bluuebunny/crossref_metadata_2025 huggingface dataset:
EXCITED MOLECULES AS THE REACTIVE SPECIES IN ACTIVE NITROGEN
Authors: Back R. A. , Menzies Margaret , Winkler C. A.
Published: May 2006

No reaction has been detected between ethylene and nitrogen molecules obtained in the thermal decomposition of metallic azides. Since such decomposition reactions apparently produce nitrogen molecules excited to the same electronic level as those present in active nitrogen formed by a condensed discharge, it might be inferred that excited molecules are not the reactive species in active nitrogen.
PREPARATION OF SOME NEW BRANCHED-CHAIN CARBOHYDRATES FROMD-α-FRUCTOHEPTONIC LACTONE
Authors: Woods R. J. , Neish A. C.
Published: May 2006

D-α-Fructoheptonic lactone (I) was oxidized with an equimolar amount of periodic acid to give formaldehyde and a hexuronic lactone (II) which was hydrolyzed to crystalline 4-C-hydroxymethyl-L-xyluronic acid (III), (68% yield). Hydrogenation of III gave an aldonic acid which was isolated as crystalline 2-C-hydroxymethyl-L-xylonic lactone (V). Reduction of V by sodium amalgam gave 2-C-hydroxymethyl-D-xylose (VI), which crystallized after purification as the 2,5-dichlorophenylhydrazone. Hydrogenation of VI gave 1,1-di(C-hydroxymethyl)-D-threitol (VII) which was purified as the crystalline hexaacetate. Treatment of III with methanolic hydrogen chloride gave a glassy material which was reduced by sodium borohydride and hydrolyzed by hydrochloric acid to give 4,4-di(C-hydroxymethyl)-D-threose (IX), which was isolated and characterized as the crystalline 2,5-dichlorophenylhydrazone. Oxidation of III by either bromine or nitric acid gave 2-C-hydroxymethyl-D-xylaric acid (IV), which was characterized as the crystalline ammonium salt.
THE SILVER CATALYZED OXIDATION OF ETHYLENE: II. KINETICS OF C2H4 OXIDATION
Authors: Orzechowski A. , MacCormack K. E.
Published: May 2006

A flow-type apparatus is described and results given for the investigation of the kinetics of the silver catalyzed oxidation of C2H4 by oxygen. Using N2 as diluent, the concentrations of both O2 and C2H4 were varied independently from 9.9 to 79.0% and 2.35 to 9.40% respectively, whilst maintaining a total pressure of 1 atmosphere. Flow rates were varied to give a range of contact times varying from 0.05 to 1 sec. Measurements were made at 234 °C and 274 °C and the data used to estimate initial reaction velocities for both EtO and CO2 formation as a function of O2 and C2H4 partial pressures. These rates were fitted successfully to equations deduced theoretically in Part IV of the present series.
THE STRUCTURE OF PROTOPINE METHIODIDE: A CORRECTION
Authors: Anet F. A. L. , Marion Léo
Published: May 2006

not available
THE PHOTOLYSIS OF DIMETHYL MERCURY IN HEXANE SOLUTION AT LOW TEMPERATURES
Authors: Derbyshire D. H. , Steacie E. W. R.
Published: May 2006

The photolysis of dimethyl mercury in solution in n-hexane has been studied over the temperature range +25 °C. to −80 °C. The results indicate that methane is produced by an abstraction reaction involving the solvent, and ethane is produced by dimerization of methyl radicals. The mechanism of the reaction is discussed, and it is concluded that the abstraction reaction involves radicals possessing considerable energy carried over from the photodissociation.
MICROCALORIMETRIC STUDIES OF POLYVINYL ACETATE SOLUTIONS
Authors: Daoust Hubert , Rinfret Marcel
Published: May 2006

A relation between intrinsic viscosity and the sign of heat of mixing of a linear polymer in different solvents has been predicted by Alfrey, Bartovics, and Mark. To verify this, the intrinsic viscosities and heats of mixing at one concentration for two samples of polyvinyl acetate in six solvents were determined. The heats of mixing have been measured with a Tian–Calvet microcalorimeter especially designed for slow processes and having a sensitivity of one thousandth of a calorie per hour. The results generally agree with the above prediction. Furthermore, the heats of mixing of two fractions of polyvinyl acetate in three solvents have been measured over a range of low concentrations to study the behavior of the quantity B from the theory of van Laar, Scatchard, and Hildebrand on energy of mixing of nonelectrolytes. It was found that B goes through a minimum at low concentrations when the mixing process is exothermic. This effect may be explained by the existence of a critical concentration below which entanglement between macromolecules ceases. For a poor solvent, B seems to be constant at high dilution.
THE ETHANOLYSIS OF 3-HYDROXY-1-(4-HYDROXY-3-METHOXYPHENYL)-2-PROPANONE IN RELATION TO LIGNIN CHEMISTRY
Authors: Gardner J. A. F.
Published: May 2006

The ketol, 3-hydroxy-1-(4-hydroxy-3-methoxyphenyl)-2-propanone, was subjected to ethanolysis and found to yield the four propylphenols which can be isolated from the ethanolysis products of isolated conifer lignin and of conifer lignin in situ. The significance of this finding is briefly discussed.
THE SYNTHESIS OF 4-DIALKYLAMINOETHYLPYRIDINES
Authors: Matuszko Anthony J. , Taurins Alfred
Published: May 2006

For the synthesis of 4-dialkylaminoethylpyridines two reactions were employed, namely, the Mannich condensation of 4-methylpyridine with formaldehyde and secondary amines, and the addition of secondary amines across the double bond of the 4-vinylpyridine.In the first reaction with diethyl-, di-isopropyl-, di-n-butylamine, pyrrolidine, and morpholine, normal Mannich bases (IV-VIII) were obtained. The unsaturated bases (X, XI) were the reaction products when dimethylamine and piperidine were used. The addition of those products 1,3-bis-(dialkylamino)-2-(4′-pyridyl)-propanes (XII, XIII) were formed when dimethyl-and diethylamine were applied.The structures of the normal Mannich bases were confirmed by the synthesis of several compounds (III, IV, VII–IX) from 4-vinylpyridine and secondary amines.
SYNTHESIS OF 1,2-DIALKYLHYDRAZINES AND THE CORRESPONDING AZOALKANES
Authors: Renaud R. , Leitch L. C.
Published: May 2006

