(C16H25N). Acetylation of dihydrolycopodine produces O-acetyldihydrolycopodine which is identical with alkaloid L2(C18H29O2N). On distillation at atmospheric pressure alkaloid L2 is pyrolyzed and gives rise to 7-methylquinoline. Alkaloids L8 and L30 which had been reported previously as different have now been found to be identical.
THE USE OF INFRARED SPECTROPHOTOMETRY FOR THE ESTIMATION OF SMALL QUANTITIES OF SOME HALOGENATED HYDROCARBONS
Authors: Breitman L. , Steacie E. W. R.
Published: May 2006

The infrared spectra of chloral, carbon tetrachloride, and chloroform have been determined between 1500 and 650 cm.−1 over a range of pressures in the gas phase. Absorption bands suitable for the quantitative analysis of binary and ternary mixtures of the components have been selected and their peak intensities shown to obey Beer's Law over the range of pressures studied. Ternary mixtures have been analyzed from the spectra with an accuracy of about 20%.The spectra of dichloromethane and methyl chloride have also been measured under comparable conditions.
THE KINETICS OF THE THERMAL DECOMPOSITION OF VINYL ISOPROPYL ETHER
Authors: Blades Arthur T.
Published: May 2006

The thermal decomposition of vinyl isopropyl ether in the presence of toluene has been studied in a flow system in the temperature range 447–521 °C. In this range, the data indicate a purely intramolecular decomposition into propylene and acetaldehyde, the activation energy for the reaction being in close agreement with that found for the decomposition of vinyl ethyl ether. At 570 °C. a minor free radical decomposition of the ether becomes apparent. Some qualitative studies of the decomposition of vinyl isobutyl ether are also reported.
THE EFFECT OF RELATIVE HUMIDITY ON THE REACTION OF NINHYDRIN WITH AMINO ACIDS ON PAPER CHROMATOGRAMS
Authors: Wellington Eunice F.
Published: May 2006

The effect of different relative humidities at 20 °C. on the colored product of ninhydrin with amino acids on paper chromatograms has been investigated. It has been shown that there is only a very narrow range of humidity (35–40%) within which maximum color development for most amino acids can be expected (aspartic acid behaves anomalously), and that the color intensity falls off rapidly on both sides of this maximum.
THE DEPENDENCE OF THE HYDROLYSIS OF DIAZOACETIC ESTER ON THE HYDROGEN ION CONCENTRATION
Authors: Willi A. V. , Robertson R. E.
Published: May 2006

The catalytic constants of the H3O+ catalyzed hydrolysis of diazoacetic ester in aqueous solutions containing sodium perchlorate have been determined at three different ionic strengths. A spectrophotometric method was used to follow the rate. The results indicate a strong positive salt effect. Measurements at the ionic strength μ = 0.110 were carried out in the pH region from 1.97 to 5.19. For solutions containing less than 10−3 N perchloric acid the pH data were taken from measurements with a. glass electrode in the kinetic cell. Within the limits of experimental error no deviations from proportionality between rate and [H3O+] were found. This result is important in connection with our findings for the benzalaniline hydrolysis since it tests the methods applied and proves that the benzalaniline example with deviations from linearity between rate and [H3O+] is a special case. The diazoacetic ester hydrolysis is not catalyzed by acetic acid molecules.
A NEW SYNTHESIS OF β-GLUCOPYRANOSIDES
Authors: Lemieux R. U. , Shyluk W. P.
Published: May 2006

Reaction of equivalent amounts of pentaacetyl-β-D-glucopyranose and methanol in benzene or chloroform solution in the presence of 0.5 or more moles of stannic chloride per mole of methanol gave 50-60% yields of methyl tetraacetyl-β-D-glucopyranoside. α-Acetochloroglucose was a by-product of the reaction. The mechanism of the reaction is discussed. The method was applicable for the preparation of phenyl tetraacetyl-β-D-glucopyranoside.
CARBODIIMIDES: PART II. THE REACTION OF SULPHONIC ACIDS WITH CARBODIIMIDES. A NEW METHOD OF PREPARATION OF SULPHONIC ANHYDRIDES
Authors: Khorana H. G.
Published: May 2006

