bluuebunny/crossref_metadata_2025 huggingface dataset:
THE REACTION OF ACTIVE NITROGEN WITH ACETYLENE
Authors: Versteeg J. , Winkler C. A.
Published: May 2006

The main products of this reaction were hydrogen cyanide and polymer that contained approximately 32% nitrogen. Yields of these substances increased to constant values with increase of acetylene flow rate. Some cyanogen and methane were also formed. The yield of cyanogen passed through a maximum with increased flow rate of acetylene, but the methane yields were quite erratic.
MICRODETERMINATION OF COBALT COLORIMETRICALLY AS THE 1-NITROSO-2-NAPHTHOL COMPLEX
Authors: Nichol W. E.
Published: May 2006

An advantage of determining cobalt with 1-nitroso-2-naphthol is that the reagent is relatively stable and forms a very stable cobalt complex. Also this cobalt complex has maximum absorption in the visible spectrum which allows determination visually or with ordinary colorimeters.The procedure is based on decreasing the iron interference by the removal of part of the iron as phosphate and on a simple purification of the carbon tetrachloride solution of the 1-nitroso-2-naphthol cobalt complex which eliminates traces of palladium, iron, etc.The method has the same order of accuracy as the o-nitrosocresol method but preparation of reagents and the analysis in general require less time.
THE DIFFUSION OF POLYISOBUTYLENE IN DIFFERENT SOLVENTS
Authors: Luner C. , Winkler C. A.
Published: May 2006

The diffusion coefficient of polyisobutylene in n-heptane has been found to decrease at first, then to increase with increasing molecular weight.
SYNTHESIS OF ORGANIC DEUTERIUM COMPOUNDS: IV. METHYL-d3 BROMIDE
Authors: Nolin B. , Leitch L. C.
Published: May 2006

Silver acetate-d3 and bromine react readily in the dry state in a sealed tube to give methyl-d3 bromide in high yield. This method is more convenient than the reduction of carbon dioxide to deuterated methyl alcohol with lithium aluminum deuteride, followed by the conversion of the alcohol into the halide, or other methods hitherto reported.
THE PAPILIONACEOUS ALKALOIDS: XVIII. LUPINUS SERICEUS PURSH.
Authors: Marion Léo , Leonard Nelson J. , Moore Barry P.
Published: May 2006

The plant investigated has been found to contain at least five alkaloids, three of which, l-sparteine, d-lupanine, and d-α-isolupanine, are of known structure. The remaining two are both isomeric with hydroxylupanine. One of these, lupilaxine, was identical with a base previously reported as occurring in Lupinuslaxus. The other, lupanoline, appeared to be new. Both these alkaloids were shown by their infrared absorption spectra to contain, like hydroxylupanine, one hydroxyl group and one carbonyl.
STUDIES ON RDX AND RELATED COMPOUNDS: IX. DETERMINATION OF NITRIC ACID AND ACETIC ANHYDRIDE IN BACHMANN LIQUORS
Authors: Betts R. H. , Stuart R. S. , Winkler C. A.
Published: May 2006

An electrometric method for determination of nitric acid in RDX(B) liquors has been developed. The method is not largely affected by ammonium nitrate and acetic anhydride. A precision of ± 0.5% may be readily obtained. Acetic anhydride in RDX(B) liquors may be determined by direct titration with standard aniline–toluene solution at 0 °C., using calcium hypochlorite as an external indicator. In routine analysis, a precision of ± 2% may be obtained.
STUDIES ON RDX AND RELATED COMPOUNDS: X. ANALYSIS FOR NITRIC ACID IN ACETIC ACID – ACETIC ANHYDRIDE MEDIA
Authors: Marcus R. A. , Winkler C. A.
Published: May 2006

An analytical method has been developed for the estimation of nitric acid in acetic acid – acetic anhydride media, with a precision of 0.3%. The procedure involves the addition of a solution of potassium acetate in acetic acid to the sample. The excess is back-titrated conductometrically with a standard solution of nitric acid in acetic acid.
BETATRON IRRADIATION OF AQUEOUS FERROUS SULPHATE SOLUTIONS
Authors: Hummel R. W. , Spinks J. W. T.
Published: May 2006

The oxidation of aerated aqueous solutions of ferrousammonium sulphate has been studied using radium gamma rays and X rays of 24.5 Mev. peak energy from a betatron. The behavior at high photon energies has been shown to be closely similar to that at lower photon energies.
ELECTROPHORESIS OF RESIN EMULSIONS: I. THE EFFECT OF EMULSIFYING AGENTS
Authors: Munro L. A. , Sexsmith F. H.
Published: May 2006

A modified Briggs electrophoretic glass cell was used to measure the mobility of over 2500 particles of vinyl acetate latices prepared with different emulsifying agents. Although anionic and cationic agents conferred negative and positive mobilities respectively, nonionic agents invariably resulted in negatively charged particles. This is attributed to partial chemical change to anionic materials or to hydrogen bonding and polarization processes. The nature of the emulsifying agent and electrolyte concentration rather than concentrations of the latex or particle size were the most significant variables affecting the mobility of any latex.
LIQUID PHASE DEHYDROGENATION OF LAURYL ALCOHOL
Authors: Halasz Alexandre
Published: May 2006

not available
THE REACTION OF 5-BROMOVANILLIN AND SODIUM METHOXIDE
Authors: McIvor R. A. , Pepper J. M.
Published: May 2006

not available
THE ELECTRODE BEHAVIOR OF MERCURY
Authors: Wiebe A. K. , Winkler C. A.
Published: May 2006