The limitations of present methods of synthesizing 1,2-dialkylhydrazines are discussed. A new method of obtaining these compounds in good yields by the reduction of azines with lithium aluminum hydride is reported. Lithium aluminum deuteride was employed as a tracer to investigate the mechanism of the reaction. The 1,2-dialkylhydrazines were oxidized to the azoparaffins in over 90% yields by mercuric oxide in water.
BENZIDINE-REARRANGEMENT DURING THE TITRATION OF AZO-COMPOUNDS WITH TITANOUS CHLORIDE
Authors: Veibel Stig
Published: May 2006

not available
THE PREPARATION OF 2,2,2-TRIFLUOROETHYLAMINE
Authors: McKay A. F. , Vavasour G. R.
Published: May 2006

not available
ANALOGUES OF 2,2′-BIPYRIDYL WITH ISOQUINOLINE AND THIAZOLE RINGS. PART II
Authors: Crowne F. R. , Breckenridge J. G.
Published: May 2006

In continuation of the work reported in Part I, several more bipyridyl analogues have been prepared and the absorption spectra of the cuprous and ferrous complexes determined. The results follow the pattern of the previous series of compounds.
THE MECHANISM OF PERSULPHATE OXIDATIONS
Authors: Eager R. L. , McCallum K. J.
Published: May 2006

It has been found that exchange between persulphate and sulphate, in both concentrated acetic acid as solvent and in aqueous solution, is not more than one half of one per cent complete in 12 hr. at 34.2 °C. This indicates that the equilibrium proposed by Levitt, [Formula: see text] probably plays no part in persulphate oxidations.
THE SYSTEM LITHIUM SULPHATE – AMMONIUM SULPHATE – WATER
Authors: Campbell A. N. , McCulloch W. J. G. , Kartzmark E. M.
Published: May 2006

The binary eutectics Li2SO4•H2O–ice and (NH4)2SO4–ice as well as the ternary eutectics Li2SO4•H2O–Li2SO4•(NH4)2SO4–ice and (NH4)2SO4–Li2SO4•(NH4)2SO4–ice have been determined as to temperature and composition. The complete solubility isotherms at 0.1°, 71.8°, and 95.2 °C. have been investigated. The enthalpies of solution of lithium sulphate monohydrate, of ammonium sulphate, and of double salt have been determined (in water at room temperature), and from these data, as well as from the solubility isotherms, it has been shown that the temperature of the transition of the double salt, Li2SO4•(NH4)2SO4, to its component single salts (in the presence of water) is approached by lowering the temperature, but this transition temperature is still far from reached when the system freezes completely.
THE REACTIONS OF ACTIVE NITROGEN WITH THE BUTANES
Authors: Back R. A. , Winkler C. A.
Published: May 2006

The main product of the reactions of active nitrogen with n- and iso-butanes at 75 °C. and 250 °C. was hydrogen cyanide. Small amounts of C2 hydrocarbons, mainly ethylene and acetylene, were produced in both reactions. Second order rate constants were calculated on the assumption that the reactive species in active nitrogen is atomic nitrogen, and that the initial attack of a nitrogen atom is the rate-controlling step. The activation energies were then estimated to be 3.6 kcal. and 3.1 kcal. and the probability factors 4.5 × 10−4 and 4.4 × 10−4, for the n-butane and isobutane reactions respectively.
THE PHOTOLYSIS OF CYCLOHEXANONE IN PRESENCE OF OXYGEN AND OF CARBON DIOXIDE
Authors: Dunn J. R. , Kutschke K. O.
Published: May 2006

not available
THE VISCOSITY OF SUSPENSIONS OF SPHERES: A NOTE ON THE PARTICLE INTERACTION COEFFICIENT
Authors: Manley R. St. J. , Mason S. G.
Published: May 2006

Measurements of the reduced viscosity of suspensions of glass spheres 5 μ diameter have been made up to concentrations of 18% by volume. The experimental results yield the empirical equation ηsp/c = 2.50 + 12.7c + … The coefficient of c, due to interactions, is in fair agreement with a value of 10.05 based upon a modification of Vand's theory which takes into account the experimentally established mechanism of two-body collisions of spheres in a velocity gradient. Several reasons for the discrepancy are suggested.
A MODIFIED KNORR PYRROLE SYNTHESIS
Authors: MacDonald S. F. , Stedman R. J.
Published: May 2006

not available
HYDROLYSIS OF CELLULOSE ACETATE SULPHATE IN ACETONE
Authors: Keirstead Karl , Myers John
Published: May 2006

When cellulose acetate sulphate is dissolved in acetone the hydrolysis of the sulphate ester is rapid compared with that of the acetate ester. In 70% acetone the relative rates are reversed. Hydrolysis of the sulphate ester in acetone is greatly affected by the temperature. At 25 °C. or greater the hydrolysis is complete after 24 hr. A potentiometric titration method has been developed for the estimation of sulphuric acid in the presence of smaller amounts of acetic acid.
THE VAPOR PHASE PARTIAL OXIDATION OF n-BUTANE—EFFECT OF PRESSURE, REACTION TIME, AND INLET GAS COMPOSITION
Authors: Quon D. , Lana I. Dalla , Govier G. W.
Published: May 2006

Data are presented on the product yields and the general course of the partial oxidation of n-butane at an ambient temperature of 725 °F., at pressures ranging from 50 to 175 p.s.i.a., reaction times of 1.0 to 4.5 sec., and inlet reactant compositions of 1.5 to 6.0 mole % n-butane and 1.5 to 6.0 mole % oxygen (the remainder being diluent nitrogen). Conditions were neither isothermal nor adiabatic and peak temperatures as much as 70 Fahrenheit degrees higher than the inlet temperatures were encountered. The reactor consisted of a 24-ft. length of 1/4-in. stainless steel pipe, immersed in a bath of boiling Aroclor 1254. Under optimum conditions, a 20% conversion of the butane to methanol, ethanol, acetaldehyde, acetone, and formaldehyde was obtained. In all the tests, an induction period of approximately 0.75 sec. was observed.
GLUTAMIC ACID AS AN ADDITION AGENT IN THE ELECTRODEPOSITION OF COPPER
Authors: Adamek S. , Winkler C. A.
Published: May 2006

