bluuebunny/crossref_metadata_2025 huggingface dataset:
PHOTOCONDUCTIVITY OF SOME POLYNUCLEAR AROMATIC HYDROCARBONS
Authors: Kommandeur J. , Korinek G. J. , Schneider W. G.
Published: May 2006

The spectral response, voltage dependence, and intensity dependence of the surface photocurrent in naphthalene, terphenyl, pyrene, stilbene, and azulene have been measured. Pyrene and naphthalene have a high sensitivity for photoconduction at the long-wavelength edge of the optical absorption spectrum. In the spectral response of pyrene three peaks appear at 4475 Å, 4275 Å, and 4100 Å. It is suggested that these peaks are due to weak optical absorptions to energy levels which are highly efficient in promoting conduction. It is possible that a similar effect occurs in naphthalene, where maximum photoconductivity coincides with a weak absorption reported by McClure and Schnepp. Azulene only shows photoconductivity at wavelengths corresponding to absorption to the second singlet state.
MOLECULAR REARRANGEMENTS IN THE REACTIONS OF OXYGEN ATOMS WITH OLEFINS
Authors: Cvetanović R. J.
Published: May 2006

Reactions of oxygen atoms with propylene, butene-1, iso-butene, cis-butene-2, trans-butene-2, cis-pentene-2, and tetramethyl ethylene have been studied at room temperature and at pressures between 50 and 600 mm. The following generalizations can be made. The oxygen atom adds predominantly to the "less-substituted" carbon atom of the olefinic double bond to form a short-lived biradical which rapidly rearranges into isomeric epoxy and carbonyl compounds. Rearrangements involve migration of radicals (including H atoms) from the carbon atom to which oxygen is attached to the other carbon atom of the original double bond. Partly inhibited rotation around the original double bond also takes place. Migration of H atoms is exclusively internal. Migration of larger radicals, such as CH3, is only partly internal: a large fraction of these radicals become completely detached from the rest of the molecule and the particular carbonyl compound is produced both by radical combination and by internal migration. The fragmentation resulting from the splitting off of a migrating radical is pressure independent. The final addition products formed are "hot" as a result of high heats of reaction and undergo decomposition if the excess energy is not removed by collisions. This second type of fragmentation is, therefore, pressure dependent. It is very extensive in the case of ethylene and appears to be completely suppressed in the investigated pressure range in the case of more complex olefins (possessing a greater number of degrees of freedom) such as butenes and higher homologues. Propylene exhibits an intermediate behavior. For orientation of addition of oxygen atoms a carbon atom of an olefinic double bond to which CH3 is attached is "less substituted" than a corresponding carbon atom to which C2H5 is attached.
STRUCTURE AND PROPERTIES OF CYCLIC COMPOUNDS: XI. DISSOCIATION CONSTANTS OF THE CYANOHYDRINS OF SOME METHYLCYCLOHEXANONES
Authors: Wheeler Owen H. , Zabicky Jacob Z.
Published: May 2006

The dissociation constants of the cyanohydrins of a series of methylcyclohexanones have been measured. The polymethylcyclohexanone cyanohydrins show increasing instability on substitution owing to the effects of "axial crowding". The cyanohydrins of 3- and 4-methylcyclohexanone were found to be more stable than that of cyclohexanone and to explain this a new concept of "equatorial interference" is introduced.
ÉTARD REACTION: I. ITS SCOPE AND LIMITATION WITH SUBSTITUTED TOLUENES
Authors: Wheeler Owen H.
Published: May 2006

The scope and limitations of the Étard oxidation of substituted toluenes to substituted benzaldehydes by chromyl chloride have been studied. The conditions of the reaction were investigated and an improved method of performing it was developed.
THE NON-ENZYMATIC HYDROLYSIS OFp-NITROPHENYL PHOSPHATE
Authors: Holbrook K. A. , Ouellet Ludovic
Published: May 2006

The kinetics of the non-enzymatic hydrolysis of p-nitrophenyl phosphate have been studied in aqueous solution in the pH range 2.6 to 9.0 and at temperatures from 68.0°to 82.0 °C. The reaction has been followed by colorimetric measurement of the nitrophenol produced by the reaction[Formula: see text]The reaction is first order with respect to p-nitrophenyl phosphate and has an activation energy of 26.0 kcal./mole at pH 2.6. An explanation has been proposed in terms of the different rates of hydrolysis of the various ionic species of the ester present in solution.
INFLUENCE OF WATER CONCENTRATION ON THE HYDROLYSIS OF UNSTABILIZED CELLULOSE NITRATE IN ACETONE/WATER SOLUTION
Authors: Gagnon Paul E. , Keirstead Karl F. , Newbold Brian T. , Thomas J.
Published: May 2006

The influence of water concentration upon the hydrolysis of the sulphate acid ester in unstabilized cotton and wood cellulose nitrates in acetone/water solution at 25° ± 0.1 °C. has been determined. When the water content of these systems was increased, the rate of hydrolysis of the sulphate acid ester in cotton or wood cellulose nitrates decreased. This effect was greatest in the first hour of hydrolysis. The presence of more than about 2% water in the acetone/water solution prevented the completion of hydrolysis after 24 hours.
L'ARYLATION DES QUINONES PAR LES SELS DE DIAZONIUM : I. SUR LA SYNTHÈSE DES MONOARYL-p-BENZOQUINONES
Authors: Brassard P. , L'Écuyer P.
Published: May 2006

not available
REACTIVITY STUDIES ON NATURAL PRODUCTS: IV. DISSOCIATION CONSTANTS OF THE CYANOHYDRINS OF SOME STEROID KETONES
Authors: Wheeler Owen H. , Mateos José L.
Published: May 2006

The dissociation constants of the cyanohydrins of 3-, 6-, and 7-ketocholestane, 3-ketocoprostane, Δ4- and Δ5-cholestenone, and Δ7-, Δ8(9)-, Δ8(14)-, and Δl4-ergosten-3-one have been measured in 80% dioxane at 25.0°. Cholestan-3-one and coprostan-3-one have essentially the same reactivity. 6- and 7-Ketocholestane show "eclipsing" effects of neighboring hydrogen atoms. Δ4- and Δ5-Cholestenone are less reactive than cholestanone owing to the electronic effect of the double bond, but Δ7-, Δ8(9)-, Δ8(14)-, and Δl4-ergostenone are more reactive, the effect decreasing with the distance of the double bond from the 3-keto group.
THE DETERMINATION IN SITU OF THE CARBON CONTENT OF SOLID PRODUCTS IN REACTION VESSELS
Authors: Tickner A. W.
Published: May 2006

not available
ELECTROLYTIC CONDUCTANCE IN HYDROGEN PEROXIDE – WATER MIXTURES: PART II. SOME MONOBASIC AND DIBASIC ACIDS
Authors: Thomas D. K. , Maass O.
Published: May 2006