Mercury electrode potentials in N/5 sulphuric acid were unaffected when the electrolyte was saturated with hydrogen, nitrogen, or helium but were markedly affected by trace amounts of oxygen or mercury ions. In the absence of oxygen and mercury ions, a constant potential of −0.61 volt (relative to a saturated calomel electrode) was observed. When current was passed for the first time across a fresh electrode face immersed in oxygen-free electrolyte (i.e. from initial potentials of about −0.6l volt), the potential build-up was nonlinear, but subsequent passage of current gave a linear build-up of potential. With traces of oxygen present, differences in the two types of curves were masked by reactions that appeared to involve oxygen or oxide on the electrode surface. The initial build-up curve was ascribed to the deposition of a monatomic hydrogen film (one atom per metal atom in the surface). The potential build-up curves probably result from a number of simultaneous reactions at the electrode.
SYNTHESIS OF ORGANIC DEUTERIUM COMPOUNDS: PART VI. FORMALDEHYDE-d2 AND FORMALDEHYDE-d
Authors: Bannard R. A. B. , Morse A. T. , Leitch L. C.
Published: May 2006

Formaldehyde-d2 was prepared in 62.5% over-all yield from 1,2-dibromoethane-d4 via the corresponding glycol diacetate and glycol. Formaldehyde-d was prepared by the same method from sym-1,2-dibromoethane-d2. From the high isotopic purity of the deuterated formaldehydes obtained, it has been definitely established that it is a pair of hydrogen atoms from the hydroxylic groups of the glycols that generates acetic acid during dialdehyde fission with lead tetraacetate. The densities and refractive indices of the deuterated ethylene glycol diacetates and ethylene glycols used as intermediates in the synthesis of the deuterated formaldehydes have been determined.
THE PHOTOLYSIS OF AZOISOPROPANE
Authors: Durham R. W. , Steacie E. W. R.
Published: May 2006

Azoisopropane has been photolyzed by 3600 Å radiation over the temperature range 30–120 °C. The effect of pressure indicates an excited molecule mechanism. Excited molecules which decompose give nitrogen and isopropyl radicals; the latter either combine, disproportionate, or react with azoisopropane. The activation energy difference between the two reactions[Formula: see text]has been found to be 6.5 ± 0.5 kcal. per mole.The difference in activation energy between the disproportionation and combination reactions is rendered ambiguous by the possibility of C3H7.N:N existing at the lower temperatures; but this is certainly small. The ratio of the rates of the two reactions is 0.5 at room temperature.
BIOCHEMISTRY OF THE USTILAGINALES: VIII. THE STRUCTURES AND CONFIGURATIONS OF THE USTILIC ACIDS
Authors: Lemieux R. U.
Published: May 2006

Methanolysis of ustilagic acid and hydrolysis of the methyl esters formed yielded a crystalline acidic fraction which was essentially a mixture of two substances termed the ustilic acids A and B. The acids were separated as their iso-propylidene derivatives. The ustilic acids cocrystallize to mixtures with melting points intermediate between those of the pure compounds. Conversion of ustilic acid A, m.p. 112–113 °C, [α]D −8° in methanol, which made up about 70% of the mixture, by hydrogenolysis to palmitic acid, by oxidation with chromic oxide to pentadecanedioic acid, and by lead tetraacetate oxidation followed by hydrogenation to 15-hydroxypentadecanoic acid showed the substance to be an optically active form of 15,16-dihydroxyhexadecanoic acid. Conversion of ustilic acid B, m.p. 140–141 °C, [α]D−10° in methanol, by sodium bismuthate oxidation followed by hydrogenation to 1,14-dihydroxytetradecane, by chromic acid oxidation of its methyl ester followed by hydrolysis of the product, and peroxide oxidation of the α-keto acid thus formed to tetradecanedioic acid, and by hydrogenolysis of the C2-carbon atom through a series of reactions to ustilic acid A, showed the substance to be an optically active form of 2,15,16-trihydroxy-hexadecanoic acid. Optically active forms of 2,15-dihydroxypentadecanoic and 2-hydroxypentadecanoic acids were prepared from ustilic acid B. Application of certain empirical rules of rotation to derivatives of these 2-hydroxyacids showed them to possess the D-configuration. Reduction of ustilic acid B with lithium aluminum hydride gave meso-1,2,15,16-tetrahydroxyhexadecane. Thus, ustilic acid B was the 2D,15D,16-trihydroxyhexadecanoic acid and the ustilic acid A was the 15D,16-dihydroxyhexadecanoic acid. Several derivatives of the above described acids were prepared.
BETATRON IRRADIATION OF WATER SATURATED WITH BENZENE
Authors: Freeman G. R. , Cleave A. B. Van , Spinks J. W.T.
Published: May 2006

The oxidation of benzene to phenol in dilute aqueous solution by Co60 gamma rays and betatron X-rays (23 Mev. peak energy) is compared with the oxidationof Fe++ to Fe+++ under similar conditions. The ratio [Formula: see text]was the same for Co60 and betatron radiations. The yield for the Co60 radiations was about 10% greater than the apparent yield for the betatron radiations, the difference probably being attributable to dose determination at high energies (>1 Mev.). It is concluded that both reactions are independent of energy and dose rate over the ranges investigated.
THE SYNTHESIS OF SYRINGALDEHYDE FROM VANILLIN
Authors: Pepper J. M. , MacDonald J. A.
Published: May 2006

Syringaldehyde has been synthesized in high yields from vanillin. The process consists of the iodination of vanillin, followed by the interaction of the resultant 5-iodovanillin with sodium methoxide in anhydrous methanol at temperatures of 130 ± 4 °C. for one hour in the presence of a copper catalyst. Along with the syringaldehyde, small amounts of unchanged 5-iodovanillin and vanillin were always found in the reaction mixture. Analysis of the final product was made by an initial separation of the components by downward paper chromatography using a mixture of petroleum ether (b.p. 100–120 °C), di-n-butyl ether, and water (10: 1: 1) as the developing agent for a period of 10 hr. The separated compounds were extracted from the paper and their concentrations in alcoholic alkaline solutions determined spectrophotometrically.Under conditions by which 5-iodovanillin was converted to syringaldehyde in better than a 95% yield, 5-bromovanillin gave only a 61% yield and 5-chlorovanillin gave no detectable amounts of syringaldehyde.
THE REACTION OF METHYL RADICALS WITH ISOBUTANE
Authors: Jones M. H. , Steacie E. W. R.
Published: May 2006