The polarization–time curves obtained in the presence of glutamic acid generally showed two distinct polarization levels, one corresponding to an induction period following an initial rapid increase of polarization from the standard surface value, and the other corresponding to a steady state period following a second rapid increase of polarization. The polarization at both levels increased with increase of glutamic acid concentration and decreased with increase of sulphuric acid concentration in the electrolyte. In general, the induction period increased, and eventually became irreproducible, with increased sulphuric acid and copper sulphate concentrations, decreased glutamic acid concentration, decreased current density, increased temperature, and addition of chloride. Addition of sufficient chloride prolonged the induction period indefinitely at a polarization level corresponding to the presence of chloride alone. Following the induction period, the concentration polarization increased with glutamic acid concentration and was considerably higher than the value obtained during the induction period. Addition of chloride decreased the concentration polarization.
PHTHALIDE FORMATION: III. CONDENSATIONS WITH 5-HYDROXY-2-METHYLBENZOIC ACID
Authors: Charlesworth E. H. , Dudley E. A. , Nishizawa E. E. , Radych W.
Published: May 2006

The product obtained from the condensation of 5-hydroxy-2-methylbenzoic acid with aqueous formaldehyde and hydrochloric acid is dependent on the temperature. If the condensation is carried out at room temperature 3-hydroxy-6-methylphthalide results. This substance can also be obtained by the demethylation of 3-methoxy-6-methylphthalide. If the condensation is carried out at the boiling point the lactone of 8-hydroxymethyl-1,3-benzodioxane-6-methyl-7-carboxylic acid results. Proof of the presence of the m-dioxane and phthalide rings in this latter substance has been established by opening these rings in succession. In both cases this has led by a series of degradative steps to 4-methoxybenzene-1,2,3,5-tetracarboxylic acid. The structure of this acid has been confirmed by its synthesis in six unambiguous steps from mesitylene.
CHLORINE ISOTOPE EFFECT IN REACTIONS OF TERT-BUTYL CHLORIDE
Authors: Bartholomew Rosalie M. , Brown F. , Lounsbury M.
Published: May 2006

When tert-butyl chloride reacts with either alcoholic silver nitrate or aqueous alcoholic sodium hydroxide the Cl35 compound reacts faster than the Cl37 compound. The ratio of the rates of reaction is[Formula: see text]
UNIT CELL, SPACE GROUP, AND INDEXED X-RAY DIFFRACTION POWDER: DATA FOR CERTAIN NARCOTICS: II. dl-METHADONE HYDROCHLORIDE, dl-METHADONE HYDROBROMIDE
Authors: Barnes W. H. , Forsyth W. J.
Published: May 2006

not available
A POLYSACCHARIDE FROM THE BLUE-GREEN ALGA, ANABAENA CYLINDRICA
Authors: Bishop C. T. , Adams G. A. , Hughes E. O.
Published: May 2006

A complex polysaccharide has been isolated from the fresh-water alga, Anabaena cylindrica, grown in a synthetic culture medium. Prolonged acid hydrolysis yielded glucose, xylose, glucuronic acid, galactose, rhamnose, and arabinose in a molar ratio of 5: 4: 4: 1: 1: 1. Chemical fractionations of the polysaccharide material from solution in cupriethylenediamine, and of its acetate from organic solvents indicated chemical homogeneity.
THE MASS SPECTRUM OF TITANIUM TETRACHLORIDE
Authors: Hogg J. E.
Published: May 2006

An investigation of the mass spectrum of titanium tetrachloride prepared from both commercial titanium dioxide and titanium minerals has been carried out, using a 180° Nier-type mass spectrometer. Values for the relative abundances of the titanium and chlorine isotopes have been found. Measurements of the singly ionized trichloride group show that any variation in the relative abundances of the isotopes of titanium contained in these samples must be less than one per cent.
THE PHOTOLYSIS OF 2,2′-AZO-BIS-ISOBUTYRONITRILE
Authors: Back R. , Sivertz C.
Published: May 2006

The photolysis of 2,2′-azo-bis-isobutyronitrile (AIN) has been studied in benzene solution through combined Corning filters 9863 and 5850 in the near ultraviolet, employing a General Electric UA-2B quartz Uviarc as a light source. An over-all quantum yield of 0.43 was found. The rate of decomposition of AIN in moles/liter seconds for this system is equal to 0.43 × [total light absorbed]. Twice this value may be taken as the rate of initiation when AIN is used as a photochemical initiator of polymerization.
THE PHOTOINITIATED ADDITION OF BUTYL MERCAPTAN TO CONJUGATED AND UNCONJUGATED DOUBLE BONDS
Authors: Back R. , Trick G. , McDonald C. , Sivertz C.
Published: May 2006

This study elucidates the details of a typical initiation encountered in polymerization. A kinetic mechanism for the photoinitiated addition of normal butyl mercaptan to single and conjugated double bonds is proposed, and the corresponding velocity constants namely the attack kα, the transfer kct, and the termination kt have been measured employing a sector method. For the concentrations employed in this work the over-all rate of addition to the double bond is determined by the transfer rate of the composite mercapto monomer radical, while the capture of initiating radicals depends on the rate of attack of the mercaptyl radicals on the double bonds. The transfer rate is about 1000 times faster for a pentenyl than for a conjugated styryl radical, while the attack step is estimated to be several hundred times faster for the conjugated monomer. These conclusions are shown to be consistent with results observed when conjugated and unconjugated monomers are in competition, and are in agreement with the quantum mechanical structure of the radicals and molecules involved. This work reports a general survey of the field, and subsequent papers will extend the observations.
INTENSITY IN THE RAMAN EFFECT: II. STANDARD RAMAN INTENSITIES AND VIBRATIONAL ASSIGNMENTS IN THE CHLOROETHANES
Authors: Allen G. , Bernstein H. J.
Published: May 2006

The standard intensities of the Raman bands of the chloroethanes without rotational isomers (Et; 1,1; 1,1,1; 1,1,1,2; penta, and hexa) have been measured in the liquid phase with a photoelectrically recording Raman spectrometer. Vibrational assignments are proposed which are consistent with the depolarization data, infrared contours, and a vibrational sum rule. The total Raman intensity is a smooth but nonlinear function of the number of chlorine atoms. The sum of the intensities of the bands assigned to hydrogen modes and that for the skeletal modes is also a smooth function of the number of substituents.
SOME CHLORINATION PRODUCTS OF BUTYNE-1, BUTYNE-2, AND PENTYNE-1
Authors: Morse A. T. , Leitch L. C.
Published: May 2006