Methane, benzene, and p-toluene sulphonic acids react instantaneously at room temperature with dicyclohexyl and di-p-tolyl carbodiimides to form the corresponding sulphonic anhydrides, VI, and disubstituted ureas, VII. The use of di-p-tolyl carbodiimide affords a convenient general method of preparation of sulphonic anhydrides.
THE STABILITY OF SOME COMPLEXES OF TRIVALENT COPPER
Authors: Lister M. W.
Published: May 2006

New methods are given for the preparation of sodium copper (111) tellurate, Na9Cu(TeO6)2.16H2O, and sodium copper (111) periodate, Na7Cu(IO6)2.20H2O, previously reported by Malatesta. Additional analytical evidence is presented that these are really compounds of trivalent copper. The dissociation of the ions in alkaline aqueous solution was examined through the ability of the uncomplexed copper to catalyze the decomposition of sodium hypochlorite. Evidence is presented that the uncomplexed copper ion is Cu(OH)4−, and this gives both a 1-1 and a 1-2 complex with both tellurate and periodate. The 1-2 complexes appear to be Cu(HTeO6)2−7 and Cu(IO6)2−7 respectively; the 1-1 complexes are less stable. The equilibrium constants for the reversible dissociation of these ions into their simpler constituents in aqueous solution at 40 °C. are as follows: tellurate, 1-1 complex K1 = 1.8 × 10−6; 1-2 complex K2 = 1.1 × 10−11; periodate, 1-1 complex K1 = 3.4 × 10−5; 1-2 complex is K2 = 8.0 × 10−11. The smaller the constant the more stable the complex ion. In the case of the tellurate complex K2 is proportional to the square of the hydroxide ion concentration and these values are for 0.400 M sodium hydroxide; with periodate K2 is independent of the hydroxide concentration. Experiments at various temperatures give 20 kcal. as the heat of the reaction forming the 1-2 tellurate complex from the simple ions, and 71/2 kcal. for the 1-2 periodate complex. The stannate, stibnate, and selenate ions showed no signs of forming analogous compounds.
A NEW SYNTHESIS OF URANIUM TRIFLUORIDE
Authors: Runnalls O. J. C.
Published: May 2006

not available
AN EFFECT OF POLYMERIZATION TEMPERATURE ON THE HUGGINS CONSTANT k′ FOR A DIENE POLYMER
Authors: Cragg L. H. , Fern G. R. H.
Published: May 2006

Samples of poly(butadiene-co-styrene) were polymerized in redox systems at 5° and −18 °C., the recipes being such as to yield samples similar in composition, in percentage conversion, and in intrinsic vistex to those prepared at 50°, 40°, 30°, and 15 °C. for an earlier study. The two samples were carefully fractionated and the viscosity functions [η], β, and k′ were determined for each of the fractions, k′ was shown to be the same for all the fractions of a given sample—an indication that there is little or no branching at these low temperatures. Comparison with the earlier results reveals, however, that for unbranched species k′ increases as the temperature of polymerization decreases, from 0.327 ± 0.008 at 50° to 0.370 ± 0.005 at −18 °C. This increase in k′ is attributed to an increase in the trans-1,4-content of the polymer.
REARRANGEMENT IN THE REACTION BETWEEN 2-PHENYLETHYLAMINE-1-C14 AND NITROUS ACID
Authors: Lee C. C. , Spinks J. W. T.
Published: May 2006

On treatment with sodium nitrite, 2-phenylethylamine-1-C14 in aqueous hydrochloric, perchloric, acetic, or glacial acetic acid gives rise to products in which the C14 atoms have been rearranged from the C-1 to the C-2 position to an extent of 20.5 to 22.5%. The results are discussed on the basis of carbonium ions as possible reaction intermediates.
THE FLOW PROPERTIES AND MESOMORPHIC BEHAVIOR OF ANHYDROUS SOAPS AT ELEVATED TEMPERATURES: PART I. SODIUM STEARATE ABOVE 200
Authors: Powell B. D. , Puddington I. E.
Published: May 2006