Measurements of the equivalent conductance of sulphuric, nitric, and hydrofluoric acids were made in water – hydrogen peroxide mixtures by means of a direct-current method. It was found that in solvents containing a high percentage of hydrogen peroxide the conductivities of these acids were extremely low, and it is proposed that this results from a marked decrease in their degrees of dissociation. This proposal is supported by similar measurements made on the system water – strong acid – weak acid.
SEVEN- AND EIGHT-MEMBERED RINGS CONTAINING CARBON AND TWO SULPHUR ATOMS
Authors: Kulka Marshall
Published: May 2006

7-Chloro-2,3-dihydrobenzo(f)-l,4-dithiepin (IV) has been synthesized from 2-(2-chloro-ethylmercapto)-5-chlorobenzyl chloride (I). Attempts to synthesize the higher homologues of IV by this method failed because the required intermediates cleaved at the alkyl–sulphur bond. A reaction product of p-chlorothiophenol, formaldehyde, and hydrogen chloride has been identified as 2,8-dichloro-6H,12H-dibenzo(b,f)-l,5-dithiocin (VI), a tricyclic system with the eight-membered ring containing two sulphur atoms.
SOME STRUCTURAL FEATURES OF DELCOSINE
Authors: Anet Ragini , Marion Léo
Published: May 2006

The alkaloid delcosine has previously been assigned tentatively the same carbon–nitrogen skeleton as lycoctonine to which it appears to be closely related in properties. Oxidation experiments now reported provide supporting evidence of the presence of two vicinal tertiary hydroxyl groups attached to a five- and a six-membered ring that are directly linked together at the two carbons carrying the hydroxyls. There is a methoxyl in a position β to the tertiary hydroxyl of the six-membered ring. Evidence is also provided as to the size of the heterocyclic ring and the presence of a methylene group next to the nitrogen.
NUCLEAR MAGNETIC RESONANCE MEASUREMENTS OF PROTON TRANSFERS IN ACETYLACETONE IN DIETHYLAMINE AND TRIETHYLAMINE
Authors: Reeves L. W. , Schneider W. G.
Published: May 2006

Solutions of acetylacetone in triethylamine are completely enolic at all dilutions studied (0.1 to 0.85 mole fraction). The nature of the proton resonance signals in the NMR spectrum indicates a proton exchange between the OH and ==CH— groups of the enol tautomer. Addition of diethylamine to acetylacetone results in the formation of a white crystalline 1:1 molecular complex which melts at 41.5 °C. The NMR spectrum of the complex reveals a simultaneous proton exchange between the amine NH group and the OH and ==CH— groups of the enol tautomer. The mechanism of this exchange is discussed. In effect the addition of amines to acetylacetone not only alters the keto–enol equilibrium very markedly, but also increases the keto–enol conversion rate. With diethylamine the conversion rate becomes sufficiently high to "average out" the individual NMR spectra of the two tautomers.
RADIOCHEMICAL EVIDENCE FOR HETEROGENEITY IN WHEAT STARCH
Authors: Perlin A. S.
Published: May 2006

Wheat starches labeled with carbon-14 have been fractionated by a novel leaching procedure to give amylose, amylopectin, and a highly-branched minor fraction designated "amylopectin C". Marked differences in the specific activity of the fractions are found. Subfractionation of amylopectin also gives products of varying specific activity. These findings provide radiochemical evidence for heterogeneity in wheat starch.
L'ARYLATION DES QUINONES PAR LES SELS DE DIAZONIUM : III. SUR LA SYNTHÈSE DES ARYL-CHLORO-p-BENZOQUINONES
Authors: Brassard P. , L'Écuyer P.
Published: May 2006

not available
SEPARATIONS OF THE PLATINUM METALS BY ION EXCHANGE
Authors: Berman S. S. , McBryde W. A. E.
Published: May 2006

Distribution coefficients for the chlorides of ruthenium, rhodium, palladium, iridium(III and IV), and platinum have been determined between the anion exchanger Amberlite IRA-400 and hydrochloric acid solutions of various molarities. Separations of various combinations of rhodium, iridium, palladium, and platinum in amounts of 0.5 mg. or less are described. When, in the course of these separations, the four metals are present together, special procedures are required to ensure complete recovery of platinum.
THE CHEMISTRY OF THE "AMINOCHROMES": PART I. THE PREPARATION AND PAPER CHROMATOGRAPHY OF PURE ADRENOCHROME
Authors: Heacock R. A. , Nerenberg C. , Payza A. N.
Published: May 2006

The preparation of adrenochrome in a pure stable crystalline form has been carried out by the silver oxide oxidation of adrenaline in methanol with the use of an anion-exchange resin (Dowex-1(Cl−)) to remove heavy metal ions from the reaction mixture prior to the isolation of the product. Its paper chromatographic behavior together with that of three derivatives (adrenolutin, adrenochrome monosemicarbazone, and adrenochrome monoisonicotinic acid hydrazide) in six different solvent systems has been examined. Water was found to be the best paper chromatographic solvent so far examined for this series of compounds.
A STUDY OF GRAFT COPOLYMERS: I. PREPARATION AND VISCOSITY BEHAVIOR
Authors: Manson J. A. , Cragg L. H.
Published: May 2006