An investigation is reported of the reaction of methyl radicals, produced in the photochemical decomposition of azomethane, with isobutane. The energy of activation of this process was found to be 6.7 ± 0.8 kcal./mole, assuming that the combination of methyl radicals has an activation energy of zero. From some experiments with n-butane, a value of 9 ± 1 kcal./mole was obtained.
UNIT CELL, SPACE GROUP, AND X-RAY POWDER DIFFRACTION DATA FOR THE ALKALOID LUPANOLINE, C15H24N2O2, AND FOR LUPANOLINE MONOHYDRATE, C15H24N2O2.H2O
Authors: Barnes W. H. , Przybylska Maria
Published: May 2006

not available
COMPARISON OF METHOXYMERCURIALS DERIVED FROM CYCLOPENTENE AND CYCLOHEXENE
Authors: Brook A. G. , Donovan R. , Wright George F
Published: May 2006

The α- and β-2-methoxycyclopentylmercuric chlorides, bromides, and iodides have been prepared. The X-ray powder patterns, dipole moments, and thermal analyses among each series have been compared with the homologous methoxycyclohexyl derivatives. In both of the series the dipole moments of the β-diastereomers are greater than those of the corresponding α -isomers. In both series the α- and β-diastereomers seem to comprise isostructural series among the three halides. This isostructural relationship seems to be reflected in the melting point composition diagrams.
LYCOPODIUM ALKALOIDS: II SOME REACTIONS OF THE PERMANGANATE OXIDATION PRODUCT OF ANOTININE
Authors: MacLean David B. , Prime H. C.
Published: May 2006

The permanganate oxidation product of annotinine is shown to be an amide that contains the ether ring of annotinine still intact. The Clemmensen reduction of this compound to the saturated base, C16H23O2N, was re-examined. A number of intermediates were isolated from the system and these were also prepared from the oxidation product by other methods. Analogous reactions of annotinine chlorohydrin were also studied. From these results suggestions are presented regarding the size of the ether ring and its position relative to the nitrogen atom.
THE REACTIVITY OF CELLULOSE: II.WATER SORPTION, HEATS OF WETTING, AND THE REACTIONS WITH THALLOUS ETHYLATE IN ETHER, NITRATION MIXTURES, AND HEAVY WATER OF COTTON LINTERS ALTERNATELY WETTED WITH WATER AND DRIED
Authors: Brickman W. James , Dunford H. Brian , Tory Elmer M. , Morrison John L. , Brown Robert K.
Published: May 2006

Cotton linters dewaxed with benzene and alcohol possess a slightly expanded structure attributed to the swelling effect of the alcohol. Storage causes a partial collapse of the linters especially so when moisture is present. Wetting with water followed by rigorous drying produces a marked reduction in accessibility, but with each additional wetting–drying cycle accessibility of the dried linters increases slightly as measured by reaction with thallous ethylate in ether, a nitration mixture, and in hydrogen–deuterium exchange. Differences in nitration found for limited reaction times are obliterated when these reaction times are extended. Increasing accessibility due to repeated wetting and drying is accompanied by lower water sorption and smaller heats of wetting. This anomaly is due to the fact that cellulose samples obtained by alternately wetting and drying dewaxed linters, when stored with a desiccant, compete for the limited amount of water present and adsorb moisture in proportion to their accessibility. Upon further exposure to water the sample of least accessibility, having adsorbed less water, can now adsorb to a greater extent than do the linters of somewhat greater accessibility.The evidence indicates that the difference in accessibility occasioned by repeated wetting and drying is of a physical rather than chemical nature.
COEXISTENCE PHENOMENA IN THE CRITICAL REGION: II. INFLUENCE OF GRAVITY ON THE COEXISTENCE CURVES OF ETHANE, ETHYLENE, AND XENON
Authors: Whiteway S. G. , Mason S. G.
Published: May 2006

Liquid–vapor coexistence curves of ethane, ethylene, and xenon have been measured in the region of the critical point. Impurities present in the ethane and ethylene gave retrograde systems; reduction of the impurities yielded coexistence curves which were flat along the temperature axis to 0.001 °C. When the height of the ethylene system was decreased the range of densities over which the curve was flat was diminished. Stirring of the system caused the curve to be rounded. Similar results, confirming those of Weinberger and Schneider, were obtained with xenon. The observed behavior is in good agreement with the hypothesis that the major part of the flat top effect is due to gravitational compression.
STUDIES OF RDX AND RELATED COMPOUNDS: XI. THE CONVERSION OF PHX TO AcAn
Authors: Marcus R. A. , Winkler C. A.
Published: May 2006

The formation of AcAn from PHX, nitric acid, and acetic anhydride has been investigated at various temperatures. The effects of added acetic acid and added salts have been determined. While the reaction is first order with respect to PHX, it is of an order 2.6 with respect to nitric acid. The reaction rate is significantly decreased by small concentrations of sodium nitrate. The reaction is also characterized by a secondary salt effect and a low apparent activation energy of about 2 kcal. mole−1. A mechanism has been suggested in qualitative, and to some extent quantitative, agreement with the experimental data. It is postulated that the conversion of PHX involves a rate-controlling ionic reaction between PHX and nitric acid, and that this is followed by a rapid acetylation of the acidic intermediate to AcAn.
SOME METHYL-SUBSTITUTED PYRIDYL AND QUINOLYLPHENYL CARBINOLS
Authors: Knott R. F. , Ciric J. , Breckenridge J. G.
Published: May 2006

not available
PHOTOLYSIS OF MERCURY DIMETHYL
Authors: Rebbert Richard E. , Steacie E. W. R.
Published: May 2006

The photolysis of mercury dimethyl was investigated over the temperature range from 125° to 250 °C. The results indicate that methane is formed only by an abstraction reaction and ethane is formed only by recombination, at least under the conditions used in these experiments. It is concluded that the activation energy of the reaction[Formula: see text]is 10.8 ± 0.3 kcal./mole.
CONTRIBUTION TO THE STUDY OF PYRAZOLONES
Authors: Gagnon Paul E. , Boivin Jean L. , Tremblay Méüde
Published: May 2006