The following new compounds were isolated from the vapor phase chlorination of butyne-1, butyne-2, and pentyne-1: 1,1,2,2-tetrachlorobutane, 2,2,3,3-tetra chlorobutane, 1,1,2,2-tetrachloropentane, trans-1,2-dichloro-1-butene, trans-2,3-dichloro-2-butene, and trans-1,2-dichloro-1-pentene. Dehydrochlorination of 1,1,2,2-tetrachlorobutane and 1,1,2,2-tetrachloropentane gave 1,1,2-trichloro-1-butene and 1,1,2-trichloro-1-pentene respectively. Partial dechlorination of 1,1,2,2-tetrachlorobutane and 1,1,2,2-tetrachloropentane gave cis and trans isomers of 1,2-dichloro-1-butene and 1,2-dichloro-1-pentene respectively. 2,2,3,3-Tetrachlorobutane gave chiefly trans-2,3-dichloro-2-butene. 1,1,1,2,2-Pentachlorobutane and 1,1,1,2,2-pentachloropentane were prepared by chlorination of 1-chloro-1-butyne and 1-chloro-1-pentyne respectively.
PRÉPARATION DE DÉRIVÉS DU PAPAVÉRINOL ET DES HYDROXYLAUDANOSINES
Authors: Ferron Jean-Louis , L'Ecuyer Philibert
Published: May 2006

not available
A MECHANISM FOR THE ANOMERIZATION OF ACETYLATED ALKYL GLYCOPYRANOSIDES
Authors: Lemieux R. U. , Shyluk W. P.
Published: May 2006

Unequivocal evidence that the anomerization of acetylated alkyl glycopyranosides can proceed by way of an intramolecular mechanism was obtained through the observation that a racemic mixture of methyl β-glucopyranoside tetraacetate with the D-isomer labelled in the methoxyl group with carbon-14 is anomerized both by titanium tetrachloride and boron trifluoride without transfer of radioactive methoxyl groups to the L-isomer. It is submitted that these intramolecular anomerizations are best rationalized as the result of an unsuccessful attempt by the environment to bring about glycosidic cleavage and proceed by way of an ion-pair intermediate in which the anion is derived from the aglycon group.
THE SOLVOLYSIS OF THE ALPHA- AND BETA-3,4,6-TRI-O-ACETYL-D-GLUCOPYRANOSYL CHLORIDES
Authors: Lemieux R. U. , Huber G.
Published: May 2006

3,4,6-Tri-O-acetyl-β-D-glucopyranosyl chloride was found to undergo solvolysis in acetic acid to form 1,3,4,6-tetra-O-acetyl-α-D-glucopyranose as the main reaction product. The much less reactive anomeric α-chloride also appeared to undergo solvolysis with extensive inversion of the anomeric center. It is submitted that the tendencies for inversion obtained in these ionic reactions are due to the conformations imposed on the intermediate ions through distribution of the positive charge to the ring oxygen and the consequent introduction of double-bond character to the carbon-1 to ring-oxygen bond.
THERMODYNAMIC CONSIDERATIONS OF SURFACE REGIONS: ADSORBATE PRESSURES, ADSORBATE MOBILITY, AND SURFACE TENSION
Authors: Flood E. A. , Huber Max
Published: May 2006

The flow of water through the micropore system of activated carbon has been described in previous papers as a hydrodynamic flow of liquid water under high pressure gradients due to surface forces. It is shown below that these high pressures are probably real and that the temperature coefficient of the flow rate is closely related to the temperature coefficient of the viscosity of liquid water. Surface tension is discussed.
AN APPARATUS FOR THE MEASUREMENT OF DIELECTRIC CONSTANTS OF ADSORBED GASES AT FREQUENCIES UP TO 100 Mc./Sec.
Authors: Waldman M. H. , McIntosh R.
Published: May 2006

The design of an apparatus suitable for the measurement of dielectric constants at frequencies up to 106 Mc./sec. is shown. The apparatus was used to measure changes in capacitance with volume adsorbed for the system sulphur dioxide – rutile at about 3.5 °C. and for frequencies of 13, 36, and 106 Mc./sec. The results failed to reveal any dispersion due to the adsorbed matter in this frequency range. The dielectric behavior observed is the same, within experimental error of a few per cent, as that found by Channen and McIntosh for the same system at 3.7 Mc./sec.
HEATS OF ADSORPTION OF KRYPTON ON HIGHLY GRAPHITIZED CARBON BLACK
Authors: Amberg C. H. , Spencer W. B. , Beebe R. A.
Published: May 2006

Calorimetric heats have been determined at −183 °C. for the adsorption of krypton on a highly graphitized sample of carbon black. This adsorption system is of particular interest because of the extreme step-wise nature of the isotherm. Both the heat-coverage curve and the isotherm appear to be indicative of a high degree of homogeneity of the adsorbing surface.
THE ADSORPTION OF ALIPHATIC ACIDS FROM AQUEOUS SOLUTIONS BY POROUS CARBONS
Authors: Morrison John L. , Miller David M.
Published: May 2006

The maximum adsorptions of the lower members of the mono- and di-carboxylic acids from aqueous solutions were determined for coconut charcoals of different degrees of activation. Based on these results, a method for estimating pore size was applied to the more finely porous charcoals. To corroborate the pore sizes estimated from acid adsorption, pore size – area distributions were calculated from measurements of the water vapor sorption isotherms of the charcoals. An alternation in the maximum amounts of adsorbed acids was observed with the more active charcoals. Acids with an even number of carbon atoms had larger adsorptions than acids with an odd number. The alternation was much more marked for the di- than for the mono-carboxylic acids. A remarkable correlation between the alternation of adsorptions and of melting points of both acid series was observed. An explanation for the general phenomenon of alternation based on rotational motion of molecules in the solid state is given as an alternative to the widely held one based on tilting of molecular chains.
KINETICS OF THE CUPRIC ACETATE CATALYZED HYDROGENATION OF DICHROMATE IN AQUEOUS SOLUTION
Authors: Peters E. , Halpern J.
Published: May 2006