Although there is a large body of literature dealing with the transition temperatures of the alkali metal salts of the fatty acids, it has not always been possible to feel confidence in their graphical determination. Hitherto few measurements have been made of the viscosity of soaps as a function of temperature and rate of shear, though such measurements promise to prove useful, as sharp changes have been observed in the regions of previously reported transition points. The viscosity apparatus is described and the results obtained with anhydrous sodium stearate given, from the aspect of transition temperatures and as a study of flow properties.
ON THE MECHANISM OF THE DISSOLUTION OF MAGNESIUM IN ACIDIC SALT SOLUTIONS: I. PHYSICAL CONTROL BY SURFACE FILMS
Authors: Casey E. J. , Bergeron R. E.
Published: May 2006

A kinetic study and analysis has been made of the effects of ionic strength, acid activity, temperature, and salt type on the dissolution of magnesium in acidic salt solutions. This is an example of the simplest type of corrosion involving hydrogen evolution. The results are interpreted in terms of the effects of the various factors on the structure of a surface film which must be magnesium oxide and/or hydroxide even in acidic solutions. The importance of internal dissolutions in the film at high concentrations of attacking reagent, for this and other cases, is shown. Owing to complex formation, under certain conditions an odd case of "chemical control" of the dissolution rate in this simplest case becomes evident. Corrosion potential measurements aid in the interpretation.
REACTIONS OF CYANOGEN IODIDE
Authors: Bodnar L. E. , Cleave A. B. Van
Published: May 2006

A series of hydrogen chloride catalyzed reactions involving cyanogen iodide as the starting material have been investigated in dioxane and in aqueous solution at 30°and 45 °C. The course of the reaction was followed by determining the decrease in the number of oxidation equivalents present. Reaction products identified were: iodine monochloride, iodine, ammonium chloride, and carbon dioxide. A possible reaction mechanism has been suggested.
α-OBSCURINE AND β-OBSCURINE: STRUCTURE STUDIES
Authors: Moore Barry P. , Marion Léo
Published: May 2006

The alkaloid hitherto described as obscurine has been shown to consist of a mixture of two bases, α-obscurine (C17H26ON2) and β-obscurine (C17H24ON2). Dehydregenation of α-obscurine by heating with palladium-charcoal gives rise to 7-methylquinoline and 6-methyl-α-pyridone. The infrared absorption spectrum of the base shows absorption bands indicative of a carbony and of a secondary amino group, possibly in a cyclic lactam, while absorption in the ultraviolet indicates the presence of a double bond conjugated with the carbonyl group. β-Obscurine on the other hand contains an α-pyridone ring as shown by its infrared absorption spectrum and also by the similarity of its ultraviolet absorption spectrum with that of 6-methyl-α-pyridone.
ORGANIC PHOSPHORUS COMPOUNDS: II: PREPARATION OF CHLOROMETHANEPHOSPHONYL DICHLORIDE
Authors: Bannard R. A. B. , Gilpin J. R. , Vavasour G. R. , McKay A. F.
Published: May 2006

Hydroxymethanephosphonic acid was prepared by treating paraformaldehyde with phosphorus trichloride at atmospheric pressure and subsequent hydrolysis of the resultant complex. Chloromethanephosphonyl dichloride was obtained by chlorination of hydroxymethanephosphonic acid with thionyl.chloride in the presence of pyridine. On the other hand hydroxymethanephosphonic acid combined slowly with phosphorus pentachloride to give the hitherto unknown dichlorophosphorylmethanephosphonyl dichloride, Cl2P(O)OCH2P(O)Cl2, together with chloromethanephosphonyl dichloride. The structure of dichlorophosphorylmethanephosphonyl dichloride was confirmed by its conversion with phosphorus pentachloride at 78 °C into chloromethanephosphonyl dichloride and phosphorus oxychloride. The preparation of chloromethanephosphonyl dichloride by interaction of paraformaldehyde and phosphorus trichloride in an autoclave at 250 °C was studied in reference to the influence of heating time on the yield.
A CONVENIENT SYNTHESIS OF DL-ORNITHINE
Authors: Gaudry Roger
Published: May 2006

