bluuebunny/crossref_metadata_2025 huggingface dataset:
DISINTEGRATION-RATE DETERMINATION BY 4π-COUNTING: PART I
Authors: Pate B. D. , Yaffe L.
Published: May 2006

The response probability of a 4π-counter has been examined and conditions determined for which the response probability is unity to within ± 0.1% for a range of nuclides. Variables examined have been the effect of polarization potential, discriminator bias, source location, counting rate, counter gas purity, thickness of conductor on source mount, for particles of various energies and from various modes of disintegration.
THE REACTION OF METHYL RADICALS WITH ACETALDEHYDE
Authors: Dodd R. E.
Published: May 2006

The rates of formation of methane and ethane in the photodecomposition of acetaldehyde have been measured between 391 and 564 °K. The rate constant for the reaction[Formula: see text]was found to be[Formula: see text]
THE VAPOR PHASE PHOTOLYSIS OF HEXAFLUOROACETONE IN THE PRESENCE OF METHANE AND ETHANE
Authors: Ayscough P. B. , Polanyi J. C. , Steacie E. W. R.
Published: May 2006

The photolytic decomposition of hexafluoroacetone by light of wavelength 3130 Å has been used to produce trifluoromethyl radicals for a study of their reactions with methane and ethane. It has been shown that these radicals abstract hydrogen with greater facility than do methyl radicals. The activation energies for the two reactions[Formula: see text]and[Formula: see text]are found to be 10.3 ± 0.5 kcal./mole and 7.5 ±0.5 kcal./mole respectively, if one can assume zero activation energy for the recombination of trifluoromethyl radicals.
PARTICLE MOTIONS IN SHEARED SUSPENSIONS III.: FURTHER OBSERVATIONS ON COLLISIONS OF SPHERES
Authors: Manley R. St. J. , Mason S. G.
Published: May 2006

Two-body interactions between glass spheres of diameters a1 and a2 caused by velocity gradients vary with a1/a2. When 1 < a1/a2 < 2, well-defined collisions similar to those previously reported for spheres of equal size can be observed. Fair agreement is found between the experimentally observed and calculated collision frequencies over a range of particle concentrations and velocity gradients. When a1/a2 > 2 the particles are separated at all times and the phenomena of interaction are more complex. Single air bubbles rotate at the same angular velocity as rigid spheres. When two air bubbles of equal size are brought into collision a doublet is formed; instead of the mirror-image separation observed with neutral rigid spheres, the doublet continues to rotate for as many as 60 rotations before coalescence occurs. Less frequently a doublet with distinct particle separation is observed. Periods of rotation of both types of doublet and certain details of the rotational orbit of a doublet of touching air bubbles have been measured and compared with values predicted from Jeffery's theoretical equations for rigid ellipsoids. Apart from their intrinsic interest, the phenomena described are of importance in theories of viscosity and coagulation of suspensions and colloidal dispersions.
THE RECIPROCAL SALT-PAIR SYSTEM: SODIUM CHLORIDE – AMMONIUM SULPHITE – SODIUM SULPHITE – AMMONIUM CHLORIDE – WATER AT 20 °C. AND 60 °C.: PART II: THE QUATERNARY SYSTEM
Authors: Labash J. A. , Lusby G. R.
Published: May 2006

In the above quaternary system at 60 °C., besides those representing the four salts at the corners of the Janecke diagram two other saturation areas were found. At 20 °C. there are three, and possibly more than three additional areas. In the course of the present work it was not possible to establish the nature of the solid phases in these additional areas of the quaternary system. However, the data of Lewis and Rivett suggest that at least some of these unknown areas may indicate the presence of different solid solutions of sodium sulphate in sodium sulphite. This quaternary system appears to be a rather complex one and much further work remains to be done in order to complete the knowledge of it at 60 °C. and 20 °C., particularly at the latter temperature.
CATALYSIS ON FILMS OF ARSENIC, ANTIMONY, AND GERMANIUM
Authors: Taylor Sir Hugh
Published: May 2006

Arsenic, antimony, and germanium films laid down on glass surfaces by decomposition of the hydrides have been studied from the standpoint of reaction kinetics in three sets of reactions: the decomposition of hydrides and deuterides, the interaction of hydrides and molecular deuterium, and the exchange reaction of hydrogen and deuterium. Only in the first of these have the surfaces marked catalytic activity. The orders of reaction and the activation energies have been determined. The accelerated catalytic influence of foreign elements, notably antimony in arsine decomposition, has been established. The results obtained contrast strikingly with the properties of clean filaments and evaporated films among the transition elements. The results emphasize the basic importance of chemical factors and de-emphasize the importance of surface cleanliness as a controlling factor in problems of chemisorption and surface catalysis.
STUDIES ON CARRAGEENIN: THE EFFECT OF SHEAR RATE ON VISCOSITY
Authors: Masson C. R. , Goring D. A. I.
Published: May 2006

The viscosity of aqueous solutions of carrageenin of high molecular weight was markedly dependent on the rate of shear. The shear-dependence increased with decrease in the concentration of added electrolyte. Because of curvature, extrapolation of [η] to zero rate of shear was not possible. The Huggins interaction coefficient, k′, increased with decrease in rate of shear; k′ also increased with increase in concentration of added electrolyte. In water, maxima of ηsp/c were observed at concentrations of carrageenin equivalent to the ionic impurities in the distilled water used. At higher concentrations the data fitted the Fuoss equation at rates of shear of 200 and 100 sec.−1 but not below 100 sec.−1 The constants A and D both increased with decrease in rate of shear.
DISINTEGRATION-RATE DETERMINATION BY 4π-COUNTING: PART II. SOURCE-MOUNT ABSORPTION CORRECTION
Authors: Pate B. D. , Yaffe L.
Published: May 2006