Graft polymers were prepared by the redox polymerization of styrene in the presence of oxidized polystyrene or copolymers of styrene and 4-vinylcyclohexene-1; the maximum number of hydroperoxide groups per thousand monomeric units in the oxidized polymers was 18. Evidence that grafting had indeed occurred was obtained from measurements of monomer disappearance, of the decrease in hydroperoxide content of the backbone polymer during reaction, and of the infrared absorption by the polymer before and after the grafting procedure.Although the experimental results clearly support the conclusion that branching occurred, values of Huggins' k′ for both unfractionated and fractionated graft polymers were no higher than for linear polystyrene (0.39 < k′ < 0.41 in butanone). It was concluded that, though k′ is sensitive to bushy branching, Huggins' k′ is not measurably affected by the presence in a polymer of a few linear branches per molecule.
HYDROGEN PEROXIDE AND ITS ANALOGUES: VIII. EXCESS FUNCTIONS FOR THE BINARY SYSTEMS H2O–H2O2 AND D2O–D2O2
Authors: Giguère Paul A. , Knop Osvald , Falk Michael
Published: May 2006

Recent volumetric and calorimetric data have been used to calculate the excess functions for mixtures of water and hydrogen peroxide over the entire concentration range. The results are compared with those for the corresponding deuterium compounds. The existing calorimetric and vapor-pressure measurements are not comprehensive nor accurate enough to support discussion of the finer details of the excess quantities. A maximum in the excess-volume curves, presumably related to the formation of the compound H2O2.2H2O, persists in the liquid mixtures over an appreciable temperature range above the melting point of that compound. A possible crystal structure is proposed for the latter.New density determinations were carried out on mixtures of heavy water and deuterium peroxide at 0° and 20 °C. and the effect of deuterium peroxide on the temperature of maximum density of heavy water was measured and compared with that of deuterated alcohols. It is concluded that the structure of liquid water is easily penetrated by hydrogen peroxide molecules.
INFLUENCE OF CALCIUM IONS ON THE MYOSIN-CATALYZED HYDROLYSIS OF ADENOSINE TRIPHOSPHATE
Authors: Pelletier G. E. , Ouellet Ludovic
Published: May 2006

The activation of the myosin-catalyzed hydrolysis of adenosine triphosphate by calcium ions has been studied at pH 7.5 over a range of temperature extending from 3° to 25 °C. There is evidence that the activation is due to the equilibrium formation of a complex between adenosine triphosphate and calcium ions.From such a reaction mechanism, values of equilibrium constants are reported for the binding of adenosine triphosphate to the myosin in the presence and in the absence of calcium ions, together with stability constants for the calcium complexes of both the adenosine triphosphate and the myosin – adenosine triphosphate. The influence of hydrogen-ion concentrations on these constants is indicated.
CHEMICAL EFFECTS OF THE Br81(γ,α) As77 REACTION IN BROMIDES
Authors: Nelson D. H. , McCallum K. J.
Published: May 2006

An investigation has been made of the chemical forms of the arsenic produced when solid bromides, following irradiation with high-energy gamma rays, are dissolved in aqueous solution. The As77 is found to appear in both the pentavalent and the trivalent forms, the ratio AsV/AsIII increasing with an increase in the number of moles of water present in the hydrated solid. For the monohydrate of lithium bromide, the ratio depends upon the pH of the solution in which the solid is dissolved.
THE CONFIGURATION OF GLYCOSIDIC LINKAGES IN OLIGOSACCHARIDES: VI. DEGRADATION OF 4-O-METHYL-D-GLUCOPYRANURONOSYL-ALDOBIURONIC ACIDS TO 2-O-(4-O-METHYL-D-GLUCOPYRANOSYL)-GYCEROLS
Authors: Gorin P. A. J. , Perlin A. S.
Published: May 2006

The configurations of glycosidic linkages in 4-O-methyl-D-glucopyranuronosyl-aldobiuronic acids can be determined by conversion to the derived 2-O-D-glucopyranosyl-glycerol hexamethyl ether, which is compared, by its infrared spectrum and specific rotation, with the sirupy hexamethyl ethers synthesized from 2-O-α- and 2-O-β-D-glucopyranosyl-glycerol. Thus, the configuration of 2-O-(4-O-methyl-D-glucopyranuronosyl)-D-xylose was shown to be α, since it was degraded to 2-O-α-D-glucopyranosyl-glycerol hexamethyl ether. The configuration of 4-O-(4-O-methyl-D-glucopyranuronosyl)-D-galactose was correlated with that of the former aldobiuronic acid, since both gave crystalline 2-O-α-(4-O-methyl-D-glucopyranosyl)-glycerol penta-p-nitrobenzoate.
THE CONDUCTANCES OF AQUEOUS SOLUTIONS OF LITHIUM CHLORATE AT 25.00 °C. AND AT 131.8 °C.
Authors: Campbell A. N. , Paterson W. G.
Published: May 2006

The conductances, densities, and viscosities of aqueous solutions of lithium chlorate have been obtained over the complete range of concentration at 131.8 °C. and up to saturation (and somewhat beyond) at 25.00 °C. The curve of specific conductance versus concentration passes through a maximum which does not shift noticeably in composition with change in temperature. There are no minima on the curves of equivalent conductance versus concentration. The relative viscosity of the solutions decreases with rise in temperature; this is the reverse of the effect usually observed.The experimental results have been compared with the calculated results, obtained by the use of the equations of Wishaw and Stokes and of Falkenhagen.
CLASSICAL APPROACH TO THE STRUCTURE OF CONDENSED–RING AROMATIC COMPOUNDS—A REJOINDER TO THE PROBLEM OF DIBENZO(cd,mn)PYRENE
Authors: Singh Lakhbir
Published: May 2006

not available
THE KINETICS OF THE THERMAL DECOMPOSITION OF ETHYL BROMIDE AND ETHYL BROMIDE-d5
Authors: Blades Arthur T.
Published: May 2006

The kinetics of the pyrolysis of ethyl bromide and ethyl bromide-d5 have been studied using the toluene carrier gas technique. Variation of the pressure in the range 0.6 to 4.4 cm. Hg reveals what is believed to be a legitimate pressure effect on the first-order rate constants. The Arrhenius rate expressions determined at 4 cm. Hg pressure are: k(ethyl bromide) = 8.5 ± 1.6 × 1012e−52,200±300/RTsec−1 (T = 523°–633 °C);k(ethyl bromide-d5) = 2.1 ± 0.4 × 1013e−54,840±300/RT sec−1 (T = 531°–635 °C).The differences in the two rate expressions are discussed.
REACTIVITY STUDIES ON NATURAL PRODUCTS: V. RATES OF BOROHYDRIDE REDUCTION OF SOME RING A AND B STEROID KETONES
Authors: Wheeler Owen H. , Mateos José L.
Published: May 2006