DL-Ornithine is readily prepared in a 68% yield by condensing 3-bromopropylphthalimide with ethyl acetamidocyanoacetate and by hydrolyzing the resulting 2-acetamido-2-carbethoxy-5-phthalimidovaleronitrile into DL-ornithine, isolated as the monohydrochloride. 3-Bromopropylphthalimide is obtained in a 57% yield from 3-aminopropanol by reaction with phthalic anhydride, followed by phosphorus tribromide.
PYRIDINE DERIVATIVES: PART VI MALONATIONS OF SUBSTITUTED NITROPYRIDINES
Authors: Gruber W.
Published: May 2006

5-Hydroxy-2-alkylpyridines (VII) were prepared by a sequence of reactions starting with the malonation of 2-chloro-5-nitropyridine with diethyl alkylmalonates. Malonation failed with 4-methoxy-3-nitropyridine (VIII) and 2-chloro-3-nitropyridine (XII), yielding decomposition products only. Reactivity of the. methoxyl groups in 4-methoxy-3-nitropyridine (VIII) and in 2-methoxy-3-nitropyridine (XV) was compared with respect to the rearrangement to N-methylpyridone, the reaction with aromatic amines, and hydrolysis with dilute acids. Methylation of 2-hydroxy-3-nitropyridine yields either 2-methoxy-3-nitropyridine (XV) or N-methyl-3-nitro-2-pyridone (XVI) as can be expected.
THE STRUCTURE AND GRIGNARD REACTION OF THE β-AMINOCROTONONITRILE
Authors: Conn Jaspar J. , Taurins Alfred
Published: May 2006

The ultraviolet absorption spectra of the low and high melting forms of β-aminocrotononitrile (I) provide evidence that both of them possess the same enamine structure. Since the existence of the polymorphic modifications of I must be excluded on the basis of the thermochemical behavior of I, the difference of the two modifications is capable of accounting for cis and trans isomerism, the low melting modification being the cis form, and the high melting modification being the trans form.In the reaction of I with aromatic Grignard reagents β-amino ketones of the type CH3—CO—CH==C(NH2)—R are formed as the main reaction products.The free radical mechanism of the formation of I is postulated.
SYNTHESIS OF ORGANIC DEUTERIUM COMPOUNDS: IX. BISTRIDEUTEROMETHYL MERCURY
Authors: Bevege E. E. , Renaud R. , Leitch L. C.
Published: May 2006

not available
THE HYDROLYSIS OF THE CONDENSED PHOSPHATES: I. SODIUM PYROPHOSPHATE AND SODIUM TRIPHOSPHATE
Authors: Crowther Joan Pedley , Westman A. E. R.
Published: May 2006

The rates of hydrolysis of sodium pyrophosphate and triphosphate in solution have been measured at 65.5 °C. over the pH range 2.0 to 12.0 and the phosphorus concentration range 0.10 to 0.25 atomic weights per liter. The reactions were found to be first order providing a constant concentration of hydrogen ion was maintained in the reaction flask. Both reactions are acid catalyzed but only the hydrolysis of triphosphate was found to be base catalyzed. Pyrophosphate and triphosphate apparently hydrolyze independently of each other.
REACTIONS OF SYRINGALDEHYDE INVOLVING HALOGENATION
Authors: Kavanagh K. R. , Pepper J. M.
Published: May 2006

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THE ORTHO–PARA CONVERSION OF HYDROGEN AND DEUTERIUM ON INHOMOGENEOUS PARAMAGNETIC SURFACES
Authors: Sandler Y. L.
Published: May 2006