The various methods in use for determining the correction for absorption due to the source mount used in a 4π-counter are discussed, and experiments conducted to test the validity of the correction, arising from these methods, for β emitters of varying end-point energies. The methods all give erroneous corrections for low energy β emitters and possible reasons for the errors introduced by the 'sandwich method' are discussed. An 'absorption curve' type method is proposed which is shown to give more accurate correction factors.
MICROCALORIMETRIC DETERMINATION OF THE CRITICAL CONCENTRATION AND THE MOLECULAR DIMENSIONS OF POLYVINYL ACETATE IN SOLUTION
Authors: Parent Michel , Rinfret Marcel
Published: May 2006

Heats of mixing of polyvinyl acetate fractions with s-tetrachloroethane and methanol have been determined for the low concentration region. At the lowest concentrations the graphs of ΔH vs. volume fraction are linear as predicted by the van Laar, Scatchard, and Hildebrand theory. As the concentration increases, an inflection point appears, the enthalpy increment being smaller for a short concentration interval and then resuming its former value up to the limit of the range studied. The position of the critical interval depends on the solvent employed and on the molecular weight of the fraction. An equation, based on Flory's theory, has been developed for predicting the critical concentration from intrinsic viscosity. Assuming that, at the critical concentration, the molecules are just coming into contact, it is possible to calculate the diameter of the sphere equivalent to a molecule. Comparison of the dimensions obtained from the critical concentration and the root-mean-square end-to-end distance of the molecule calculated by the Flory equation leads to agreement within 10%.
SOME THERMODYNAMIC CONSIDERATIONS OF SURFACE REGIONS: SURFACE TENSION, ADSORPTION, AND ADSORPTION HYSTERESIS
Authors: Flood E. A.
Published: May 2006

Thermodynamic conditions for equilibrium between bodies which exert forces upon one another are discussed. The two bodies are treated as assemblies of infinitesimal volumes of pure components and the influence of the mutual potential fields examined. The results provide a thermodynamic description of surface tension and certain types of adsorption phenomena, as well as throwing considerable light on adsorption hysteresis.
THE PHOTOLYSIS OF METHYL ETHYL KETONE
Authors: Ausloos P. , Steacie E. W. R.
Published: May 2006

Methyl ethyl ketone has been photolyzed at temperatures between 25° and 240 °C., at varying pressures and intensities. Azomethane has also been photolyzed in the presence of methyl ethyl ketone. It is concluded that the ratio of disproportionation to recombination for a methyl and an ethyl radical is of the order of 0.04. The activation energy for the abstraction of hydrogen from the ketone by methyl is 7.4 ± 0.1 kcal., and by ethyl it is 8.0 ± 0.1 kcal.
THE DEGRADATION OF CARRAGEENIN: II. INFLUENCE OF FURTHER VARIABLES
Authors: Masson C. R. , Santry D. , Caines G. W.
Published: May 2006

A further study has been made of the degradation of carrageenin in aqueous solution. An 80 °C. extract of Chondrus crispus degraded more rapidly than a preparation from which a 30 °C. extract had been first removed. The latter preparation could be degraded to a lower limiting intrinsic viscosity under suitable conditions. Degradation was mainly random, but a more rapid initial degradation was observed under all conditions studied. The presence of dissolved oxygen accelerated the reaction above 60 °C. Maximum stability was observed in an inert atmosphere at pH 9 in the presence of salts. Hydroxymethylfurfural and formic acid were identified as products, the yield of the former being higher than from D-galactose alone. The results have been discussed in the light of recent work on the constitution of the polysaccharide.
LIGHT ABSORPTION STUDIES: PART I. ULTRAVIOLET ABSORPTION SPECTRA OF SUBSTITUTED ACETOPHENONES
Authors: Forbes W. F. , Mueller W. A.
Published: May 2006

The steric hindrance postulated by Arnold and co-workers to account for anomalous reaction rates of some substituted acetophenones has been verified by means of ultraviolet light absorption data. The spectra of a number of other substituted acetophenones have been discussed in terms of the electronic and steric effects of substituents.
THE EFFECT OF BORIC ACID ON THE GROWTH OF ETHYLENE DIAMINE TARTRATE CRYSTALS
Authors: Booth A. H. , Buckley H. E.
Published: May 2006

When present in ethylene diamine tartrate (EDT) solutions in small concentration boric acid produces many crystallographic phenomena associated with specific adsorption on crystal faces; especially habit modification and growth inhibition. These effects are typical of those given, incidentally, by "growth improvers", and it is concluded that boric acid would be a logical choice for intensive testing as a flaw suppressor in the solutions from which large single crystals of EDT are grown.
THE REACTION OF NITRAMINES WITH HYDROCHLORIC ACID
Authors: McKay A. F. , Hatton W. G. , Skulski M.
Published: May 2006

A facile process for the conversion of N-(β-nitraminoethyl)-N′-substituted-N″-nitroguanidines into the reactive N-(β-chloroethyl)-N′-substituted-N″-nitroguanidines has been developed. N-(β-Nitraminoethyl)-N′-phenyl-N″-nitroguanidine on standing in concentrated hydrochloric acid solution gives a mixture of N-(β-chloroethyl)-N′-phenyl-N″-nitroguanidine and 1-nitro-2-phenylamino-2-imidazoline. N-(β-Chloroethyl)-N′-diethyl-N″-nitroguanidine, which is prepared in a similar manner, is unstable at room temperature and it slowly cyclizes to give 1-nitro-2-diethylamino-2-imidazoline. Some new nitroguanidine derivatives formed from the reaction of amines with methylnitrosonitroguanidine also are described.
MECHANISM FOR THE FORMATION OF GUANIDINE FROM UREA AND AMMONIUM SULPHAMATE
Authors: Boivin Jean L. , Lovecy A. L.
Published: May 2006