The rates of reduction of 3-, 6-, and 7-cholestanone, coprostan-3-one, Δ4- and Δ5-cholesten-3-one, and Δ8(14)-ergosten-3-one with sodium borohydride in isopropanol have been measured. The proportions of α- and β-isomers formed were determined in most cases and the corresponding rates of equatorial and axial reduction obtained. Δ5-Cholesten-3-one and 6- and 7-cholestanone are reduced at a slower rate and Δ5-cholesten-3-one and Δ8(14)-ergosten-3-one at a higher rate than the saturated 3-ketosteroids.
THE EFFECT OF ADDITION OF POTASH TO NICKEL CHROMITE CATALYSTS
Authors: Rowlinson H. C.
Published: May 2006

Experiments are described on the dehydrogenation of butene-1 in the presence of steam, over three nickel chromite catalysts. These are: (a) pure nickel chromite, (b) nickel chromite pellets impregnated with potash from solution, and (c) a catalyst with potash added before the nickel oxide and chromium sesquioxide are combined. The oxidation state of the catalyst largely affects the products, for overreduction causes disruption of the hydrocarbons. The effect of the potash is to prevent this overreduction and thus to improve selectivity to butadiene. There is a difference between the behavior of catalysts with surface potash (type b) and those where the potash is distributed through the mass (type c). This difference is explained by the formation of large pores on reduction of type (c) catalysts.
THE SYSTEM KOH–K2CO3–H2O AT LOW TEMPERATURES: I. PHASE EQUILIBRIA
Authors: Lang A. A. , Sukava A. J.
Published: May 2006

Phase diagrams for the system KOH–K2CO3–H2O were determined for 25°, 10°, 0°, −10°, −20°, −40°, and −60°. The stable hydrates of potassium hydroxide were the di- and tetra-hydrates; those of potassium carbonate were the sesqui- and hexa-hydrates. No compound formation between KOH and K2CO3 was detected.
KINETIC LAWS FOR SURFACE REACTIONS IN FLOW SYSTEMS
Authors: Laidler K. J.
Published: May 2006

A general differential equation is set up for the flow of reactant gases through a catalytic reactor, account being taken of changes in volume as the reaction proceeds and of the possibility that the catalyst surface is not completely available. Integrated solutions are given for three special cases and are presented in graphical form: (1) first-order reaction, the result being applicable whether the surface is completely available or not (Fig. 1); (2) second-order reaction with the surface completely available (Fig. 2); (3) second-order reaction with only a small fraction of the surface available (Fig. 3). The treatment is related to previous treatments of Hulburt, Thiele, and Wheeler.
THE STRUCTURES OF α- AND β-PARACHLORAL
Authors: Novak A. , Whalley E.
Published: May 2006

The infrared and proton magnetic resonance spectra of α- and β-parachloral have been investigated and the dipole moment of α-parachloral has been determined. The results show that both isomers have the chair configuration of the ring and that α-parachloral has symmetry CS, with one axial and two equatorial CCl3 groups and that β-parachloral has symmetry C3v with three equatorial CCl3 groups.
GASEOUS AND LIQUID STATES OF AGGREGATION IN THE SUPERCRITICAL REGION
Authors: Smith F. G.
Published: May 2006

not available
ULTRASONIC ABSORPTION IN BUTYRIC ACID
Authors: White P. , Benson G. C.
Published: May 2006

Ultrasonic absorption has been measured in pure butyric acid by a pulse technique from 0 ° to 40 °C. and values of the relaxation frequency obtained. The activation energy of the relaxation process is shown to be 1.1 kcal./mole. These results are compared with published values for acetic and propionic acids and possible relaxation processes are discussed.
A SPECTROPHOTOMETRIC DETERMINATION OF RHODIUM WITH TIN (II) BROMIDE
Authors: Berman S. S. , Ironside R.
Published: May 2006

Rhodium salts react with a solution of tin (II) bromide in hydrobromic acid to produce an intense yellow color suitable for a spectrophotometric determination of rhodium. The method described is relatively simple and is the most sensitive for this metal published to date. Several factors influencing the intensity and stability of the colored species, whose nature is unknown, are described. Since the other platinum metals and base metals interfere it is necessary to isolate the rhodium prior to its determination. However, a fair estimation of rhodium can be made even when equivalent quantities of iridium are present. The procedure may be adapted, with a small loss in sensitivity, to determine rhodium in solutions which have been fumed with sulphuric acid.
THE REACTIONS OF DIMETHYL- AND TRIMETHYL-AMINES WITH ATOMIC HYDROGEN
Authors: George Z. M. , Wright A. N. , Winkler C. A.
Published: May 2006

The reactions of hydrogen atoms with dimethyl- and trimethyl-amines produced mainly methane, together with relatively large quantities of ethane and small amounts of hydrogen cyanide. Dimethylamine was also a product of the trimethylamine reaction.
HYDROGEN BONDING IN THE AMINE HYDROHALIDES: I. GENERAL ASPECTS
Authors: Chenon Bernadette , Sandorfy C.
Published: May 2006

The infrared spectra of 17 amine hydrohalides have been measured in the solid state, in aqueous solutions, and in their conjugate amine. Their NH+ stretching and scissoring bands are discussed.The stretching bands of hydrogen-bonded aliphatic and aromatic amine hydrohalides fall into the same part of the spectrum. In the solid state, the hydrogen bonds are of type [Formula: see text] The aliphatic amine salts usually exhibit many sharp bands, while the aromatic amine salts have broad but composite bands. Tertiary amine salts show a hypsochromic shift in the order hydrochloride, hydrobromide, hydriodide; primary and secondary aliphatic amine salts show a slight bathochromic shift in the same order. Primary and secondary aromatic amine salts behave less regularly, although in most cases the shift is hypsochromic. These facts can be explained qualitatively by considering the charge distribution in the ionized amino groups and the contribution of electrostatic and delocalization effects to the energy of the hydrogen bonds.The anharmonicity of the potential surface which causes the appearance of strong combination bands may lead to the broadening of bands or to many sharp bands. There is no parallelism in this latter case between shift and broadening of the bands.The assignment of a strong band which appears in many cases near 2000 cm−1 is discussed.The above-mentioned characteristic band shifting is absent in the spectra of aqueous solutions and it is concluded that in this case hydrogen bonding is not of the [Formula: see text] but of the [Formula: see text] type.
PEROXIDES IN THE COMBUSTION OF ISOBUTANE
Authors: Taylor G. W.
Published: May 2006