The kinetics of the magnetic ortho–para conversion of hydrogen and deuterium on neodymium oxalate and hemin crystals has been determined over a wide temperature range in a static system. In these cases a similar type of rate curve is obtained: at high and at low temperatures the rate decreases with temperature, while in the intermediate region the rate increases with temperature. The behavior is explained in terms of an energetic surface heterogeneity. In case of neodymium oxalate two distinctly different groups of sites appear to be active having energy barriers to migration of the adsorbed hydrogen at considerably different height. The conversion mechanism of the "trapped" gas is assumed to be similar to the mechanism in liquids where repeated collisions are also assumed to occur.
STUDIES IN THE POLYOXYPHENOL SERIES: VI. THE OXIDATION OF PYROGALLOL AND VANILLIN BY ALKALINE HYPOIODITE AND HYPOCHLORITE
Authors: Thorn G. Denis , Purves C. B.
Published: May 2006

Approximately 0.003 M solutions of pyrogallol and of vanillin in boric acid – sodium hydroxide buffers were used at 25 °C. to reduce hypoiodite and hypochlorite solutions made from sixfold molar amounts of the halogens. In all four cases the reduction reached a maximum in a narrow range near pH 9, and with hypoiodite the production of iodoform was restricted to this range. Slower secondary reductions were superimposed on very fast primary reactions. When oxidized with an equimolar amount of halogen near pH 8.5, vanillin gave a 90% yield of 5-iodovanillin and 65% of the 5-chloro derivative. These yields decreased with increasing alkalinity as the halogenations became slower. A new, simple preparation of trichloropyrogallol in 72% yield consisted of carrying out the chlorination with 3 moles of hypochlorite at pH 12. An equilibrium between pyrogallol–hypoiodite and 3-hydroxy-1,2-benzoquinone–iodide appeared to exist at the same pH.
THE SILVER CATALYZED OXIDATION OF ETHYLENE: I. SLOW PROCESSES ON THE CATALYST SURFACE
Authors: Orzechowski A. , MacCormack K. E.
Published: May 2006

In the silver catalyzed oxidation of ethylene or ethylene oxide (EtO), the silver catalyst activity measured under constant standard conditions in a flow system was found to be dependent on the conditions of previous catalyst treatment such as reaction temperature and reactant composition. The results are explained on the basis of slow establishment of equilibrium respecting fixation of stably sorbed oxygen atoms and surface products of oxidation. It is emphasized that in view of the slow processes observed, the kinetic measurements must be punctuated by frequent stabilizing check runs in order to maintain the catalyst in the same reference state.
THE VISCOSITY OF GASES AND THE THEORY OF CORRESPONDING STATES
Authors: Whalley E.
Published: May 2006

The viscosity of gases is examined using the theory of corresponding states. The curve of reduced viscosity plotted against reduced temperature is compared with the theoretical curves obtained for several intermolecular potentials. The approximate Sutherland equation gives the best fit and it is suggested that this be used to extrapolate viscosities to high temperatures where experimental data are not available. The reduced viscosity – reduced temperature plot can be used for estimating the viscosities of simple gases from critical data, or critical data from the viscosities.
IRRADIATION OF CHLOROFORM–WATER SYSTEMS WITH CO60 GAMMA-RAYS AND BETATRON X RAYS
Authors: Hummel R. W. , Cleave A. B. Van , Spinks J. W. T.
Published: May 2006

The production of acid from two commercial brands of chloroform, on exposure to Co60 gamma-rays and high energy X rays from a betatron, has been measured. Inhibitor-free chloroform liberates acid in amounts varying linearly with the radiation dose. The specific yield, in micromoles of acid produced per liter of chloroform per kiloroentgen, varies inversely as the square root of the dose rate. The specific yields are slightly less for betatron radiations, compared with Co60 gamma-rays. The average lifetime of the free radical chains is about one second.
HYDROGEN PEROXIDE AND ITS ANALOGUES: V. PHASE EQUILIBRIA IN THE SYSTEM D2O–D2O2
Authors: Giguère Paul A. , Secco E. A.
Published: May 2006