The over-all mechanism of the formation of guanidine from urea and ammonium sulphamate is briefly discussed. Experimental results are presented, indicating that primary formation of the ammonium salt of ureasulphonic acid and subsequent dissociation into cyanamide and ammonium sulphate, which further react to form guanidine in the known manner, constitute the main steps in the process.
MESYL DERIVATIVES OF HYDRAZINE
Authors: Newcombe Alan G.
Published: May 2006

Monomesylhydrazide, 1-acetyl,2-mesylhydrazide, and sym-dimesylhydrazide were obtained by means of the Schotten–Baumann reaction. For comparison with these compounds the hydrazinium dimesylate, hydrazinium monomesylate, monomesylhydrazide mesylate, and monoacetylhydrazide mesylate were prepared. The preparation of dimesyldiimide by the action of metallic sodium on N,N-dichloromesylamide was attempted.
THE VIBRATIONAL SPECTRUM OF THE SULPHITE ION IN SODIUM SULPHITE
Authors: Evans J. C. , Bernstein H. J.
Published: May 2006

not available
THE FORMATION OF MOLECULAR COMPLEXES BETWEEN SOLID UREA AND n-OCTANE VAPOR
Authors: McAdie H. G. , Frost G. B.
Published: May 2006

not available
LCAO MO CALCULATIONS ON SATURATED HYDROCARBONS AND THEIR SUBSTITUTED DERIVATIVES
Authors: Sandorfy C.
Published: May 2006

The simple semiempirical molecular orbital method was applied to saturated hydrocarbons in three different approximations. Electronic charge distribution diagrams were obtained. Characteristic differences between saturated and conjugated compounds concerning bond localization and the effect of an electronegative substituent can be interpreted on the basis of these diagrams. The 1s electrons of the hydrogens are introduced for the first time in semiempirical molecular orbital calculations.
SOME NEW REACTIONS AND DERIVATIVES OF KOJIC ACID
Authors: Beélik Andrew , Purves C. B.
Published: May 2006

The stability of the ring structure in kojic acid toward various reagents was investigated. Cleavage to an open-chain, dienol derivative in N sodium hydroxide at 25°, or fragmentation of the structure, was very slow. The benzoyl group in the fifth (phenolic) position of dibenzoylkojic acid was removed by hydroxylamine hydrochloride in pyridine so selectively that the method was of value in synthesizing certain new derivatives. Although catalytic hydrogenation readily reduced the pyrone ring in kojic acid to undefined substances, zinc dust in glacial acetic acid reduced the hydroxymethyl group in the dibenzoate to a methyl group and yielded benzoylallomaltol. The ring in dibenzoylkojic acid was apparently opened, with retention of both benzoyl groups, by semicarbazide hydrochloride and pyridine to yield two isomeric "disemicarbazones", C22H22N6O7, decomp., 215° and 172–173°, respectively. The higher-melting isomer when boiled with dilute acid gave a compound C21H15N3O5, m.p. 244°, which was apparently cyclic; the same isomer with nitrous acid yielded two isomeric, apparently open-chain "monosemicarbazones", C21H19N3O7, decomp., 215° and 178–179°, respectively. The structures of these five compounds were not determined. The following substances were thought to be new: sodium kojate, a white powder, and its crystalline tetrahydrate; 5-hydroxy-2-(methoxymethyl)-γ-pyrone, m.p. 75–76°, and its crystalline aluminum salt, decomp. 270–271°; molecular addition compound of dibenzoylkojic acid and benzoic acid, m.p. 120–121°; 2-(acetoxymethyl)-5-benzoxy-γ-pyrone, m.p. 144°; 2-(benzoxymethyl)-5-hydroxy-γ-pyrone, m.p. 180–181°; and 2-(benzoxymethyl)-5-methoxy-γ-pyrone, m.p. 110–111°. A more convenient synthesis was discovered for 5-benzoxy-2-(hydroxymethyl)-γ-pyrone, and the published melting point was revised from 136° to 143–144°; the melting point of 5-benzoxy-2-(triphenylmethoxymethyl)-γ-pyrone was revised from 206–08° to 213–214°.
LONDON – VAN DER WAALS ATTRACTIVE FORCES BETWEEN GLASS SURFACES
Authors: Howe P. G. , Benton D. P. , Puddington I. E.
Published: May 2006

The attractive force between a pyrex glass bead and plate has been measured using a sensitive pendulum-type apparatus. The force required for separation of the bead from the plate has been shown to be strongly time dependent, a phenomenon which appears not to have been reported previously for adhesions in gaseous media. The observed results have been shown to be consistent with the theoretical London – van der Waals interaction. The estimated value of the London force constant is compared with that obtained by other workers.
TEMPERATURE COEFFICIENTS IN HYDROCARBON OXIDATION
Authors: Shu Nan-Chiang Wu , Bardwell J.
Published: May 2006

The oxidation of gaseous butane has been investigated in the range 260 °C. to 540 °C. with reaction vessels differing greatly in surface to volume ratio. Increased surface area retards the reaction. The rate–temperature relation shows a maximum and a minimum. At low temperatures the rate is very sensitive to temperature, the apparent activation energy being greater than 100 kcal. The abnormal temperature coefficients are shown to arise in part from the differing response to temperature of the branching reactions and the initiation reactions, and in part from the occurrence of competing reactions.
SOME FERRIC HALIDE COMPLEXES, AND TERNARY COMPLEXES WITH THIOCYANATE IONS
Authors: Lister M. W. , Rivington D. E.
Published: May 2006