A survey has been made of the nature of the peroxides occurring in the combustion of isobutane below and above the lower cool-flame limit. The peroxides were resolved and partially identified by paper chromatography. Below the cool-flame limit, the peroxide is found to be mostly tert-butyl hydroperoxide, with some hydrogen peroxide, but as the cool-flame limit is approached the proportion of tert-butyl hydroperoxide declines, while that of hydrogen peroxide increases. In addition, peroxides identified as aldehyde and acid peroxides increase as the cool-flame limit is approached. No tert-butyl hydroperoxide appears to survive the cool flame, although copious quantities of aldehyde peroxide and hydrogen peroxide remain.
REACTIONS OF ALKOXY RADICALS: V. PHOTOLYSIS OF DI-t-BUTYL PEROXIDE
Authors: McMillan Garnett , Wijnen M. H. J.
Published: May 2006

The photolysis of di-t-butyl peroxide has been investigated over the temperature range 25 ° to 79 °C. As reaction products were observed: acetone, t-butyl alcohol, methyl t-butyl ether, i-butylene oxide, ethane, methane, and carbon monoxide. The following reactions, involving the t-butoxy radical, have been studied:[Formula: see text]An activation energy difference of E2 − E6 = 3 kcal has been obtained.
THE REACTION OF CYANOGEN BROMIDE WITH THE SODIUM SALTS OF CARBOXYLIC ACIDS: II. THE REACTION OF CYANOGEN BROMIDE WITH THE SODIUM SALTS OF ALIPHATIC ACIDS
Authors: Douglas D. E. , Burditt Anna Mary
Published: May 2006

Cyanogen bromide reacts with the sodium salts of lower aliphatic acids at 250-300 °C to form an α-keto isocyanate as the primary product. The latter undergoes subsequent pyrolytic decomposition to a nitrile and carbon dioxide. A mechanism is proposed to account for the observed interchange of labelled carbon atoms between the CN group of the cyanogen bromide and the carboxyl group of the salt in the over-all reaction.
STUDIES ON THE MECHANISMS OF CYCLIZATION OF RING A OF STEROIDS DURING THE REFORMATSKY REACTION
Authors: Heard R. D. H. , Balla G. A. , Jamieson J. R. , Ziegler P.
Published: May 2006

The Reformatsky reaction of 3,5-seco-5-ketocholestan-3-oic acid methyl ester with methyl bromoacetate yielded 2-carbohydroxycholestenone, cholestenone, and 4-carbomethoxycholestenone. The appearance of these products indicated that cyclization of ring A proceeded along two different paths; this conclusion was confirmed by the use of methyl bromoacetate-1-C14 and -2-C14.
A STUDY OF SILVER NITRATE SOLUTIONS IN GAS CHROMATOGRAPHY
Authors: Bednas M. E. , Russell D. S.
Published: May 2006

Silver nitrate, dissolved in some organic solvents, has formed a relatively specific medium for the gas chromatographic separation of olefins. Columns formed from ethylene glycol and glycerin solutions of silver nitrate are comparable, but those formed from the polyethylene glycol solutions are considerably less effective. These silver nitrate solutions were stable below 65 °C, but began to decompose slowly at 85 °C.
DIACETYLENE: PREPARATION, PURIFICATION, AND ULTRAVIOLET SPECTRUM
Authors: Georgieff K. K. , Richard Y.
Published: May 2006

Diacetylene was prepared by the reaction of 1,4-dichloro-2-butyne with sodium hydroxide. Three modifications of procedure were tried to determine which gave the highest yield and purest product. Evidence that the by-product is 2-chloro-2-butene-3-yne is presented. Several methods for purifying the diacetylene were investigated. The ultraviolet spectrum with molar extinction coefficients is given.
MICROCALORIMETRIC AND KINETIC STUDIES OF THE α-CHYMOTRYPSIN – HYDROCINNAMIC ESTER – HYDROCINNAMIC ACID SYSTEM
Authors: Canady William J. , Laidler Keith J.
Published: May 2006

Using a microcalorimeter of the Tian–Calvet type the heat of binding of hydrocinnamic acid to a-chymotrypsin has been measured in aqueous solution over a range of pH values. The heat evolved was found to vary from about 5 to about 28 kcal per mole as the pH was varied from 5.1 to 7.8. In order to see whether these heats are due to the binding of the inhibitor at the active center of the enzyme, heats were also measured at pH 7.1 by a kinetic method, the inhibitor constant being determined over a range of temperatures; the heat calculated in this way was consistent with the microcalorimetric value. The kinetic work also gave rise to entropies of binding of the inhibitor and the substrate (methyl hydrocinnamate); these entropies are negative, the significance of which is discussed in terms of the mode of binding. It is suggested that the results are best explained on the hypothesis that the active center of the enzyme contains, in addition to the ordinary acidic and basic sites, a negatively charged group that interacts electrostatically with the anion of hydrocinnamic acid.
POLYOXYETHYLENEGLYCOL ETHERS. PART II
Authors: Gingras B. A. , Bayley C. H.
Published: May 2006

not available
THE ULTRAVIOLET AND INFRARED SPECTRA OF VICINAL-TRIAZOLE DERIVATIVES
Authors: Lieber E. , Rao C. N. R. , Chao T. S. , Rubinstein H.
Published: May 2006

not available
FUSED HETEROCYCLICS PART II. SYNTHESIS OF QUINOLINO-(2:3:3′:2′)-QUINOLINE: AN ISOMER OF CALYCANINE
Authors: Anet Ragini
Published: May 2006

The constitution of calycanine, a dehydrogenation product of the alkaloid calycanthine, is discussed. Calycanine dipicrate has been prepared, and, on the basis of its analysis and the infrared spectrum of calycanine, a quinolinoquinoline structure has been put forward for calycanine. The synthesis of quinolino-(2:3:3′:2′)-quinoline is described.
ELECTROLYSIS OF LITHIUM HYDRIDE
Authors: Weinberger M. A. , Mousseau T. J. , Maass O.
Published: May 2006