The cooling curves of a number of solutions of deuterium peroxide in heavy water in the concentration range 11% to 95% were measured in order to determine the solid-liquid phase diagram for that binary system. The apparatus of Herington and Handley, which uses a pulsing pressure for stirring the solutions, and a thermistor, was found to be particularly suitable for that purpose. As could be expected the freezing-point curve of the deuterated compounds is closely similar to that of the hydrogen compounds, being shifted up only by about 4° for water-rich solutions and by 2° for peroxide-rich solutions. The melting point of the addition compound, D2O.2D2O very nearly coincides with one of the eutectic points at 46.2% D2O2 and −51.5 °C.; the other eutectic point is at 60.5% D2O2 and −55.1 °C. By extrapolation the melting point of pure deuterium peroxide is found to be 1.5 °C. as compared with −0.43 °C. for hydrogen peroxide. Concentrated solutions of deuterium peroxide exhibit an extreme tendency to supercool, resulting sometimes in formation of glasses even at liquid-air temperature. The previous results of Foley and Giguère for the system H2O–H2O2 were confirmed, specially as regards the melting point of the addition compound H2O2•2H2O.
THE PRODUCTION OF ISOCYANATES BY THE THERMAL DECOMPOSITION OF PSEUDOUREAS
Authors: Robinson J. R.
Published: May 2006

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EFFECT OF GELATIN ON THE CHANGES IN INITIAL CATHODE POLARIZATION DURING ELECTRODEPOSITION OF COPPER
Authors: Parsons B. I. , Winkler C. A.
Published: May 2006

In the absence of addition agent, the cathode polarization during initial electrolysis of copper from a solution of acid copper sulphate rose almost instantaneously from zero to approximately the steady state polarization. When gelatin was present in the electrolyte, the polarization generally increased to a maximum, Pmax, (in time tmax) then decreased to a minimum, Pmin, (in-time tmin) beyond which it increased to the steady state value, Ps. Generally, Pmax increased to a steady value with an increase in the time, T0, the electrode was in contact with the electrolyte before electrolysis was begun. At low, moderate, and high current densities respectively, tmax increased continuously, passed through a maximum, and decreased continuously with T0.The behavior of tmin approximately paralleled that of tmax. The polarization was linear in the logarithm of the current density; tmax and tmin decreased with increase in current density. The polarization values increased and tmax decreased, with increase in gelatin concentration. Increase of temperature had approximately the same effect as decrease in current density. With both chloride and gelatin present, Pmax was practically independent of T0 and chloride concentration, while Pmin and Ps showed minimum values at about 2 mgm./l. chloride.
THE REACTIONS OF METHYL AND ETHYL RADICALS WITH DIETHYL KETONE
Authors: Ausloos P. , Steacie E. W. R.
Published: May 2006

The hydrogen-abstraction reactions of methyl and ethyl radicals from diethyl ketone have been studied in the temperature range 25 to 160 °C. Azomethane and azoethane were used as photochemical sources of methyl and ethyl radicals. The activation energies found were 7.0 and 7.6 kcal., respectively, for the reactions:[Formula: see text][Formula: see text]If the combination of both methyl and ethyl radicals is assumed to occur at every collision, the steric factors for the two reactions are E1 = 7.4 × 10−4, E2 = 7.1 × 10−4.
THE C14 ISOTOPE EFFECT IN THE CONDENSATION OF BENZOYLBENZOIC ACID-CARBOXYL-C14 TO ANTHRAQUINONE-9-C14
Authors: Stevens W. H. , Crowder D. A.
Published: May 2006

Benzoylbenzoic acid-carboxyl-C14 has been synthesized. The C14 isotope effect in the condensation of this acid to anthraquinone-9-C14 in concentrated sulphuric acid has been measured and the ratio of the reaction rates, k(14)/k(12), found to be 1.074 ± 0.003. It is suggested that this result supports the mechanism for this reaction proposed by Newman.
THE AERATION PRODUCTS OF DISODIUM ETHYLENEBISDITHIOCARBAMATE
Authors: Thorn G. D. , Ludwig R. A.
Published: May 2006

The aeration of dilute solutions of disodium ethylenebisdithiocarbamate yields hexahydro-1,3,6-thiadiazepine-2,7-dithione (I), polymeric I, 2-imidazolidinethione, and elemental sulphur. I with ammonia gives mainly hexahydro-1,3,5-triazepine-2,4-dithione. I and polymeric I have high antifungal activity.
UNIT CELL, SPACE GROUP, AND INDEXED X-RAY DIFFRACTION POWDER DATA FOR CERTAIN NARCOTICS: IV. PROTOPINE
Authors: Barnes W. H. , Forsyth W. J.
Published: May 2006