A spectrophotometric study of solutions containing ferric and bromide ions; ferric, bromide, and thiocyanate ions; and ferric, chloride, and thiocyanate ions is reported. The measurements were made at constant temperature and ionic strength. The data were interpreted with the help of the results from the first paper of this series. The data show that FeBr++ and FeBr2+ are formed, and values are obtained for the equilibrium constants for their formation from simple ions, and for the extinction coefficients of FeBr++. When thiocyanate is also present, the data can best be interpreted by assuming that FeSCNBr+ or FeSCNCl+ is formed. At high chloride concentrations it seems necessary to postulate also FeCl2+ and FeSCN•Cl2. Estimates are made for the equilibrium constants for the formation of all these species from simple ions. As with the corresponding sulphate complexes, there seems to be no particular reluctance to form mixed complexes such as FeSCNCl+, as compared with the 'simple' complexes such as FeCl2+.
A SYNTHESIS OF L-ISOGLUTAMINE FROM γ-BENZYL GLUTAMATE
Authors: Kraml M. , Bouthillier L. P.
Published: May 2006

not available
A DIELECTRIC STUDY OF PLASTICIZED POLYVINYLIDENE CHLORIDE
Authors: Funt B. L. , Sutherland T. H.
Published: May 2006

The electrical response of plasticized polyvinylidene chloride has been studied over a wide range of frequency, temperature, and plasticizer content. The dispersion region was shifted to lower temperatures at a given frequency on the addition of alpha chloronaphthalene as plasticizer, but remained practically unchanged with hexachlorobenzene as plasticizer. Comparison was made with mechanical measurements for plasticized vinylidene chloride copolymers and reasonable agreement between electrical and mechanical properties was found. Enthalpies and entropies for dielectric relaxation were calculated on the theory of absolute reaction rates and were compared with values for plasticized polyvinyl chloride. A calculation of plasticizer efficiency from electrical measurements was attempted on the basis of a method suggested by Dyson. An interesting empirical relationship between enthalpy and entropy of activation and plasticizer content in polyvinyl chloride and polyvinylidene chloride is presented.
SOLUBILITY CRITERIA FOR THE EXISTENCE OF HYDROXYAPATITE
Authors: Clark J. S.
Published: May 2006

The solubilities of synthetic basic calcium phosphate precipitates in carbon dioxide free aqueous systems were studied over a wide range of conditions. The pH of the suspensions and the calcium and phosphate concentrations in the solutions were determined both after precipitation and after dissolution of the solid phases. Solubility criteria applied to these measurements indicated that hydroxyapatite has a definite solubility product.
PERIODATE–PERMANGANATE OXIDATIONS: II. DETERMINATION OF TERMINAL METHYLENE GROUPS
Authors: Lemieux R. U. , Rudloff E. Von
Published: May 2006

The periodate–permanganate oxidation of a terminal methylene group can be made to produce formaldehyde in high although not quantitative yield. Since the yields compare favorably with those obtained by ozonolysis, the reagent can serve as the basis for a convenient micromethod for the estimation of terminal methylene groups. The less than theoretical yields of formaldehyde are believed mainly due to the conversion of the olefin in part to α-hydroxyaldehyde in the initial stage of the reaction.
THE VIBRATIONAL SPECTRA OF CH2=CHCl AND CH2=CDCl
Authors: Evans J. C. , Bernstein H. J.
Published: May 2006

The infrared and Raman spectra of CH2=CDCl and the Raman spectrum of CH2=CHCl have been obtained and depolarization ratios of the Raman bands have been measured. The spectra of the two molecules have been correlated.
THE MESOMORPHIC BEHAVIOR OF ANHYDROUS SOAPS: PART II. DENSITIES OF ALKALI METAL STEARATES
Authors: Benton D. P. , Howe P. G. , Farnand R. , Puddington I. E.
Published: May 2006

The densities of the series of alkali metal stearates and of a number of sodium stearates having substituents in the hydrocarbon chain have been measured over a temperature range of 25–380 °C. Discontinuities in the density–temperature relationships indicate the transitions between the various mesomorphic forms in which these soaps exist and the results are compared with transition data obtained by an optical method, described in Part I of this series. Mesomorphism is found to be much less pronounced in the substituted stearates examined than in the normal soaps.
THE PREPARATION OF o- AND p-ACETAMINOBENZALDEHYDES
Authors: Brown J. J. , Brown R. K.
Published: May 2006

Treatment of N,N-diacetyl-o-toluidine with N-bromosuccinimide followed by hydrolysis of the intermediate dibromo compound gave o-acetaminobenzaldehyde. The reaction was applied successfully to N,N-diacetyl-p-toluidine, N,N-diacetyl-4-chloro-o-toluidine, 2,4-bis(diacetamino)toluene, and 4-acetoxy-N,N-diacetyl-o-toluidine.
DEGRADATION OF D-GLUCOSE-1-C14 TO TRIOSE-REDUCTONE-C14
Authors: Bauer H. F. , Teed Carol
Published: May 2006

Triose-reductone-C14 was obtained by treating D-glucose-1-C14 with sodium hydroxide in the presence of lead acetate at elevated temperatures. Carbon atoms four, five, and six, as well as carbon atoms one, two, and three, of the D-glucose molecule are shown to contribute to the triose-reductone yield. The formation of triose-reductone was found not to be accompanied by glycerol formation. Mechanisms for fragmentation of reducing sugars are discussed in the light of these findings.
SYNTHESIS OF DEUTERATED DIMETHYL CARBONATE
Authors: Renaud R. , Leitch L. C.
Published: May 2006

not available
THE NATURAL ABUNDANCES OF THE URANIUM ISOTOPES
Authors: Lounsbury M.
Published: May 2006