In aqueous solution, cupric acetate was found to act as a homogeneous catalyst for the reduction of dichromate by hydrogen, i.e.[Formula: see text]

The paper describes a kinetic study of this reaction. Rates were determined at temperatures between 80° and 140 °C. and hydrogen partial pressures up to 27 atmospheres. The rate is independent of the dichromate concentration but varies directly with the partial pressure of hydrogen and is nearly proportional to the concentration of cupric acetate. The activation energy is 24,600 calories per mole. Cupric acetate, apparently acting as a true catalyst, activates the hydrogen through formation of a complex with it. An extension of the mechanism proposed earlier for the reaction of cupric acetate itself with hydrogen also accounts for the kinetics of the dichromate reaction.
THE BIOGENESIS OF ALKALOIDS: XIV. A STUDY OF THE BIOSYNTHESIS OF DAMASCENINE AND TRIGONELLINE
Authors: Leete Edward , Marion Léo , Spenser Ian D.
Published: May 2006

Tryptophan-3-C14was prepared from methyl labelled sodium acetate and fed to mature Nigella damascena L. plants. Radioactivity was translocated throughout the plant, but no activity was detected in the damascenine isolated from it. Similarly the radioactive tryptophan was fed to pea seedlings and trigonelline detected in the plant extracts. This was also inactive, and these results are discussed.
SOME OBSERVATIONS ON CYANIC ACID AND CYANATES
Authors: Lister M. W.
Published: May 2006

Various reactions of cyanic acid and the cyanate ion have been examined. Cyanic acid, in the presence of added hydrochloric or nitric acid, decomposes quantitatively according to the equation: HNCO + H3O+ → CO2 + NH4+. The rate constant for this reaction was measured over a range of temperature and ionic strength, and was found to be 0.86 mole liter−1 min.−1 at unit ionic strength and 1.5 °C. The activation energy is [Formula: see text] The effect of ionic strength on the reaction with hydrochloric acid closely parallels that on the activity coefficients of the acid itself. Without added acid cyanic acid decomposes by a first order reaction: HNCO + 2H2O → NH4HCO3, followed by a rapid second stage: NH4HCO3 + HNCO → NH4NCO + H2CO3. This reaction has a rate constant of 0.011 min.−1 at 0 °C. and an activation energy of 16 kcal. There is also a few per cent of some side reaction. Cyanate ions in alkaline solution decompose thus: OCN− + 2H2O → NH4+ + CO3−−. This reaction was examined over a range of temperature and ionic strength: it is first order with k = 3.0 × 10−3 min.−1at 100 °C. (0.3 ionic strength) and [Formula: see text] activation energy. The rate is somewhat dependent on hydroxide concentration, when this is fairly low. The reaction is catalyzed by carbonate, but not by a number of other anions that were examined. The rate of the catalyzed reaction is proportional to the carbonate concentration, but independent of cyanate, at least over a considerable range. The ionization constant of cyanic acid has been measured by a method that avoids errors from hydrolysis; the value obtained was 2.0 × 10−4. The oxidation of cyanate by hypochlorite and by chlorine was examined more briefly.
UNIT CELL, SPACE GROUP, AND INDEXED X-RAY DIFFRACTION POWDER DATA FOR CERTAIN NARCOTICS: VI. NARCOTINE
Authors: Barnes W. H.
Published: May 2006

not available
THE SYNTHESIS OF HEMOPYRROLE-DICARBOXYLIC ACID AND OF SOME DIPYRROMETHENES
Authors: MacDonald S. F. , Stedman R. J.
Published: May 2006

The pyrrole IIe was obtained through the known IIc and hydrolyzed to IIIb. This last could be partially decarboxylated to hemopyrrole-dicarboxylic acid IIIc or, with formic acid, converted into the dipyrromethene VIIb. The isomeric dipyrromethene VIIa was obtained analogously.
STUDIES ON CARRAGEENIN: COMPARISON OF FRACTIONS OBTAINED WITH POTASSIUM CHLORIDE AND BY SUCCESSIVE EXTRACTION AT ELEVATED TEMPERATURES
Authors: Goring D. A. I. , Young E. Gordon
Published: May 2006

Carrageenin was fractionated with potassium chloride and by successive extractions at elevated temperatures. Measurements were made of sulphate content, optical rotation, gel strength, intrinsic viscosity, sedimentation rate, and ionic mobility. The results indicated three components extractable at 30 °C., 60°C., and 100–120 °C. The 60 °C. extract had a high gel strength while the components extracted at 30 °C. and 100–120 °C. showed low gelling tendencies. The two non-gelling components were concentrated in the supernatant liquid when fractionated with potassium chloride.
THE PHOTO-OXIDATION OF AZOMETHANE
Authors: Hoey G. R. , Kutschke K. O.
Published: May 2006

The photo-oxidation of azomethane has been studied at low oxygen pressures (0.02 to 1 mm.) in the temperature range ca. 25 °C. to 161 °C. The primary process in the normal photolysis of azomethane is essentially unaffected by the presence of oxygen. Carbon monoxide is probably a secondary product of the oxidation of methyl radicals. Carbon dioxide formation is quite small, and therefore neither methyl radicals nor CH3N=N—CH2 radicals are oxidized appreciably to carbon dioxide. Nitrous oxide, which is a major product of the oxidation, is most likely formed from the oxidation of CH3N=NCH2 radicals. The suggested mechanism of N2O formation is:[Formula: see text]

The reaction of methyl radicals with oxygen was found to proceed with a negligible activation energy and a steric factor of the order of 10−2. Evidence for the occurrence of the reactions[Formula: see text]at room temperature was obtained.
THE PREPARATION OF DICYANODIACETYLENE
Authors: Brockman F. J.
Published: May 2006

The preparation of dicyanodiacetylene as reported by Moureu and Bongrand has been investigated more fully and a procedure developed whereby yields as high as 36% have been obtained.
HYDROGEN PEROXIDE AND ITS ANALOGUES: VI. INFRARED SPECTRA OF H2O2, D2O2, AND HDO2
Authors: Bain Osias , Giguère Paul A.
Published: May 2006