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DETERMINATION OF THE ABSOLUTE FISSION YIELD OF Ba140 IN THERMAL NEUTRON FISSION OF U235
Authors: Yaffe L. , Thode H. G. , Merritt W. F. , Hawkings R. C. , Brown F. , Bartholomew Rosalie M.
Published: May 2006

The absolute fission yield of Ba140 in the thermal neutron fission of U235 has been determined to be (6.32 ± 0.24)%. The reaction B10(n, α)Li7 was used as a neutron monitor and the B10/B11 ratio determined mass spectrometrically before and after neutron bombardment. The Ba140 disintegration rate was determined using 4π counting techniques. The half-life of La140 has been found to be 40.31 ± 0.06 hr.
n-EICOSENOIC ACID IN SOME NATURAL GLYCERIDE OILS
Authors: Hopkins C. Y. , Chisholm Mary J.
Published: May 2006

n-Eicosenoic acid (as acid or ester) was isolated from the following oils: rutabaga seed (Brassica napobrassica Mill.), frenchweed seed (Thlaspi arvense L.), dogfish liver (Squalus acanthias L.), and the blubber oil of the beluga or white whale (Delphinapterus leucas [Pallas]).The eicosenoic acid from each of these materials was found to have the unsaturation in the 11,12 position. The content of eicosenoic acid in the four oils is estimated as follows (% of the total fatty acids): rutabaga 6, frenchweed 7, dogfish liver 11, beluga 4. The best sources, in respect to yield and purity, were frenchweed seed and rutabaga seed.The frenchweed oil had the following fatty acid composition (% total fatty acid): saturated acids 3, oleic 16, linoleic 25, linolenic 12, eicosenoic 7, erucic 37.9-Hexadecenoic acid was identified as a constituent of dogfish liver oil and beluga oil.
SOME ASPECTS OF THE TOLUENE PYROLYSIS
Authors: Blades Arthur T. , Steacie E. W. R.
Published: May 2006

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LYCOCTONINE: THE ENVIRONMENT OF THE NITROGEN
Authors: Edwards O. E. , Marion Léo
Published: May 2006

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CONSTITUTION OF A HEMICELLULOSE FROM WHEAT BRAN
Authors: Adams G. A.
Published: May 2006

The hemicellulose prepared from wheat bran by alkaline extraction was an acidic polysaccharide containing arabinose (50.0%), xylose (38.5%), and uronic acid (9.0%). Graded hydrolysis with 0.02 N oxalic acid preferentially released 65% of the arabinose with only a small simultaneous production of xylose. Hydrolysis of the full methylated hemicellulose yielded 2,3,4-tri-O-methyl-, 2,3-di-O-methyl-, 2-O-methyl-, and free D-xylose; 2,3,5-tri-O-methyl-, 2,5-di-O-methyl-, and probably 3- and 5-O-methyl-L-arabinose. These data, together with those from periodate oxidation, strongly suggested that the molecule was a highly branched araboxylan. Viscosity measurements and reducing power determinations indicated a degree of polymerization of 300.
ESSAI DE SYNTHÈSES PSEUDOPHYSIOLOGIQUES DE 6,7-DIMÉTHOXYISOQUINOLÉINES
Authors: Ferron Jean-Louis , L'Ecuyer Philibert
Published: May 2006

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INVESTIGATION OF THE PHYSICALLY ADSORBED STATE BY MEANS OF DIELECTRIC MEASUREMENTS
Authors: Channen E. W. , McIntosh R.
Published: May 2006