Using a surface-ionization mass spectrometer, the natural U238/U235 abundance ratio in uranium obtained from Great Bear Lake Pitchblende has been measured to be 137.80 ± 0.14. From a survey of results reported in the literature on U234 a best value of 17,325 ± 550 was estimated for the natural U238/U234 abundance ratio. The corresponding isotopic abundances are 0.7204 ± 0.0007 atom % and 0.00573 ± 0.00018 atom % for U235 and U234, respectively.
RECOMBINATION OF RECOIL FRAGMENTS IN NEUTRON-IRRADIATED POTASSIUM CHROMATE
Authors: Maddock A. G. , Maine M. M. de
Published: May 2006

The kinetics of the process whereby the retention increases on heating previously neutron-irradiated potassium chromate have been investigated. The results cannot be explained by any unimolecular or bimolecular mechanism, nor by a combination of a few such steps. The data are not compatible with the commoner diffusion-controlled mechanisms. Experiments on solid solutions of potassium chromate in potassium fluoberyllate suggest that the process involves the recombination of the fragments from individual rupture events. A tentative hypothesis, analogous to the theory of the formation of very thin oxide films on metals, is advanced and it accounts for all the existing data.
A SYNTHESIS OF 5-O-METHYL D-GLUCOSE AND OF 2-O-METHYL D-GLYCERONAMIDE
Authors: Jones J. K. N.
Published: May 2006

A preparation of 5-O-methyl D-glucose from 1,2-O-isopropylidene D-glucurone is described. Oxidation of the D-glucose derivative with periodate gave 2-O-methyl D-glycerose from which 2-O-methyl D-glyceronamide was prepared.
ORGANIC DEUTERIUM COMPOUNDS: XV. SYNTHESIS OF SOME DEUTERATED ALKANES
Authors: Leblanc Mary Elaine , Morse A. T. , Leitch L. C.
Published: May 2006

An improved method of preparing deuterated alkanes from the halides has been developed. Dehalogenation of ethyl iodide, 1,1-dibromoethane, and 1,1,1-trichloroethane with zinc dust in deuterium oxide – dioxane solutions, or even with deuterium oxide alone, gave excellent yields of ethane-d1, ethane-1,1-d2, and ethane-1,1,1-d3. Methane-d1, -d2, -d3, and -d4 were prepared similarly from methyl iodide, dibromomethane, chloroform, and carbon tetrachloride respectively. The isotopic purity of the products was over 90 mol.%. The reaction is also applicable to higher alkyl halides.
A LOW-TEMPERATURE APPARATUS FOR SINGLE-CRYSTAL X-RAY GONIOMETERS
Authors: Harding T. T.
Published: May 2006

An apparatus is described which may be used to grow and maintain single crystals at temperatures down to approximately −180 °C. The crystals may be grown directly upon the head of the X-ray goniometer in order to permit the recording of data required for the investigation of the crystalline structure of substances which exist in the liquid or gaseous states at ordinary temperatures.
THE NUMBER OF SUBUNITS IN THE MOLECULE OF HORSE HEMOGLOBIN
Authors: Reichmann M. E. , Colvin J. Ross
Published: May 2006

The molecular weights of horse hemoglobin, horse globin, and performic acid oxidized horse globin were determined by osmotic pressure, by an approach to equilibrium sedimentation, and by light scattering (except hemoglobin) at pH 1.5 to 2.5 in 0.05 M NaCl. Sedimentation coefficients were determined for these materials over the same pH range and electrophoretic analyses were made from pH 1.5 to 4.0. The results show that in dilute salt solutions below pH 2.5 horse hemoglobin dissociates to four subunits all approximately equal in mass but at least two of which differ electrokinetically and therefore in composition. The subunits are probably held together in the native hemoglobin molecule only by non-covalent bonds.
SOME XANTHATE METHYL ESTERS OF GLUCOSE
Authors: Sanyal Amiya K. , Purves C. B.
Published: May 2006

The following compounds were thought to be new: 1,2-mono-O-isopropylidene-D-glucofuranose-3-S-methyl xanthate, m.p. 102°, [Formula: see text] −27.8°; methyl-4,6-O-benzylidene-α-D-glucopyranoside-2,3-di-S-methyl xanthate, m.p. 100°, [Formula: see text] −18.1°; and 1,2;3,5-di-O-methylene-α-D-glucofuranose-6-S-methyl xanthate, m.p. 99°, [Formula: see text] +27.3° in chloroform. Partial hydrolysis of the isopropylidene and methylene derivatives yielded some glucose-3-S-methyl xanthate and glucose-6-S-methyl xanthate as crude sirups. The 6-xanthate greatly excelled the 3-xanthate in stability toward acid. The chromatographic behavior of both was determined.
THE PAPILIONACEOUS ALKALOIDS: XXII. PUSILLINE; ITS IDENTITY WITH β-ISOSPARTEINE
Authors: Greenhalgh R. , Marion Léo
Published: May 2006

l-Pusilline is shown to be identical with β-isosparteine by direct comparison of the bases and of their salts. By mild oxidation with mercuric acetate followed by catalytic hydrogenation, pusilline is converted to d-sparteine, thus confirming its identity with l-β-isosparteine. The sparteine obtained from β-isosparteine derived from lupanoline was d-sparteine, and not the l-form as reported. Oxidation of β-isosparteine with potassium permanganate gives rise to a hydrated 10,17-dioxo-derivative.
ÉTUDES SUR LA SYNTHÈSE DE L’HYDROXYPROLINE À PARTIR DE DÉRIVÉS DE L’ACIDE 2-AMINO-4-PENTÈNOÏQUE
Authors: Gaudry Roger , Berlinguet Louis , Langis André , Paris Gérard
Published: May 2006