The absorption spectrum of hydrogen peroxide was re-examined with a prism instrument in the region 1.5 to 25 μ. A pair of well-resolved perpendicular bands arising from torsional oscillation of the OH groups were found centered about 460 and 575 cm.−1. The overtone band at 3.8 μ was shown to be a hybrid with prominent rotational structure and some indications of doubling. Its assignment to the combination ν2+ν6 implies a positive anharmonicity. Four new overtone bands were observed in liquid hydrogen peroxide. The infrared spectrum of deuterium peroxide was measured for the first time in the solid and vapor states. The vapor bands are quite different in appearance from those of hydrogen peroxide. One of the fundamentals, the asymmetric O—D stretching at 2661 cm−1, was resolved sufficiently to allow calculation of the rotational constants of the isotopic molecule. Mixtures of the two peroxides containing around 40% of HDO2 were also investigated; from the results the frequency of the as yet unobserved symmetric modes ν1 and ν2 could be estimated with fair certainty. The O—O stretching vibration at 11μ was too weak to be located definitely in the spectra of the gaseous peroxides. The structural parameters of the H2O2 molecule are now established as follows:[Formula: see text]

The O—H and O—D stretching bands were studied in solutions of the three isotopic peroxides in carbon tetrachloride.
INTERDIFFUSION OF POLYISOBUTYLENE AND CYCLOHEXANE
Authors: Kelly J. , Hutcheon A. T.
Published: May 2006

not available
UNIT CELL, SPACE GROUP, AND INDEXED X-RAY DIFFRACTION POWDER DATA FOR CERTAIN NARCOTICS VII. MORPHINE HYDROCHLORIDE TRIHYDRATE, AND THE DIHYDRATES OF MORPHINE HYDROBROMIDE, MORPHINE HYDRIODIDE, CODEINE HYDROCHLORIDE, CODEINE HYDROBROMIDE, CODEINE HYDRIODIDE
Authors: Barnes W. H. , Lindsey June M.
Published: May 2006

not available
THE IDENTITY OF CRYPTOCAVINE AND CRYPTOPINE
Authors: Thomas A. F. , Marion Léo , Manske R. H. F.
Published: May 2006

not available
COMPRESSIBILITY OF GASES AT HIGH TEMPERATURES: IX. SECOND VIRIAL COEFFICIENTS AND THE INTERMOLECULAR POTENTIAL OF NEON
Authors: Nicholson G. A. , Schneider W. G.
Published: May 2006

The second virial coefficients of neon have been determined in the temperature range 0° to 700 °C. and the pressure range 10 to 80 atmospheres. These data were combined with published low temperature (−150° to 0 °C.) second virial data, to investigate the intermolecular potentials of neon using both a Lennard-Jones potential, with a 9th and 12th power repulsion term, and also a modified Buckingham exponential–six potential. The agreement between observed and calculated values of B(T) was excellent for both the exponential–six and the Lennard-Jones 12:6 potentials and slightly less satisfactory for the Lennard-Jones 9:6 potential.
THE COMPRESSIBILITY OF GASES AT HIGH TEMPERATURES: X. XENON IN THE TEMPERATURE RANGE 0° TO 700 °C. AND THE PRESSURE RANGE 8 TO 50 ATMOSPHERES
Authors: Whalley E. , Lupien Y. , Schneider W. G.
Published: May 2006

The virial coefficients of xenon have been measured in the temperature and pressure range described. The results are compared with previous measurements.
IDENTIFICATION OF SPRUCE SULPHITE LIQUOR COMPONENTS
Authors: Kvasnicka E. A. , McLaughlin R. R.
Published: May 2006

Spruce sulphite liquor was extracted with butyl acetate. By means of solvent fractionation, chromatography, and countercurrent distribution, vanilloyl methyl ketone, vanillin, dihydroconiferyl alcohol, 3,3′-dimethoxy-4,4′-dihy-droxystilbene, and a new phenolic compound, C20H24O5, were isolated and identified.
A NEW TYPE OF CELLULOSE ETHER: THE PREPARATION AND PROPERTIES OF THE ω-(p-AMINOACETOPHENONE) ETHER OF CELLULOSE
Authors: McLaughlin R. R. , Mutton D. B.
Published: May 2006

With the object of preparing a cellulose ether containing diazotizable amino groups, seven different forms of cellulose, or cellulose derivatives, were treated with 10 different reagents under a variety of conditions. Reasons why only one reagent under one set of conditions gave a product with a substantial degree of substitution (0.35) and with satisfactory physical properties are presented. This resulting ether, the ω-(P-aminoacetophenone) ether of cellulose, was prepared by the reaction between ω-chloro-P-aminoacetophenone and ethanol-washed soda-cellulose (from wood pulp, cotton, paper, or rayon). It can be (a) diazotized and coupled with any of the usual reagents to yield cellulose-azo colors, (b) xanthated, before or after coupling, and spun as rayon filament; if uncoupled at this point it can be diazotized and coupled, (c) dyed directly with acid dyes, (d) rendered organo-soluble by nitration, and (e) carboxymethylated after coupling to yield colored, water-soluble derivatives. It is insoluble in the usual cellulose reagents, and is as stable to acid and alkaline hydrolysis as cellulose.
REACTIONS BETWEEN SOLID CALCIUM CARBONATE AND ORTHOPHOSPHATE SOLUTIONS
Authors: Clark J. S. , Turner R. C.
Published: May 2006

Studies of the reactions between solid calcium carbonate and orthophosphate solutions at low partial pressures of carbon dioxide indicated that hydroxyapatite was the stable product formed in these systems. Hydroxyapatite precipitated directly even though dicalcium phosphate formed initially under certain conditions. The reactions with orthophosphate did not seriously disturb the normal calcium carbonate equilibrium with the solution.
THE TERTIARYBUTYLBENZENES: I. ALKYLATION OF 1,4-DI-t-BUTYLBENZENE WITH t-BUTYL CHLORIDE
Authors: Barclay L. Ross C. , Betts Eileen E.
Published: May 2006

The alkylation of P-di-t-butylbenzene with excess t-butyl chloride in the presence of aluminum chloride in the cold produces a new aromatic hydrocarbon, m.p. 218.5–219°. Evidence is given for the presence of an alicyclic nucleus in this hydrocarbon which analyzes for C22H34. The preparation of nitro and amino derivatives from this hydrocarbon is described. The alkylation of benzene under similar conditions yielded some 1,3,5-tri-t-butylbenzene, and an improved method of preparation of this hydrocarbon from P-di-t-butylbenzene is given.
OXIDE COMPLEXES FORMED IN THE SYSTEMS PLATINUM METALS: ALKALI CARBONATES: OXYGEN
Authors: Scheer J. J. , Arkel A. E. Van , Heyding R. D.
Published: May 2006