A method has been developed whereby current yields of as high as 70% of anodically discharged hydrogen can be maintained during continuous electrolysis of lithium hydride at or just below its melting point. Efforts to utilize this process for the separation of hydrogen and deuterium were unsuccessful.
THE DETERMINATION OF UO3 AND U3O8 IN BROWN OXIDE
Authors: Stonhill L. G.
Published: May 2006

Investigations leading to a method for the analysis of mixtures of the oxides UO3, U3O8, and UO2 are described.Uranic oxide is extracted with hot ammonium citrate solution, uranic and uranous-uranic oxides are determined together by solution in phosphoric acid followed by titration of U(VI) with titanous sulphate, and uranous oxide found by difference.
THE GAS PHASE REACTIONS OF PERFLUORO-n-PROPYL RADICALS WITH METHANE AND ETHANE
Authors: Giacometti G. , Steacie E. W. R.
Published: May 2006

The rate constants and activation energies for the reactions of C3F7 radicals with methane and ethane have been measured by photolyzing mixtures of C3F7COC3F7 and hydrocarbon with 3130 Å light. Photolysis of mixtures of the ketone, methane, and deuterium has been used to check previous measurements on the reaction of C3F7 and deuterium.
UNSYMMETRICALLY SUBSTITUTED 3,3′-METHYLENE BRIDGED 2,2′-DIHYDROXYCHROMONES
Authors: Abramovitch R. A. , Gear J. R.
Published: May 2006

Unsymmetrically substituted dicoumarol derivatives have been synthesized by taking advantage of the fact that 4-hydroxycoumarins will undergo the Mannich reaction at C3 and also take part in Michael-type addition reactions. In the presence of methyl iodide, 4-hydroxy-3-N-piperidinomethylcoumarin and 4-hydroxycoumarin gave dicoumarol. By using monosubstituted 4-hydroxycoumarins a variety of unsymmetrically substituted dicoumarols have been prepared in good yield. The infrared spectra of some of the intermediates and products are reported and discussed.
THE KINETICS OF RADICAL REACTIONS IN THE TRACKS OF FAST ELECTRONS. A DETAILED STUDY OF THE SAMUEL–MAGEE MODEL FOR THE RADIATION CHEMISTRY OF WATER
Authors: Dyne P. J. , Kennedy J. M.
Published: May 2006

The kinetic behavior of a γ-ray spur produced in water, having H and OH radicals distributed spatially in the manner suggested by Samuel and Magee, has been studied using an electronic computer. The variation in yield of the molecular products H2, H2O2, and H2O with rate constants, diffusion constants, and spur size has been obtained. The model gives agreement with experiment choosing spurs with a small "radius" of the order of 10 Å. On simple assumptions, however, the model predicts no difference in the molecular yields between heavy and light water and no isotopic separation in the formation of molecular hydrogen from isotopically enriched light water. Various special assumptions needed to give agreement with experiment for these isotope effects are discussed. The observed isotopic separation in the formation of molecular hydrogen is attributed to the preferential dissociation of an H atom from an excited HDO molecule. It is found that the yield of molecular hydrogen is less sensitive to the presence of scavengers than the yield of hydrogen peroxide.
FATTY ACIDS OF THE SEED OIL OF CARDIOSPERMUM HALICACABUM
Authors: Chisholm Mary J. , Hopkins C. Y.
Published: May 2006

The seed oil of Cardiospermumhalicacabum L., family Sapindaceae, was found to have 11-eicosenoic acid as the major fatty acid in its glycerides. In this respect it is unique among the true natural fats. The amount of eicosenoic acid in the sample examined was 42% of the total long-chain fatty acids. The identity and amounts of the principal fatty acids of the oil were determined by gas chromatography and by distillation of the methyl esters. The estimated percentages were: palmitic 3, linolenic 8, linoleic 8, oleic 22, stearic 2, eicosenoic 42, arachidic 10. In addition, there was evidence of small proportions (1–2%) of a low-molecular-weight acid and of C22 acids.
GUANIDINE COMPOUNDS. II. PREPARATION OF MONO- AND N,N-DI-ALKYLGUANIDINES
Authors: Bannard R. A. B. , Casselman A. A. , Cockburn W. F. , Brown G. M.
Published: May 2006

1-Guanyl-3,5-dimethylpyrazole nitrate is superior to S-methylisothiouronium sulphate as a reagent for preparation of simple salts of mono- and N,N-di-alkylguanidines from cyclohexylamine, trans-2-aminocyclohexanol, pyrrolidine, and piperidine. S-Methylisothiouronium sulphate, however, gave a higher conversion in the case of dimethylamine. Cyanamide is not as useful a guanylating agent as those mentioned above. The paper chromatography of the mono- and N,N-di-alkylguanidines and the parent amines was studied using four solvent systems.
THE CHEMISTRY OF THE "AMINOCHROMES": PART II. THE PREPARATION, PAPER CHROMATOGRAPHY, AND SPECTROSCOPIC PROPERTIES OF PURE ADRENOLUTIN; THE INFRARED SPECTRUM OF ADRENOCHROME
Authors: Heacock R. A. , Mahon M. E.
Published: May 2006

The preparation of adrenolutin monohydrate in pure crystalline form has been carried out by the alkaline rearrangement of aqueous solutions of adrenochrome, prepared from the silver oxide oxidation of adrenaline in aqueous solution. An anion-exchange resin (Dowex-1 (Cl−)) was employed to remove inorganic contaminants from the reaction mixture prior to treatment with alkali. The pure anhydrous material has been prepared by the high vacuum sublimation of the monohydrate. The paper chromatographic, spectroscopic, and fluorimetric characteristics of adrenolutin have been investigated. On the basis of the infrared spectrum it is suggested that in the solid state, adrenolutin exists in the keto form, i.e. 2,3-dihydro-5,6-dihydroxy-N-methyl-3-ketoindole. The infrared spectrum of adrenochrome, in the solid state, agrees with the zwitterionic formulation suggested for this compound.
LIGHT-SCATTERING STUDIES ON ALUMINUM DISTEARATE
Authors: Leger A. E. , Hyde J. C. , Sheffer H.
Published: May 2006