A systematic investigation of the synthesis of 4-hydroxy-DL-proline and 2-amino-4-dihydroxyvaleric acid has been made, starting from the following derivatives of 2-amino-4-pentenoic acid: ethyl allylacetamidomalonate, ethyl allylacetamidocyanoacetate, 2-phthalimidopentenoic acid, allylacetamido-malonic acid, acetylallylglycine, 5-allylhydantoin, and 3-phenyl-5-allylhydantoin. Chlorine or bromine was added to the double bond of these compounds, and the reaction products were either derivatives of 5-halogenated-4-valerolactones or derivatives of 4,5-dihalogenated pentanoic acids, depending on whether the carboxyl group of the pentanoic acid was free or not when the halogenation reaction was carried out. Acid hydrolysis followed by treatment with barium hydroxide always gave mixtures, in different ratio, of 4-hydroxy-DL-proline and 2-amino-4,5-dihydroxyvaleric acid which were analyzed and isolated as the copper salts. In the case of 5-(2,3-dibromopropyl)hydantoin and 3-phenyl-5-(2,3-dibromopropyl)hydantoin, no cyclization could be obtained.
SYNTHESES AND ABSORPTION SPECTRA OF 1-CHLOROPHENYL-3-PHENYL-4-ALKYL-5-PYRAZOLONES AND PYRAZOLONES-4-C14
Authors: Gagnon Paul E. , Boivin Jean L. , Laflamme Yvon
Published: May 2006

Monosubstituted benzoylacetic esters C6H5COCH(R)CO2C2H5 (R = H, CnH2n+1 (n = 1 to 9), and C6H5CH2) obtained by the condensation of n-alkyl halides with ethyl benzoylacetate were reacted with o-, m-, and p-chlorophenyl hydrazines to give 1-chlorophenyl-3-phenyl-4-alkyl-5-pyrazolones. Pyrazolones-4-C14 were prepared by the action of the same hydrazines on ethyl benzoylacetate-α-C14 obtained from benzoyl chloride and ethyl malonate-2-C14. Their activities were 801, 894, and 847 c./min. respectively. The ultraviolet and infrared absorption spectra of all the pyrazolones were determined and the most probable structures ascribed to the compounds.
EFFECT OF COMPLEXING ON THE HOMOGENEOUS CATALYTIC ACTIVATION OF HYDROGEN BY CUPRIC SALTS
Authors: Peters E. , Halpern J.
Published: May 2006

The effects of various organic and inorganic complex-forming reagents on the homogeneous catalytic activation of H2 by Cu++ in aqueous solution have been determined. The catalytic activities of the cupric complexes decrease in the order: butyrate, propionate > acetate > SO4− > Cl− > H2O (i.e. the uncomplexed Cu++ ion) > glycine, ethylenediamine. The mechanism of the activation process is discussed.
UNIT CELL, SPACE GROUP, AND INDEXED X-RAY DIFFRACTION POWDER DATA FOR POTASSIUM HYDROGEN MALONATE, KHC3H2O4
Authors: Gupta M. P. , Barnes W. H.
Published: May 2006

not available
A NEW METHOD FOR PREPARING HYDROXYETHYL ETHERS OF GLUCOSE
Authors: Shyluk W. P. , Timell T. E.
Published: May 2006

Three monosubstituted hydroxyethyl ethers of D-glucose have been synthesized by a novel method involving reduction of the corresponding carboxymethyl derivatives with lithium aluminum hydride. This technique also allowed introduction for the first time of hydroxyethyl substituents containing polyethylene oxide chains of a definite length in the glucose molecule, as exemplified by the synthesis of 3-O-hydroxyethoxyethyl-D-glucose.
HYDROGEN OVERPOTENTIAL ON ALUMINUM
Authors: Hansen D. J. , Wetmore F. E. W.
Published: May 2006

The hydrogen overpotential of pure and impure aluminum in 0.1 N H2SO4 at 25° has been studied. The effect of the autocorrosion of the metal has been interpreted and the role of impurities in determining the overpotential and the rest potential has been shown. As well, the build-up and decay of the overpotential has been studied; the behavior is much more complicated than that of noble metals.
SKELETAL SILVER CATALYSTS FOR THE OXIDATION OF ETHYLENE TO ETHYLENE OXIDE
Authors: Cambron A. , Alexander W. A.
Published: May 2006

Skeletal silver catalysts of high specific activity have been prepared by the removal of calcium from calcium–silver alloys. The activity of these catalysts in the oxidation of ethylene to ethylene oxide has been investigated. Catalysts prepared by the removal of the other alkaline earth metals from their alloys with silver have also been studied. It has been found that catalysts prepared from calcium–silver alloys show a higher specific activity and are more stable and more conveniently prepared than the catalysts from the other silver alloys investigated.
THE SURFACE ENERGIES OF CALCIUM OXIDE AND CALCIUM HYDROXIDE
Authors: Brunauer Stephen , Kantro D. L. , Weise C. H.
Published: May 2006

The total surface energies (or surface enthalpies) of calcium oxide and calcium hydroxide were determined by measuring the heats of solution in 2 N nitric acid of calcium oxide and calcium hydroxide having high and low specific surface areas, and by determining the surface areas by the B.E.T. method, using nitrogen as adsorbate. The molecular area of nitrogen was taken to be 16.2 Å2 at 77.3 °K. Precision determinations of the lattice parameters indicated that the high and low surface substances had the same unit cell dimensions, and X-ray line broadening measurements indicated that the crystals were perfect or nearly perfect. The surface energy of calcium oxide at 23 °C. was found to be 1310 ± 200 erg/cm.2, which compares well with the theoretical value of 1100 erg/cm.2 The surface energy of calcium hydroxide at 23 °C. was found to be 1180 ± 100 erg/cm.2 The heat of the reaction CaO (c, 23°) + H2O (l, 23°) = Ca(OH)2 (c, 23°), for crystals having negligible specific surface areas, was found to be −15,620 cal.
THE PREPARATION AND SOME CLEAVAGE REACTIONS OF ALKYL AND SUBSTITUTED ALKYL METHANESULPHONATES: THE SYNTHESIS OF FLUORIDES, IODIDES, AND THIOCYANATES
Authors: Pattison F. L. M. , Millington J. E.
Published: May 2006