On heating mixtures of a platinum metal with an alkali carbonate in different ratios and at different temperatures in an oxygen stream, two kinds of compounds are formed:(1) the cubic compounds NaxPt3O4 and NaxPd3O4,and(2) a series of oxide complexes with compositions ABO2 or A2BO3, both isomorphous with Na2SnO3.
GLYCERIDE SYNTHESIS: I. SYNTHESIS OF SYMMETRICAL DIGLYCERIDES FROM DIHYDROXY ACETONE AND ALLYL ALCOHOL
Authors: Barry P. J. , Craig B. M.
Published: May 2006

1,3-Distearoxy acetone and 1,3-dipalmitoxy acetone were prepared by interesterification of the methyl esters of the fatty acids with 1,3-dipropionoxy acetone diethyl mercaptal. The 1,3-diglycerides were obtained by hydrogenation of the ketone group. Allyl tetrahydropyranyl ether was oxidized to 1-tetra-hydropyranyl glycerol which was acetylated and interesterified with methyl esters of fatty acids to produce 1,3-diglycerides.
TETRAETHYL PYROPHOSPHATE LABELED WITH PHOSPHORUS-32
Authors: Robinson J. R.
Published: May 2006

not available
STUDIES IN THE POLYOXYPHENOL SERIES: IX. THE SYNTHESIS OF PAPAVERINE AND PAPAVERALDINE BY THE POMERANZ-FRITSCH METHOD
Authors: Guthrie Donald A. , Frank Arlen W. , Purves C. B.
Published: May 2006

Fritsch's cyclization of N-(α-veratrylveratrylidene)-aminoacetal in sulphuric acid was shown to give 1.1% of papaverine and 23% of an isomer, m.p. 164.5–165.5 °C.; hydrochloride, m.p. 212 °C. decomp., which was supposed to be 4,5-bis(3,4-dimethoxyphenyl)-2H-pyrrolenine, produced by an internal condensation of the acetal or the corresponding aldehyde with the reactive methylene group. A similar structure was proposed for another unidentified isomer prepared by Schlittler and Müller. Hydrogenation of Fritsch's acetal gave N-(α-veratryl-veratryl)-aminoacetal, m.p. 69.5–70 °C., which was cyclized to a base, m.p. 155.5–156 °C.; N-acetyl derivative, m.p. 203.5–204 °C., formulated as 2,3-bis(3,4-dimethoxyphenyl)-3-pyrroline. Substances presumed to be the intermediate aldehyde and aldol were isolated as colorless oils. Condensation of the diketone veratril with aminoacetal, followed by cyclization of the crude product, constituted a new two-step synthesis of papaveraldine in 8% yield, and the reduction of the latter to papaverine was known.Other crystalline compounds prepared incidentally and thought to be new were veratril monoanil, m.p. 172–173 °C.; α,α′-biveratrylideneaminoacetal, m.p. 101–102 °C.; a compound formulated as 2,3-bis(3,4-dimethoxyphenyl)-4-ethylmer-captopyrrolidine hydrochloride, m.p. 184–185 °C; from this an unidentified mercury complex, m.p. 109 °C. decomp.; 4,4′dibenzyloxy-3,3′-dimethoxy-desoxybenzoin, m.p. 141–142 °C; and its oxime, m.p. 137.5 °C.
FREE RADICAL RECOMBINATION IN THE PHOTOLYSIS OF ACETONE
Authors: Naldrett S. N.
Published: May 2006

(CH3CO)2-1-C14 (I) was prepared by irradiating (CH3)2CO in the presence of CH3I-C14. Acetone was then irradiated at room temperature with light of 2537 Å in the presence of (I). Radioactivity was found in all products which contained methyl groups but not in any carbon monoxide product. The amount of carbon-14 ultimately found in acetone confirms that the quantum efficiency of the primary photolytic process is nearly unity and that extensive recombination of methyl and acetyl radicals to form acetone is responsible for the low over-all quantum efficiency of decomposition.
THE RECIPROCAL SALT-PAIR SYSTEM: SODIUM CHLORIDE – AMMONIUM SULPHITE – SODIUM SULPHITE – AMMONIUM CHLORIDE – WATER AT 20 °C. AND 60 °C.: PART I. TERNARY SYSTEMS
Authors: Labash J. A. , Lusby G. R.
Published: May 2006

Solubility data have been obtained at 20 °C. and 60 °C. for the following ternary systems:[Formula: see text]No evidence of the formation of double salts or of solid solutions in the first three systems was obtained. Ammonium sulphite monohydrate does not appear to dehydrate at 60 °C. in solutions saturated with sodium sulphite or ammonium chloride. In the study of the NaCl–NH4Cl–H2O system, the data agree with average values obtained from the literature and some discrepancies in the published data have been noted. In the NaCl–Na2SO3–H2O system some anomalous results can be explained on the basis of the existence of solid solutions of the hydrated and anhydrous forms of sodium sulphite and sodium sulphate.
COMBINATION AND DISPROPORTIONATION OF ETHYL RADICALS: INFLUENCE OF THE REACTION H+C2H5 = C2H6
Authors: Smith Moyra J. , Beatty Patricia M. , Pinder J. A. , Roy D. J. Le
Published: May 2006

The mercury (3P1) photosensitized hydrogenation of ethylene has been studied at room temperature as a function of ethylene concentration, mercury concentration, and light intensity. In addition to combination and disproportionation, ethyl radicals have been shown to take part in the reaction[Formula: see text]The conditions favoring this reaction have been established and anomalous values previously found for the ratio of ethane to butane have been explained. The value obtained for the ratio of the rate constants for the disproportionation and combination of ethyl radicals, 0.15 ±.01, is in excellent agreement with the values obtained by other methods. Hexane formation is of some importance at low light intensities and high ethylene concentrations, and is adequately accounted for by the reactions[Formula: see text]
PRELIMINARY STUDY OF PHOTOCHEMICAL BEHAVIOR IN THE SYSTEM NITROGEN DIOXIDE – ETHANE
Authors: Rohr T. M. , Noyes Jr. W. Albert
Published: May 2006