A light-scattering study of aluminum distearate in dilute benzene solution suggests that it is a linear molecule of random coil shape. This is further substantiated by intrinsic viscosity – molecular weight data, the constancy of the ratio of the molecular weight to the square of the radius of gyration (Rg), the value of Φ in Flory's intrinsic viscosity – molecular weight relationship, and the close agreement between the theoretical and experimental results found for the unit length of the polymer chain. This average unit length has been calculated to be 4.46 Å.
RESONANCE PARAMETERS FROM REACTIVITY CONSTANTS
Authors: Rao C. N. Ramachandra , Goldman G. K.
Published: May 2006

not available
SUR LA SYNTHÈSE DE FORMYLDIPHÉNYL ÉTHERS POLYSUBSTITUÉS
Authors: Constantin R. , L'Écuyer P.
Published: May 2006

Bon nombre de formyldiphényl éthers ont été synthétisés en faisant réagir certains phénols avec la 2-chloro-5-nitrobenzaldéhyde ou la 3-nitro-4-chlorobenzaldéhyde. Plusieurs l'ont été en condensant le tosylate de la 5-nitrovanilline ou de la 4-hydroxy-3-nitrobenzaldéhyde avec divers phénols. Ces derniers ne donnent pas d'éthers avec la 2-chloro-5-nitrobenzaldéhyde; mais, cependant, les phénolates alcalins réagissent avec cette aldéhyde en solution alcoolique diluée. Par une série de réactions, les 2,2'-diméthoxy-4,4'-diformyl-6-nitro-, 2,2'-diméthoxy-4,4'-diformyl-, 2,2'-diméthoxy- 4,4'-bis-(β-carboxyvinyl)- et 2,2'-diméthoxy-4,4'-bis-(β-carboxyéthyl)-diphényl éthers ont été prepares.
ON THE SPECTRAL RESPONSE OF PHOTOCONDUCTION IN THIN SINGLE CRYSTALS OF ANTHRACENE
Authors: Ferguson J. , Schneider W. G.
Published: May 2006

The photoconduction of thin crystals of anthracene (sublimation flakes) has been studied as a function of the wavelength of the incident light as well as the geometry of the "surface cell" arrangement. With spot electrodes on one face of the crystal, the spectral response showed a very pronounced difference depending on whether the electrode face or the opposite face was illuminated. In the latter case the spectral response followed the absorption curve of the crystal, whereas when the electrode face was illuminated the photoconductivity was a minimum at wavelengths corresponding to maximum extinction coefficients of the crystal.
INFRARED SPECTRA AND STRUCTURE OF SELENIOUS ACID
Authors: Falk Michael , Giguère Paul A.
Published: May 2006

The infrared spectra of selenious acid both crystalline and in solution in water and methanol were recorded from 2 to 30 μ. Assignment of the various frequencies is made on the basis of the crystal structure as determined from X-ray data. It is shown that the molecules have the symmetrical form (a), the asymmetrical one (b) proposed by Venkateswaran being[Formula: see text]ruled out. The spectra of solutions in H2O and D2O confirm the existence of discrete H2SeO3 and D2SeO3 molecules with no indication of uncombined SeO2 molecules even at high concentrations. This behavior is contrasted with that of SO2 solutions.
THE STRUCTURE OF PYRROLE SALTS AND THE BASIC STRENGTHS OF SOME SIMPLE PYRROLES
Authors: Bullock E.
Published: May 2006

The infrared spectra of hydrohalide salts of some substituted pyrroles are typical of secondary amine salts. Unlike the free base, cryptopyrrole hydrochloride is easily hydrogenated. The basic strengths of cryptopyrrole and 2,4-dimethylpyrrole are calculated from ultraviolet spectroscopic data.
FISSION OF EXCITED HEAVY NUCLEI
Authors: Pate B. D.
Published: May 2006

The results of published calculations on the prompt nuclear cascade and nuclear evaporation processes are combined with some assumptions regarding the nuclear fission process and fission widths to calculate the average neutron-to-proton ratios of fission products from Th + 8-Mev protons, Th + 87-Mev protons, and U + 450-Mev protons. Comparison of the results with experimental data indicates that the fission charge distribution mode characterized by the equal charge displacement hypothesis, hitherto considered a low energy phenomenon, persists in uranium and thorium up to the highest energy studied. There is also some evidence that fission occurs in excited heavy nuclei before complete de-excitation by particle emission, in agreement with other experimental work.
THE PREPARATION OF SOME DERIVATIVES OF D-RIBONO-1→4-LACTONE AND D-RIBITOL
Authors: Hough L. , Jones J. K. N. , Mitchell D. L.
Published: May 2006

Reaction of D-ribono-1→4-lactone with acetone gave the 2,3-O-isopropylidene derivative from which 5-O-methyl-D-ribitol, 5-deoxy-D-ribitol, and 2,3-O-isopropyIidene-D-ribitol were prepared.
THE REACTION OF 2,2-DIPHENYL-1-PICRYLHYDRAZYL WITH SECONDARY AMINES
Authors: Hazell J. E. , Russell K. E.
Published: May 2006

The reaction of DPPH (2,2-diphenyl-1-picrylhydrazyl) with N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, diphenylamine, and methylaniline has been studied and has been shown to be primarily a hydrogen abstraction process. Two moles DPPH react with 1–1.15 moles secondary amine to give 1.7–1.8 moles 2,2-diphenyl-1-picrylhydrazine and further products.The reaction between DPPH and N-phenyl-1-naphthylamine is first order with respect to each reactant. The reaction of DPPH with the other amines is retarded by the major product 2,2-diphenyl-1-picrylhydrazine and the kinetics of the over-all reaction are complex. However second-order rate constants and activation energies have been obtained using initial rates of reaction. Possible reaction mechanisms are discussed.
NOTE ON THE INDUCTIVE AND MESOMERIC EFFECTS IN SUBSTITUTED BENZENE DERIVATIVES
Authors: Sandorfy C.
Published: May 2006

not available
AN INFRARED CELL FOR SMALL GAS SAMPLES
Authors: Russell D. S.
Published: May 2006

not available
ORGANIC DEUTERIUM COMPOUNDS: XXI. SYNTHESIS OF DEUTERATED AZOBISMETHANE
Authors: Morse A. T. , Massiah T. F. , Leitch L. C.
Published: May 2006

Deuterated azobismethane was synthesized in the conventional way from dimethyl sulphate and hydrazine.
A NOTE ON THE ELECTRICAL CONDUCTANCES OF DIELECTRIC FLUIDS IN ULTRASONIC FIELDS
Authors: Berkowitz N.
Published: May 2006