Representative esters of methanesulphonic acid were synthesized, and cleaved to form the corresponding fluorides, iodides, and thiocyanates. From this work was developed a convenient laboratory procedure for converting alcohols to fluorides.
REACTION OF OXYGEN ATOMS WITH ACETALDEHYDE
Authors: Cvetanović R. J.
Published: May 2006

Reaction of oxygen atoms, produced by mercury photosensitized decomposition of nitrous oxide, with acetaldehyde has been studied at room temperature. The major products of the reaction are water and biacetyl and the only primary process appears to be[Formula: see text]followed by[Formula: see text]and[Formula: see text]At room temperature oxygen atoms react with acetaldehyde 0.7 ± 0.1 times as fast as with ethylene, so that the activation energy of reaction [1] is likely to be close to 3 kcal./mole.
THE STRUCTURES AND CHEMISTRY OF THE PRODUCTS FROM THE REACTION OF AMINO ALCOHOLS WITH CARBON DISULPHIDE
Authors: Skulski M. , Garmaise D. L. , McKay A. F.
Published: May 2006

A study of the infrared spectra of the oxazoline derivatives, which are formed by the condensation of carbon disulphide with amino alcohols, shows that they possess the oxazolidine-2-thione structure rather than the tautomeric 2-thiol-2-oxazoline structure. 2-Benzylamino-4,4-dimethyl-2-oxazoline was formed by the reaction of benzylamine with 2-methylmercapto-4,4-dimethyl-2-oxazolinium iodide. 5-Diethylaminomethyl-2-oxazolidone and its methylation product also have been prepared.
THE ULTRAVIOLET ABSORPTION SPECTRA OF METHYL-1,2-BENZANTHRACENES
Authors: Sandorfy C. , Jones R. Norman
Published: May 2006

The ultraviolet absorption spectra of 1,2-benzanthracene, all twelve mono-methyl derivatives, and six dimethyl derivatives have been measured (a) at room temperature in n-heptane solution, (b) at −100 °C. in n-pentane solution. An analysis of the band envelopes indicates that most of the absorption between 33,000 and 25,000 cm.−1 arises from two series of overlapping bands. The members of each series are spaced at intervals of approximately 1400 cm.−1. The spacing between the two band series and their relative intensities are dependent on the nature and position of the alkyl substituents. Absorption between 40,000 and 33,000 cm.−1 can be treated in a similar manner. Other fine structure is also observed. It is considered most probable that each of the overlapping series of bands is associated with a separate electronic excitation. The significance of these observations is considered in relation to the theoretical treatments of the energy levels of 1,2-benzanthracene as developed by Klevens and Platt and by Moffitt.
MOLECULAR INTERACTION OF HYDROGEN CHLORIDE WITH π-ORBITAL DONOR MOLECULES: I. ALKENES AND ALKYNES
Authors: Cook D. , Lupien Y. , Schneider W. G.
Published: May 2006

Hydrogen chloride, which is a convenient small molecule “acceptor”, was used to study the donor capacity of π-orbitals in a number of ethylenic and acetylenic hydrocarbons. The composition of the molecular addition compounds formed between these hydrocarbons and hydrogen chloride was determined by thermal analysis. The freezing-point diagrams for hydrogen chloride with a number of lower alkene homologues and with several alkyne homologues are reported. The addition compounds formed by the alkenes have HCl:hydrocarbon molecular ratios of 1:1 and 2:1. An exception is 2-methyl-butene-2 which undergoes rapid chemical reaction with HCl even at low temperatures. The HCl-complexes formed by the alkynes have molecular ratios 1:1, 2:1, and 4:1. Addition compounds of this type are not formed by the saturated hydrocarbons ethane and propane and therefore they must be attributed to specific forces of interaction of HCl with π-orbitals of the unsaturated hydrocarbons. It is suggested that weak hydrogen bonds are formed between the acid acceptor and the donor π-orbitals. To account for the 2:1 complex in the alkenes and the 4:1 complex in the alkynes it is necessary to postulate that each π-orbital can accommodate two molecules of HCl.
MOLECULAR INTERACTION OF HYDROGEN CHLORIDE WITH π-ORBITAL DONOR MOLECULES: II. BENZENE AND METHYL BENZENES
Authors: Cook D. , Lupien Y. , Schneider W. G.
Published: May 2006

Freezing-point diagrams of the binary systems consisting of hydrogen chloride with each of the hydrocarbons benzene, toluene, o-xylene, m-xylene, p-xylene, and mesitylene were determined. The phase diagrams exhibit 1:1 complexes in each of these systems. Toluene shows an exceptional behavior in that an additional compound containing two molecules of hydrocarbon per molecule of hydrogen chloride is also formed. The 1:1 complexes are attributed to weak hydrogen bonds formed between the acid and the π-orbital donors of the hydrocarbon. Colored complexes with HCl are formed by trans-stilbene and anthracene. The saturated cyclic hydrocarbons cyclohexane and cyclopropane form no addition compounds with hydrogen chloride.
THE HYDROLYSIS OF THE CONDENSED PHOSPHATES: III. SODIUM TETRAMETAPHOSPHATE AND SODIUM TETRAPHOSPHATE
Authors: Crowther Joan , Westman A. E. R.
Published: May 2006