The addition of ethane to nitrogen dioxide either during exposure to radiation transmitted by pyrex, or afterwards, reduces the amount of oxygen formed. At room temperature this is apparently due to the effectiveness of ethane in promoting the reverse reaction of nitric oxide and oxygen to form nitrogen dioxide. At temperatures over 100° there is a reaction which uses oxygen atoms produced in the primary process. Nitroethane (or nitrosoethane) is formed along with carbon monoxide, carbon dioxide, and some methane. The results suggest that acetaldehyde is an intermediate, but acetaldehyde could not be detected because it would react thermally with nitrogen dioxide. It is not possible to give a complete explanation of the results, but suggestions can be made which might form the basis for later work.
FURTHER DEGRADATION REACTIONS OF ANNOTININE
Authors: Anet F. A. L. , Marion Léo
Published: May 2006

Both the hydroxylactone obtained by the action of chromous chloride on annotinine chlorohydrin, and the unsaturated lactone B prepared by the action of the same reagent on the hydroxylactone, contain a secondary nitrogen and a vinyl group. The unsaturated lactone A which accompanies the hydroxylactone is a cyclic allylamine which on oxidation with potassium permanganate yields an amino acid C14H19O4N. These facts make it possible to explain the reaction of chromous chloride with annotinine chlorohydrin. The amino acid can be de-hydrogenated to an acid containing a free carboxyl and a lactamic grouping (C14H15O3N) but no longer containing a lactone ring. The lactamic acid which seems to contain a benzene ring is readily decarboxylated to a neutral substance C13H15ON, showing color reactions and ultraviolet absorption similar to those of strychnine.
THE MECHANISM OF THE HYDRATION OF CALCIUM OXIDE
Authors: Birss Fraser W. , Thorvaldson T.
Published: May 2006

Three samples of calcium oxide, designated as A, B, and C, were prepared from calcium carbonate labelled with calcium-45. A was heated to constant weight at 700 °C.; B was heated an additional three hours at 1400 to 1550 °C.; and C was heated six hours at the same temperature. The samples were hydrated in a supersaturated lime solution at 21 °C., the development of activity and the changes in concentration of the solution being determined. The activity entering the solution accounted, according to theory, for the following percentages of the samples passing through the solution during the hydration: A, 27%; B, 57%; C, 94%. These results indicate that sample C ("dead-burnt" lime) hydrated by a "through-solution" mechanism, but that A and B either hydrated partly according to some other mechanism, such as a vapor phase process in the pores of the particles of lime, or the calcium ions failed to reach the bulk of the hydrating liquid before precipitation as calcium hydroxide.
THE ADSORPTION OF NITROGEN, OXYGEN, AND ARGON BY GRAPHITE
Authors: McDermot H. L. , Arnell J. C.
Published: May 2006

The adsorption of nitrogen, oxygen, and argon by three Acheson graphites has been measured at liquid nitrogen and liquid oxygen temperatures. The isotherms were Type II in the B.E.T. classification and displayed two kinds of hysteresis. The first kind was attributed to the presence of pores in the graphite and the second kind to intercrystalline swelling.
SIMULTANEOUS SURFACE EXCHANGE STUDIES USING BOTH CATION AND ANION
Authors: Stow R. M. , Spinks J. W. T.
Published: May 2006

Labelled Sr++ and SO4= have been used simultaneously to measure the apparent surface area of a SrSO4 precipitate by the direct radioactive method. The values found differ by about 90%. By contrast, when labelled Pb++ and SO4= are used to measure the apparent surface area of PbSO4, the values found are in close agreement. The results are discussed with reference to the kinetics of surface exchange reactions.
CYSTINE AS AN ADDITION AGENT IN THE ELECTRODEPOSITION OF COPPER
Authors: Sukava A. J. , Winkler C. A.
Published: May 2006

The steady state polarization of 100 mv. in acid copper sulphate electrolyte, at 2 amp./dm.2, appears to consist of 45 to 50 mv. activation overpotential to deposit aquo–copper complexes, 20 to 25 mv. concentration polarization, and about 30 mv. polarization due to hydrogen ion interference. The presence of cystine in the electrolyte gave rise to polarization–time curves similar to those observed previously with gelatine. The increase of polarization caused by cystine appears to be due to an obstructive effect of adsorbed cystine (or its copper complex), together with an increase of concentration polarization. Cystine alone probably does not affect the activation overpotential. Addition of sufficient chloride virtually eliminated the polarization due to obstruction by cystine, possibly by acting as an electron bridge or by forming more readily dischargeable chloro–cystine–copper complexes. Chloride also eliminated the increment in concentration polarization caused by cystine. Attainment of a minimum total steady state polarization of about 40 mv. in the presence of cystine and chloride appeared to reflect an increase of surface, hence a decrease of true current density with time of deposition. The addition agent behavior of methionine was, in most respects, similar to that of cystine. The behavior of thiourea at low concentrations appeared to be complicated, but the effects of chloride were similar to those observed with gelatine.
THE PHOTOINITIATED ADDITION OF MERCAPTANS TO OLEFINS: II. THE KINETICS OF THE ADDITION OF n-BUTYL MERCAPTAN TO 1-PENTENE
Authors: Onyszchuk M. , Sivertz C.
Published: May 2006

The detailed kinetics involved in the photoinitiated addition of n-butyl mercaptan to 1-pentene is presented. It has been shown that side reactions such as propagation and α-dehydrogenation are relatively negligible and the principal mechanism comprises attack by thiyl radical followed by transfer with mercaptan by the alkyl radical. The velocity constant of the attack step is estimated to be 7 × 106 and that of the transfer step 1.4 × 106 liters/mole-sec. These values together with approximate termination velocity constants are shown to explain the kinetics over a wide range of concentration.
OLIGOSACCHARIDES OF XYLOSE FROM WHEAT STRAW HEMICELLULOSE
Authors: Bishop C. T.
Published: May 2006

A series of oligosaccharides were prepared by autoclaving wheat straw hemicellulose at 120 °C. in distilled water. The di- to the hepta-saccharide inclusive were shown to be members of the (1 → 4)-β-D-xylopyranose series. The octasaccharide was shown to be doubly branched. Certain aspects of the structure of wheat straw hemicellulose are discussed on the basis of these results.