1,4-Diphenyl-3-carbethoxy-5-aminopyrazole yielded 1,4-diphenyl-5-aminopyrazole by hydrolysis and decarboxylation. The phenylhydrazone of ethyl phenyloxalacetate gave a pyrazolone which was transformed into 1,4-diphenyl-3-amino-5-pyrazolone. The 2,4-diphenyl-3-amino-5-pyrazolone was obtained from ethyl phenylcyanoacetate and phenylhydrazine by heating in acetic acid. 4-Alkyl-3-hydroxy- and 3-amino-5-pyrazolones and 4,4-dialkyl-3-oxo- and 3-imino-5-pyrazolones, substituted in position 2 by carbanilino or α- or β-naphthyl groups, were prepared from ethyl mono- or disubstituted malonates and cyanoacetates, 4-phenylsemicarbazide, and α- and β-naphthylhydrazines. Ultraviolet absorption spectra were determined in neutral and acid solutions.
STEROIDS: II. REACTION OF AMINES WITH CHOLESTERYL CHLOROFORMATE AND PYROLYSIS OF N-BENZYL CHOLESTERYL CARBAMATE
Authors: McKay A. F. , Vavasour G. R.
Published: May 2006

Cholesteryl chloroformate can be used to isolate small amounts of amines from aqueous solutions as N-substituted cholesteryl carbamates. These derivatives are easily isolated and identified. Their possible use for, the identification of amines obtained in degradative studies is discussed. The thermal decomposition of N-benzyl cholesteryl carbamate gives carbon dioxide, cholesterol, cholest-3,5-diene, and sym-dibenzylurea. A mechanism of formation of these products is discussed.
THE POTENTIOMETRIC TITRATION OF CARBONATE SOLUTIONS CONTAINING URANIUM
Authors: Halpern J.
Published: May 2006

Potentiometric titrations with hydrochloric acid were carried out on standard sodium carbonate solutions containing varying amounts of uranyl nitrate. The results confirmed the fact that uranium is present in such solutions as the complex ion [Formula: see text]. It was found that only the free CO3−− is titrated with H+ up to the first end point at pH = 8. 2. The complex ion is very stable and is decomposed only on further addition of acid when the complexed CO3−− along with the HCO3− in the solution is converted to carbonic acid before the second end point. The pH at which the second end point occurs is lowered from its normal value of 4.0 in the presence of uranium. This effect is attributed to hydrolysis of the UO2++ ion. The necessary corrections for determining carbonate and bicarbonate in the presence of uranium are given.
THE pH DEPENDENCE OF THE ADSORPTION ISOTHERM AND ABSORPTION SPECTRUM OF METHYL ORANGE BOUND TO HUMAN AND BOVINE SERUM ALBUMIN
Authors: Colvin J. Ross
Published: May 2006

The difference between adsorption isotherms and absorption spectra of methyl orange bound to human and to bovine albumin at pH 6.8, 9.1, and 11.0 has been studied. Exaltation of the spectrum of methyl orange bound to human albumin is not necessarily correlated with total binding capacity. However, above pH 6.8, heterogeneity of the binding sites for methyl orange on human albumin increases so markedly that it is reflected in an appreciable increase in extinction coefficient for the first three or four anions bound. The exaltation is accompanied by an increased −ΔF° of binding. Increase in ionic strength diminishes exaltation, and denaturation of the protein destroys it. These effects were not observed for bovine albumin. Results are interpreted in terms of a limited reversible expansion of the human protein molecules, without unfolding, due to intramolecular, electrostatic repulsion between groups.
THE SENSITIVITY OF INITIATOR EXPLOSIVES TO MECHANICAL IMPACT
Authors: Hollies N. R. S. , Legge N. R. , Morrison John L.
Published: May 2006

An original ball-drop impact apparatus has been constructed and used to test the sensitivities of dextrin lead azide and mercury fulminate to mechanical impact. Ball masses and heights were both varied. Both the net kinetic energy and the change of momentum gave continuous functions with the percentage of detonations. Comparisons of the absolute values of the net kinetic energy and the change of momentum with another reported in the literature suggest that momentum is the more important factor in determining the probability of detonation. Values for the momentum at 50% detonations for lead azide and mercury fulminate are 4.6 × 104 and 2.6 × 104 c.g.s. units, respectively, with an area of contact of about 0.08 cm2. The corresponding times of impact were found to be about 2.2 × 10−4 and 1.9 × 10−4 sec.
STUDIES OF LIGNIN BIOSYNTHESIS USING ISOTOPIC CARBON: II. SHORT-TERM EXPERIMENTS WITH C14O2
Authors: Brown Stewart A. , Tanner K. G. , Stone J. E.
Published: May 2006

The formation of lignin in wheat plants from C14O2, during the period of rapid lignification, has been studied over the first few hours of photosynthesis by measuring the incorporation of carbon-14 into the guaiacyl and syringyl portions of the lignin molecule. Plants grown 62 days from seeding were exposed to 20 microcuries of C14O2 in a closed chamber for 20 min., and grown for periods of 1 to 24 hr. in a normal atmosphere before harvesting. Synthesis of lignin is most rapid four to six hours from activation, the syringyl residues apparently being formed more slowly than the guaiacyl. A slower rate of formation persists for the remainder of a one-day period, probably as a result of recycling in the carbon pool. Cellulose acquires carbon-14 more rapidly than lignin during the period immediately following administration of C14O2, but after three or four hours when synthesis of lignin has become rapid, the total carbon-14 content of both components reaches about the same value.
VITAMIN K1 LABELED WITH C14
Authors: Lee C. C. , Hoskin F. C. G. , Trevoy L. W. , Jaques L. B. , Spinks J. W. T.
Published: May 2006

not available
THE HYDROGENOLYSIS OF 3-HYDROXYMETHYLINDOLE AND OTHER INDOLE DERIVATIVES WITH LITHIUM ALUMINUM HYDRIDE
Authors: Leete Edward , Marion Léo
Published: May 2006