Dielectric data obtained for a variety of adsorbates on porous silica gel and on nonporous rutile are summarized. Four methods of computing the polarizabilities or dielectric constants of the adsorbed matter are outlined and applied using the primary experimental data of capacitance change and volume adsorbed. All four methods contain somewhat arbitrary assumptions and at best are semi-empirical. None predicts values of the electrical constants of the adsorbed species which appear reasonable in all cases. It is concluded that an interpretation of the phenomena revealed by the primary data is not possible until improved methods of computing the polarizability of adsorbed material are developed.
USE OF INTERPOLATION THEORY IN THE ANALYSIS OF GAS ADSORPTION ISOTHERMS: I. THEORY
Authors: Honig J. M. , Rosenbloom P. C.
Published: May 2006

The theory presented in this paper permits the determination of extremal bounds for a given adsorbate–adsorbent system within which the adsorption isotherms must fall if certain assumptions pertaining to the nature of the adsorption process are applicable. The use of interpolation theory in estimating lower and upper bounds on physical quantities of interest in adsorption theory is also discussed.
SURFACE ENERGIES OF THE ALKALI HALIDES
Authors: Benson G. C. , Benson G. W.
Published: May 2006

Previous theoretical calculations and experimental measurements of the surface energies or enthalpies of the alkali halides are reviewed briefly. A new attempt to determine the surface enthalpy associated with the {100} face of sodium chloride from a calorimetric study of the effect of particle size on the heat of solution is described. The result (305 ergs/cm.2 at 25 °C.) appears to be larger than might be predicted on the basis of the classical Born-Mayer theory.
A LOW TEMPERATURE PARTICLE SIZE EFFECT ON THE HEAT CAPACITY OF SODIUM CHLORIDE
Authors: Patterson D. , Morrison J. A. , Thompson F. W.
Published: May 2006

An effect of particle size upon the heat capacity of sodium chloride has been found in the temperature range 9° to 21°K. The experiments were done with three NaCl samples of specific surfaces between 38 and 59 sq. meters per gm. The observed effect has the temperature dependence predicted by theory but its magnitude is three to four times larger than expected. It is unlikely that adsorbed gases have made any significant contribution in the experiments. The accuracy with which the specific heat and surface area differences have been determined is not high enough to show definitely whether or not the surface specific heat is an extensive property of the surface.
REVERSIBILITY IN PHYSICAL ADSORPTION
Authors: Pace E. L. , Dennis K. S. , Greene S. A. , Heric E. L.
Published: May 2006

The question of reversibility and equilibrium is considered in relation to the physical adsorption of gases on finely divided solid surfaces. Conclusions are drawn from calorimetric measurements of (1) adsorption isotherms, (2) integral, differential, and isosteric heats of adsorption, and (3) heat capacity of the adsorbed phase for surface coverages of the order of a monolayer or less. In line with the preceding, results are presented and discussed for calorimetric studies involving (1) heats of adsorption and heat capacities of methane adsorbed on rutile between 80 and 140°K., (2) heats of adsorption of argon on rutile between 60 and 90°K., and (3) the zero point entropy of krypton adsorbed on rutile at a coverage of about 0.57 of the monolayer capacity.
ON THE CALCULATION OF THERMAL TRANSPIRATION
Authors: Liang S. Chu
Published: May 2006

The equation proposed earlier has been derived from a new kinetic concept. It is shown to be a reasonable approximation of this new consideration. The equation is also shown to be mathematically consistent with the general fact that when the thermomolecular pressure difference is plotted against the normally measured pressure, a single maximum is obtained. The curves calculated from this equation are shown to agree closely with those from the Weber equation using van Itterbeek and de Grande's data. The practical use of the equation is discussed.
THE ADSORPTION OF ARGON ON SOME VACUUM DEHYDRATED SALTS
Authors: Quinn H. W. , Missen R. W. , Frost G. B.
Published: May 2006

Isotherms for the adsorption of argon on amorphous products formed by the vacuum dehydration of several hydrated salts have been determined. These have shown that the adsorption is physical and that dehydration results in the formation of products of large capillary volume. The probable distribution of capillary diameters has been estimated and correlated with the effect of water vapor at low pressures in catalyzing the crystallization of the amorphous intermediates. Consideration of these findings, in the light of data for the heats of transition from the amorphous to the crystalline state, suggests that the X-ray amorphous character is not entirely due to the capillary structure but that other changes occur. The possible nature of these is discussed.