The electrical conductances of ethyl bromide, n-propyl bromide, n-butyl bromide, methanol, and ethanol in ultrasonic fields have been measured at frequencies between 250 kc/s and 2 Mc/s and intensities between 0.7 and 24 w/cm2. Measurements were made at room temperature, using a simple d-c. technique. It is shown that a simple transient increase in conductance, such as has previously been observed by Seidl, may be confined to unassociated fluids and that it can occasionally give way to a much more complex—and not as yet fully understood—behavior pattern.
URONIC ACIDS FROM WHITE SPRUCE (PICEA GLAUCA (MOENCH) VOSS)
Authors: Adams G. A.
Published: May 2006

Acid hydrolysis of extractive-free white spruce wood produced a number of neutral and acidic sugars and oligosaccharides. The acidic components were isolated and three of these were shown to be 4-O-methyl-D-glucuronic acid, 2-O-(4-O-methyl-α-D-glucopyranosyluronic acid)-D-xylose, and tentatively O-(4-O-methyl-α-D-glucopyranosyluronic acid)-(1→ 2)-O-β-D-xylopyranosyl-(1→ 4)-D-xylopyranose.
PHOTOCHEMICAL SEPARATION OF MERCURY ISOTOPES: II. THE REACTION OF Hg2026(3P1) ATOMS, PHOTOEXCITED IN NATURAL MERCURY VAPOR, WITH WATER VAPOR AND OTHER HgO-FORMING SUBSTRATES
Authors: Pertel R. , Gunning H. E.
Published: May 2006

An investigation has been made of the reaction of Hg202(3P1) atoms, photoexcited in natural mercury vapor, with several HgO-forming substrates, including water vapor, nitrous oxide, and oxygen. The reactions were carried out under flow conditions at room temperature. Emphasis has been placed on the Hg202 content of the HgO product. Enrichment in Hg202 would be evidence of the primary formation of a mercury compound.In the reactions with nitrous oxide and oxygen, it was found that the HgO product contained the normal abundance of Hg202. With water vapor, a product containing up to 35% Hg202 was obtained, compared to the normal abundance of 29.8%. The addition of 1,3-butadiene to the water vapor substrate was found to have a marked effect on the enrichment in Hg202 in the HgO product. A product containing 85% Hg202 was recovered when the substrate contained 21 mole % of added butadiene. A systematic study of the effect of butadiene concentration on the enrichment reaction showed that the Hg202 content remains constant for butadiene concentrations exceeding approximately 10 mole %. The water–butadiene reaction is recommended as a simple method for preparing Hg202 from natural mercury.The factors influencing the enrichment process are discussed, together with the significance of the results with respect to the mechanisms of decomposition of the molecules studied.
FORMATION OF AN ORGANOCHROMIUM COMPOUND IN THE REDUCTION OF CHLOROFORM BY CHROMOUS PERCHLORATE
Authors: Anet F. A. L.
Published: May 2006

The reduction of chloroform by chromous perchlorate in aqueous solution gave chloropentaaquochromium(III) perchlorate and dichloromethylpentaaquochromium(III) perchlorate in equimolecular amounts.
RADIOLYSIS OF TETRACHLOROETHYLENE
Authors: Sutherland J. W. , Spinks J. W. T.
Published: May 2006

When tetrachloroethylene is irradiated with Co60 gamma rays in the presence of oxygen or air, the main products are trichloroacetyl chloride, phosgene, and oxalyl chloride. The reaction is a chain reaction. Possible reaction mechanisms are discussed.
ISOMERIC 5-(SUBSTITUTED)AMINOTHIATRIAZOLE AND 1-SUBSTITUTED-TETRAZOLINETHIONES
Authors: Lieber Eugene , Ramachandran J.
Published: May 2006

The reaction of organic isothiocyanates with sodium azide in ethanol and water has been investigated. Water is shown to be the more advantageous solvent for this reaction giving higher yields and initially purer 1-substituted-tetrazoline-5-thiones. A series of these latter compounds was made by this procedure. The yield of product appears to be dependent on the electrical properties of the substituent of the isothiocyanate, the yields decreasing as the electron-donating properties increase. A series of new 4-substituted-thiosemicarbazides has been prepared and converted by diazotization to the corresponding 5-(substituted)aminothiatriazoles. A theory to account for the differences in the mode of reaction of hydrazoic acid and azide ion is presented and discussed. The basic conversion of 5-(substituted)aminothiatriazoles to 1-substituted-tetrazolinethiones may involve a simple dearrangement–rearrangement mechanism complicated by side reactions. A summary of known isomeric 5-(substituted)aminothiatriazoles and 1-substituted-tetrazolinethiones is presented.
SYNTHESIS OF ALKYL 1-PHENYL-5-CHLORO-1,2,3-TRIAZOLE-4-CARBOXYLATE
Authors: Lieber Eugene , Chao T. S. , Rao C. N. R.
Published: May 2006

not available
Symposium on Charge Transfer Processes: A REPORT ON A SYMPOSIUM HELD BY THE PHYSICAL CHEMISTRY DIVISION OF THE CHEMICAL INSTITUTE OF CANADA
Authors: Conway B. E.
Published: May 2006

not available
ON THE EQUIVALENT REDOX POTENTIAL OF AQUEOUS SOLUTIONS UNDER IONIZING RADIATION
Authors: Henderson I. H. S. , Lovering E. G. , Haines R. L. , Casey E. J.
Published: May 2006

A study of the electrochemical behavior of aqueous solutions irradiated by Co60γ- and 50–300-kv X-rays is being carried out. Results are presented which show that aqueous solutions of various electrolytes over a pH range of 0.0 to 14.0 attain a steady-state potential under irradiation.This steady-state potential, whose existence was postulated by Dainton and Collinson (who called it the equivalent redox potential), has been determined to be −0.85 v with respect to a hydrogen electrode in the same solution. This value is a property of water and is independent of pH, solute, temperature and radiation energy, and intensity within the ranges investigated.Electrodes under irradiation sometimes show potentials different from the potential of the bulk electrolyte. This is considered to be a result of selective adsorption of one or more primary or secondary radiation products. These transient phenomena depend upon source intensity and solute concentration and disappear when irradiation is stopped.