Indole-3-aldehyde, indole-3-carboxylic acid and its ethyl ester were reduced by excess lithium aluminum hydride to skatole. The expected reduction product, 3-hydroxymethylindole, was obtained by the action of sodium hydroxide on gramine methiodide. It and its alkyl ethers were readily reduced to skatole. 3-Hydroxymethylindole underwent self-condensation to 3,3′-di-indolylmethane in neutral and alkaline media, and with acidic reagents was converted to an oxygen-free polymeric substance. The mechanism of these reactions and of the hydrogenolysis is discussed
PREPARATION OF DINITRO-n-ALKYL PHENOLS
Authors: Dutton G. G. S. , Briggs T. I. , Brown B. R. , Powell R. K.
Published: May 2006

The preparation of a series of dinitro-n-alkyl phenols is described. The dinitrophenols were characterized as their piperidine, morpholine, and cyclohexylamine salts. In the course of the work some new derivatives of these n-alkyl phenols and intermediate hydroxyketones were obtained.
A NEW MECHANISM FOR PERSULPHATE OXIDATIONS
Authors: Levitt Leonard S.
Published: May 2006

A new mechanism for oxidations by persulphate is presented, wherein it is postulated that the persulphate ion dissociates reversibly, by means of a heterolytic cleavage, into a sulphate ion and a molecule of sulphur tetroxide. Sulphur tetroxide is considered to be the active oxidizing species, combining reversibly with the substrate to form a complex whose subsequent decomposition gives the principal reaction products. The very small equilibrium concentration of sulphur tetroxide becomes the limiting factor in the rate of oxidation when a readily oxidizable substrate is present in relatively high concentration. The mechanism is applied to the data of Eager and Winkler for the oxidation of mercaptans, in which a limiting rate was attained above a certain mercaptan concentration. An empirical equation relating the rate constant to the mercaptan concentration is developed to fit the experimental data. Rate equations showing the rate dependence on mercaptan concentration are derived from the proposed mechanism and are found to be of the same form as the empirical equation. The mechanism is applied also to the persulphate oxidation of water.
A NOTE ON THE VALIDITY OF THE GIBBS-DALTON LAW AS APPLIED TO DILUTE MIXTURES OF WATER VAPOR WITH HYDROGEN, HELIUM, AND ARGON AT ROOM TEMPERATURES
Authors: Flood E. A.
Published: May 2006

Water vapor at room temperature and at pressures in the neighborhood of 10 mm. Hg behaves as a vacuum to each of the three gases hydrogen, helium, and argon, at pressures up to about 100 mm. Hg. The thermodynamic potentials of constituent gases in such mixtures of water vapor and hydrogen, water vapor and helium, etc. probably do not differ from those of the pure components, at equal volume concentrations, by more than 0.3%. Thus these gas mixtures obey the Gibbs–Dalton Law very closely and accordingly must also obey Dalton's Law. Velocity distribution functions of these gases under our experimental conditions are essentially Maxwellian.
NOTE ON THE DIELECTRIC CONSTANTS OF ETHYL CHLORIDE AND n-BUTANE ADSORBED ON NONPOROUS TiO2
Authors: Waldman M. H. , Snelgrove J. A. , Mcintosh R.
Published: May 2006

The dielectric constants of ethyl chloride and n-butane adsorbed on nonporous TiO2 were measured. The plot of capacity change versus volume adsorbed was found to reveal two linear sections in the case of ethyl chloride with an abrupt change in the slope of the plot occurring at the Vm value calculated using the B.E.T. or Hüttig adsorption equations. With n-butane the plot was linear beyond Vm. For ethyl chloride on rutile a slight temperature dependence in the polarization was observed for the volume of gas adsorbed above Vm, while a negligible temperature dependence was noted for the portion below Vm. It is postulated that the observations with the polar gas on the nonporous rutile can be explained by a change from oscillatory to rotational motion of the adsorbed molecule after the monolayer is complete. It was noted that gases adsorbed on nonporous TiO2 behaved differently from gases adsorbed on porous silica gel. This appears to lead to the necessity of postulating changes of density for the adsorbed phase on silica gel.
THE INFRARED SPECTRA OF ALPHA AND BETA OXIMES
Authors: Palm Ann , Werbin Harold
Published: May 2006

The spectra of several isomeric oximes in the solid state were examined in the range 700–3600 cm−1. The associated OH stretching frequency near 3250 cm.−1 in the α oximes is displaced towards lower frequency in the β oximes. The region of the OH stretching mode of several oximes was also studied in benzene and chloroform solutions. The frequencies near 1300 cm.−1 and 920 cm.−1are tentatively assigned to the OH deformation and the N-OH stretching modes, respectively. No consistent differences are observed between the α and the β oximes with respect to these vibrations. The band at approximately 1640 cm.−1 ascribed to the C==N vibration remains essentially unchanged in the spectra of the two isomeric forms.
THE ELECTRICAL CONDUCTIVITY OF MOLTEN OXIDES
Authors: Arkel A. E. Van , Flood E. A. , Bright Norman F. H.
Published: May 2006

Electrical conductivities of some molten oxides have been determined. In order of decreasing equivalent conductances at their melting points the oxides investigated were: Li2O, PbO, TeO2, MoO3, Bi2O3, V2O5, Sb2O3, and CrO3. The variation of the observed values of the specific conductivities, K, with the absolute temperature, T, can be described by an equation of the form,[Formula: see text]where A, B, C, etc. are constants. While the experimental data are adequately described by an equation of this form containing only the constants A and B, a slightly better fit is obtained using three constants. The conductivities of the molten oxides follow a pattern of variation from element to element which is substantially the same as that of the molten halides. For elements giving more than one oxide stable in the molten state, the oxide corresponding to the highest state of valency has the lowest conductivity.
THE ALPHA AND BETA 1,3,4,6-TETRAACETYL-D-GLUCOPYRANOSES AND THEIR CHLOROACETYL DERIVATIVES
Authors: Lemieux R. U. , Huber G.
Published: May 2006

Reaction of 3,4,6-triacetyl-β-D-glucopyranosyl chloride with silver acetate in acetic acid gave 1,3,4,6-tetraacetyl-α-D-glucopyranose, m.p. 97–98 °C., [α]D + 145° (chloroform). 3,4,6,-Triacetyl-α-D-glucopyrartosyl chloride, m.p. 93–94 °C., [α]D + 185° (chloroform), prepared from the β-anomer by isomerization in acetone, with silver acetate in acetic acid gave 1,3,4,6-tetraacetyl-β-D-glucopyranose, m.p. 137–138 °C., [α]D + 26° (chloroform). The structures of these glucose tetraacetates were established by the interconversion of chloroacetyl derivatives.
BIOCHEMISTRY OF THE USTILAGINALES: IX. THE β-D-CELLOBIOSIDE UNITS OF THE USTILAGIC ACIDS
Authors: Lemieux R. U. , Thorn J. A. , Bauer H. F.
Published: May 2006

The two D-glucose residues in the two main components of the ustilagic acid mixture are shown to be present as β-D-cellobiopyranoside units.
THE REDUCTION OF AROMATIC NITRO COMPOUNDS MAGNESIUM AND METHYL ALCOHOL
Authors: Keirstead Karl F.
Published: May 2006

A study has been made of the reduction of substituted nitro compounds by magnesium in methyl alcohol. Some nitro compounds smoothly reduce to the corresponding azoxy compounds, while others yield a complex mixture of azo, azoxy, and other compounds. An investigation has been made of the various factors affecting the velocity of the reaction and the relative proportion of the products. An attempt is made to clarify the various reactions taking place.
STUDIES ON THE GLYCOPROTEINS OF THE DOMESTIC FOWL: I. A MODIFICATION OF THE METHOD OF ELSON AND MORGAN FOR THE DETERMINATION OF HEXOSAMINE, AND ITS APPLICABILITY TO TISSUE HYDROLYZATES
Authors: Anastassiadis P. A. , Common R. H.
Published: May 2006

The method of Elson and Morgan for the determination of hexosamine has been studied spectrophotometrically with the object of applying the method to the analysis of tissue hydrolyzates. It has been shown that it is possible by appropriate blanks to correct for interference due to humin. It has been found necessary (a) to increase the strength of the buffer solution in order to stablize the pH and, in extreme cases, first to neutralize the dried hydrolyzate; and (b) to increase the amount of acetylacetone. These modifications also reduce interference by hydroxyproline to a minimum. The use of an appropriate excess of acetylacetone was found to depress the formation of the secondary chromogen during acetylation. A procedure based on these findings is proposed for the direct determination of hexosamine in acid hydrolyzates of tissues.
THE ELECTRODE BEHAVIOR OF COPPER
Authors: Wiebe A. K. , Winkler C. A.
Published: May 2006

Potentials ranging from −0.063 volt to +0.044 volt were observed for freshly prepared copper electrodes in sulphuric acid. The potential was dependent upon concentration of the electrolyte, the gas with which the electrolyte was saturated, the nature of the electrode surface, and the intensity of the stirring. The rate of potential decay was influenced by the nature of the dissolved gas and concentration of the electrolyte. When current was passed for the first time across a freshly prepared electrode face, the potential build-up was nonlinear, but subsequent passage of current gave a linear build-up of potential. The apparent capacitance at a copper cathode increased with the time allowed for the potential to decay after current had been passed. It was also dependent upon the current used to measure it, and appeared to be somewhat affected by the area of the cathode. Reliable estimates of the surface areas of the electrodes appeared to be possible from the times required for the electrodes to reach maximum potentials.
FATTY ACIDS OF FILBERT OIL AND NASTURTIUM SEED OIL
Authors: Chisholm Mary J. , Hopkins C. Y.
Published: May 2006

The fatty acids of a sample of filbert kernel oil (Corylusavellana L.) were examined by means of ester distillation and low-temperature crystallization. Stearic, oleic, and linoleic acids were identified but eicosenoic acid was not found although earlier workers had reported its presence in considerable amount in samples from the same species. Nasturtium seed oil (Tropaeolummajus L. var.), examined in the same way, was found to contain about 20% of 11-eicosenoic acid. An estimate is given of the fatty acid composition of the two oils.
IRRADIATION OF ONE MOLAR AQUEOUS CHLORAL HYDRATE SOLUTION WITH Co60-GAMMA-RAYS AND BETATRON X RAYS
Authors: Freeman G. R. , Cleave A. B. Van , Spinks J. W. T.
Published: May 2006

The production of acid by irradiation of 1 M chloral hydrate solutions is proportional to the dose at a given dose rate. The specific yield is the same for Co60 γ-rays as for 23 Mev. peak energy X rays and is a linear function of the inverse of the square root of the close rate. The reaction is apparently a chain reaction.
LIQUID-PHASE OXIDATION OF p-CYMENE: NATURE OF INTERMEDIATE HYDROPEROXIDES AND RELATIVE ACTIVITY OF THE ALKYL GROUPS
Authors: Serif G. S. , Hunt C. F. , Bourns A. N.
Published: May 2006

A study has been made of the liquid-phase oxidation of p-cymene with elemental oxygen using emulsion and photochemical procedures with the object of determining (a) the nature of the resulting hydroperoxides and their decomposition products, and (b) the relative activity of the methyl and isopropyl side chains.The following compounds have been shown to be present in the emulsion oxidation product: 2-p-tolyl-2-propyl hydroperoxide, 2-p-tolyl-2-propanol, p-isopropylbenzyl alcohol, p-methylacetophenone, cumic acid, p-(α-hydroperoxyisopropyl) benzoic acid, p-(α-hydroxyisopropyl) benzoic acid, and p-acetyl-benzoic acid. The two hydroperoxides have been isolated and characterized. By chromatographic separation of the carboxylic acids and fractional distillation of the alcohols formed by lithium aluminum hydride reduction of all other products, the relative susceptibility of the methyl and isopropyl groups to oxidative attack has been shown to be 1:4.In the photochemical oxidation, hydroperoxide decomposition was very small and the product was shown to consist of 20% p-isopropylbenzyl hydroperoxide and 80% of 2-p-tolyl-2-propyl hydroperoxide. The relative extent of oxidative attack at the two positions was therefore identical in the two oxidations.
THE EFFECT OF PHYSICAL ADSORPTION ON THE ELECTRICAL RESISTANCE OF ACTIVE CARBON
Authors: Smeltzer W. W. , McIntosh R.
Published: May 2006

The change of the electrical resistance of active carbon rods due to the reversible adsorption of vapors is described. The effects of six saturated hydrocarbons and ethyl chloride were studied. An interesting regularity in the results obtained with the hydrocarbons was found, namely that the extent of the resistance change at a given temperature and volume adsorbed is proportional to the number of carbon atoms in the adsorbate molecule. The alteration of the electrical conductivity of the active carbon by the physically adsorbed vapors and the adsorption isotherms are not modified by small quantities of chemisorbed oxygen. Ethyl chloride exhibits a more complex behavior than the hydrocarbons. It is argued that the resistance measurements may be utilized to support the viewpoint that physically adsorbed saturated hydrocarbon molecules tend to lie flat on the adsorbent surface. Several possible explanations of the findings are examined and proved to be inadequate.
SULPHUR ISOTOPE EFFECTS IN THE BISULPHITE ADDITION REACTION OF ALDEHYDES AND KETONES: I. EQUILIBRIUM EFFECT AND THE STRUCTURE OF THE ADDITION PRODUCT
Authors: Sheppard W. A. , Bourns A. N.
Published: May 2006

Equilibrium constants for the isotopic exchange reaction between bisulphite ion and the addition product of eight aldehydes and ketones have been measured.[Formula: see text]At 25 °C., values ranging from 1.021 for acetone to 1.010 for anisaldehyde have been observed. Since constants of this magnitude are to be expected only if the bonding of the sulphur atom is different in the bisulphite ion and the addition product, these results are considered to confirm the carbon-sulphur bond structure of the latter. This conclusion is supported by the small constant, 1.002, obtained for the diethyl sulphate and ethyl hydrogen sulphate isotopic exchange in which the bonding of sulphur is essentially the same in the two reacting species.
THE ACTION OF HYDROXYLAMINE ON METHYL ALPHA- AND BETA-D-GLUCOPYRANOSIDE TETRANITRATE IN PYRIDINE
Authors: Hayward L. D. , Purves C. B.
Published: May 2006

The methyl glucoside tetranitrates reacted vigorously at room temperature with an excess of hydroxylamine base dissolved in anhydrous pyridine. Gas consisting of 91% nitrogen and amounting to 1.25 to 1.3 moles per mole was evolved within 20 min. and only a little more during the next 12 hr. Approximately 1.35 moles of nitrate groups in the original tetranitrate had been replaced by hydroxyl groups, for the most part at least without Walden inversions or other change, because hydrogenation of the sirupy product reduced it in more than 80% yield to crystalline methyl glucoside. The product from methyl-β-glucoside tetranitrate consisted of the 2,3,6-trinitrate (28%), the 3,6-dinitrate (17%), and an unidentified trinitrate (8%) which might have been a mixture.The structures of the first two compounds were confirmed by preparing the fully methylated derivatives, denitrating the latter, and identifying the resulting known, partly methylated methyl-β-glucosides. New syntheses of methyl-β-glucoside-3,6-dinitrate, methyl 2,4-dimethyl-β-glucoside, and methyl-4-methyl-β-glucoside were found.
MONO- AND DIPOTASSIUM AMINOMETHIONATE
Authors: Bannard R. A. B. , Ross J. H.
Published: May 2006

not available
CYCLIC THIOUREAS
Authors: McKay A. F. , Vavasour G. R.
Published: May 2006

1-β-Hydroxyethylimidazolidine-2-thione was prepared from 1-amino-5-hydroxy-3-azapentane and carbon disulphide. Since its properties differ from those claimed by Sergeyev and Kolychev (7) for this compound prepared from ethylene oxide and thiocyanic acid, its structure was confirmed by conversion to 1-β-hydroxyethyl-2-benzylamino-2-imidazoline. The latter compound was prepared for comparison from the known 1-β-hydroxyethyl-2-nitramino-2-imidazoline.
METHYL ETHYL KETONE IN THE PHOTOLYSIS OF ACETONE VAPOR
Authors: Mandelcorn L. , Steacie E. W. R.
Published: May 2006

By mass spectrometric analyses, methyl ethyl ketone was determined as a product of the photolysis of acetone between 100 and 284 °C. According to the postulated mechanism, methyl ethyl ketone together with methane and ethane accounted for approximately 95% of the methyl radicals produced.
THE ALKALOIDS OF PAPAVERACEOUS PLANTS: L. DICRANOSTIGMA LACTUCOIDES HOOK. F. ET THOMS. AND BOCCONIA PEARCEI HUTCHINSON
Authors: Manske R. H. F.
Published: May 2006

Dicranostigma franchetianum has been renamed Stylophorum franchetianum (Prain) comb. nov. because its alkaloids are the same as those of S. diphyllum. It is proposed to retain the name D. lactucoides because the contained alkaloids, namely protopine, isocorydine, sanguinarine, and chelerythrine present a combination hitherto encountered only in a Glaucium. Bocconia pearcei was shown to contain, in addition to chelerythrine (and presumably sanguinarine), small amounts of protopine and allocryptopine.
THE EFFECT OF TEMPERATURE ON SUSPENSIONS OF GLASS BEADS IN TOLUENE CONTAINING VARIOUS PERCENTAGES OF WATER
Authors: Eggleton A. E. J. , Puddington I. E.
Published: May 2006

The influence of temperature on the sedimentation volume and relative yield values of suspensions of spherical glass beads in toluene containing varying percentages of water has been measured. The increased sedimentation volume and yield value, due to the presence of water, found at room temperature virtually disappeared below approximately 0 °C. This is in agreement with the theory which ascribes the effect of water to its interfacial tension against toluene. At temperatures above 0 °C. there was a gradual fall in the sedimentation volume and yield value from the maximum found at 0 °C. This is attributed to the increasing solubility of water in toluene. Suspensions containing no water or only a small quantity showed an unexpected steady increase in sedimentation volume and yield value as the temperature was lowered to −60 °C. This effect was also observed with a suspension of glass beads in pentane. The results indicate a close connection between yield value and equilibrium sedimentation volume.
HYDROGEN PEROXIDE: THE LOW TEMPERATURE HEAT CAPACITY OF THE SOLID AND THE THIRD LAW ENTROPY
Authors: Giguère Paul A. , Liu I. D. , Dugdale J. S. , Morrison J. A.
Published: May 2006

The heat capacity of crystalline hydrogen peroxide between 12° K. and the melting point has been determined with a low temperature adiabatic calorimeter. The heat of fusion was also measured and found to be 2987 ± 3 cal./mole. The two samples of hydrogen peroxide used were 99.97 mole % pure as deduced from behavior on melting and from premelting heat capacities; the triple point was estimated to be 272.74 K.The only anomaly observed in the heat capacity measurements was the absorption of 1.3 cal./mole at 216.8 ± 0.15° K., the lower eutectic temperature of H2O-H2O2 solutions. Such an effect is to be expected if the only significant impurity is water. The entropy of hydrogen peroxide as an ideal gas at 1 atm. pressure and 25° C. computed from the thermal measurements is 55.76 ± 0.12 cal./mole deg. Comparison of this datum with the recalculated statistical entropy leads to a value of 3.5 kcal./mole for the height of a hypothetical single barrier hindering internal rotation in the molecule. From these results it is concluded that hydrogen peroxide does not consist of two tautomeric modifications.
PREPARATION OF ION-EXCHANGE RESINS
Authors: Spinner I. H. , Ciric J. , Graydon W. F.
Published: May 2006

Ion-exchange resins as membranes and in granular form have been prepared by the copolymerization of divinylbenzene with various esters of p-styrene-sulphonic acid and subsequent hydrolysis. The synthesis of the sulphonated styrene monomers is described. Equilibrium data for the sodium–hydrogen ion exchange on a resin prepared in this manner are discussed in terms of postulated variations of sulphonate group environment.
CARBODIIMIDES: PART IV. THE FISSION OF N,N′-DI-p-TOLYL-O-BENZYL AND-O-ALLYL PSEUDOUREA ETHERS IN THE PRESENCE OF ACIDS
Authors: Khorana H. G.
Published: May 2006

N,N′-di-p-tolyl-O-benzyl pseudourea ether has been shown to form, in the presence of acids, a mixture of the corresponding benzyl ester and unchanged acid, di-p-tolyl urea and an isomer of the urea ether which is concluded to be N-(2-benzyl-p-tolyl)-N′-p-tolyl urea. The transient coloration (to orange red) of the reaction mixture affords strong evidence for the intermediate formation of benzyl cations. The fission of N,N′-di-p-tolyl-O-allyl pseudourea ether follows an analogous course.
ANNOTININE: THE REACTIONS OF THE CYCLIC ETHER FUNCTION
Authors: Meier H. L. , Meister P. D. , Marion Léo
Published: May 2006

Treatment of annotinine chlorohydrin with chromous chloride has been found to produce not only the already reported unsaturated lactone A (C16H21O2N), but also a second unsaturated lactone B (C16H21(23)O2N), and a hydroxylactone (C16H23O3N). Under the action of a concentrated solution of the same reagent the hydroxylactone is converted to the unsaturated lactone B. On hydrogenation the latter gives a dihydrolactone B which seems to contain a secondary amino group. Annotinine hydrate on treatment with thionyl chloride gives an unsaturated chlorolactone (C16H20O2NCl) which can be hydrogenated and subsequently dechlorinated to produce a third lactone C, different from either of dihydrolactones A or B, but which like the latter seems to contain an imino group. Oxidation of annotinine hydrate with chromic acid produces a hydroxyketone which can be converted into an oxime and, therefore, one of the hydroxyls of the hydrate is secondary while the other is probably tertiary. On the other hand, oxidation of annotinine with potassium permanganate gives rise to a lactam which by the Clemmensen reduction is converted to a mixture of lactam chlorohydrin and dihydrolactone A.
ANNOTININE: THE LACTONE RING
Authors: Meier H. L. , Marion Léo
Published: May 2006

The action of lithium aluminum hydride in dioxane solution on annotinine reduces the lactone and gives rise to a dihydroxy ether while the same reaction in tetrahydrofuran causes scission of the cyclic ether as well and produces a trihydroxy compound. The same trihydroxy compound is also obtainable by the similar reduction of annotinine chlorohydrin. Treatment of the trihydroxy compound with thionyl chloride converts it to a chlorine-containing sulphite ester which under the action of chromous chloride yields an unsaturated dihydroxy compound A, while under the conditions of the Clemmensen reaction, it yields an isomeric unsaturated dihydroxy compound B. Annotinine reacts with phenyl-lithium to give what seems to be a tetrahydroxy compound (C28H35O4N) which is oxidized by chromic acid to C28H33O4N. These reactions lead to two conclusions: (a) that hydrochloric acid and lithium aluminum hydride open the cyclic ether of annotinine in the same way, and (b) that the hydroxyl involved in the lactone is tertiary.
THE PHOTOLYSIS OF ACETONE ABOVE 300 °C
Authors: Mandelcorn L. , Steacie E. W. R.
Published: May 2006

Acetone has been photolyzed at temperatures above 300 °C. The formation of ethylene becomes of increasing importance at higher temperatures. The normal kinetics of the reaction are followed, however, and ethylene does not appear to be formed at the expense of ethane or methane.
SULPHUR ISOTOPE EFFECTS IN THE BISULPHITE ADDITION REACTION OF ALDEHYDES AND KETONES: II. BOND-FORMATION EFFECT
Authors: Sheppard W. A. , Bader R. F. W. , Bourns A. N.
Published: May 2006

The relative rates of formation of C12—S32 and C12—S34 bonds in the bisulphite addition reaction of heptanal, benzaldehyde, anisaldehyde, and 2-heptanone have been measured and found to approximate unity. This result has been interpreted in terms of the Bigeleisen treatment of isotope effects in unidirectional processes.