The rates of hydrolysis of sodium tetrametaphosphate and tetraphosphate (in the presence of tetrametaphosphate) have been measured at 65.5 °C. over the pH range 2.5 to 13.3. Tetrametaphosphate anions hydrolyze to tetraphosphate which in turn hydrolyzes to triphosphate and orthophosphate and not to pyrophosphate. Thus the terminal oxygen bridges in the tetraphosphate and not the central one are attacked preferentially. The reactions were first order and acid catalyzed. The tetrametaphosphate hydrolysis was also base catalyzed with a minimum rate in solutions of pH approximately 7.5. The rate of hydrolysis of tetraphosphate was greater than triphosphate at the hydrogen ion concentrations studied. Hydrolysis of a sodium phosphate glass indicated that preferential attack on terminal oxygen bridges takes place also with higher polymers. However, trimetaphosphate is formed at the same time.
STUDIES IN THE WAGNER-MEERWEIN REARRANGEMENT. PART I
Authors: Anet F. A. L. , Bavin P. M. G.
Published: May 2006

The preparation by a convenient route of 9-methyl, ethyl, isopropyl, l-butyl, and benzyl phenanthrenes is described. This consists of the alkylation of methyl fluorene-9-carboxylate under mild conditions, reduction of the ester group with lithium aluminum hydride, and then tosylation of the carbinol. The tosyl esters so prepared rearrange to alkylphenanthrenes with simultaneous loss of the elements of toluenesulphonic acid, when heated alone or in formic acid. Dehydration of the carbinols at 160 ° with polyphosphoric acid also promotes rearrangement.
A LOW TEMPERATURE CELL FOR USE WITH THE CARY ULTRAVIOLET SPECTROPHOTOMETER
Authors: Jones R. N. , Keir D. S.
Published: May 2006

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PHOTOLYSIS OF KETENE IN THE PRESENCE OF HYDROGEN
Authors: Chanmugam J. , Burton Milton
Published: May 2006

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THE VIBRATIONAL SPECTRA OF ISOBUTANE AND ISOBUTANE-d1
Authors: Evans J. C. , Bernstein H. J.
Published: May 2006

The Raman spectra of liquid (CH3)3CH and (CH3)3CD were obtained photo-electrically and intensities and depolarization ratios measured. The infrared spectra of the corresponding gases were obtained from 3 to 35 μ. A vibrational assignment consistent with depolarization ratios and band contours has been made for the molecules on the basis of C3ν symmetry and their spectra correlated.
ADSORPTION OF OXYGEN BY A SILVER CATALYST
Authors: Smeltzer W. W. , Tollefson E. L. , Cambron A.
Published: May 2006

An apparatus is described to measure volumetrically the amount of gas adsorbed by a catalyst at constant pressure and at exposure times as short as 0.1 min. The volumes of oxygen adsorbed by a technical silver catalyst at pressures of 200, 400, and 700 mm. and in the temperature range of 180° to 300°C. have been measured. Surface area determinations of 0.33 to 0.38 sq. meter per gm. of catalyst by physical adsorption and chemisorption methods show that each silver atom of the surface is associated with approximately one oxygen adatom at a monolayer coverage. The initial rate of adsorption of oxygen is directly proportional to its pressure. Observed transitions in the oxygen adsorption rates indicate that more than one type of oxygen complex occurs on the catalyst surface. The Elovich equation provides the best approximation of the adsorption rate data but is of limited applicability in interpretation of the mechanism of adsorption. Values of 22–29 kcal./mole and 17–25 kcal./mole have been calculated for the apparent activation energy and isosteric heat of adsorption respectively.
THE REACTIONS OF ACTIVE NITROGEN WITH ALKYL CHLORIDES
Authors: Dunford B. , Evans H. G. V. , Winkler C. A.
Published: May 2006

The reactions of active nitrogen with methyl, ethyl, vinyl, propyl, and isopropyl chlorides yielded hydrogen cyanide and hydrogen chloride as the main products. Small amounts of cyanogen and a polymer were formed from all the halides, and all except methyl chloride also yielded small amounts of C2 and C3 hydrocarbons. The observed changes in amounts of products recovered with different reactant flow rates were characteristic of a fast reaction in which complete consumption of either reactant occurs when the other is present in excess. Mechanisms for the reactions are suggested on the basis that relatively long-lived complexes are formed in the initial attack of a nitrogen atom on the alkyl chloride.
THE LIMITING HEAT OF SOLUTION OF PLUTONIUM IN SOME RARE EARTH METALS
Authors: McKenzie D. E. , Jenkinson W. M. , Denovan A. S.
Published: May 2006

The distribution of plutonium between neutron-irradiated uranium and some rare earth metals has been examined as a function of temperature in the range 1160° to 1350 °C. The results are used to calculate [Formula: see text] the limiting partial molal heat content of plutonium, at 1250 °C. in lanthanum, cerium, neodymium, and a commercial preparation of mixed rare earths (misch metal). The following values (in kilocalories) were obtained: lanthanum 2.9, cerium 1.1, neodymium 0.0, and misch metal 1.1. The maximum error associated with these values is ±0.4 kilocalories.
FURTHER OBSERVATIONS ON THE LEAD TETRAACETATE OXIDATION OF REDUCING DISACCHARIDES
Authors: Charlson A. J. , Perlin A. S.
Published: May 2006

Evidence is presented which supports an earlier suggestion that the linkage-position in a reducing disaccharide may be determined readily by lead tetraacetate oxidation. Compounds examined include aldose and ketose disaccharides and aldobiuronic acids. Two types of reaction—one catalyzed by potassium acetate and the other non-catalyzed—are employed jointly to illustrate oxidation patterns which clearly differentiate each position of the biose linkage. Partial degradation of reducing disaccharides by lead tetraacetate oxidation is illustrated by the preparation of 2-O-α- and 2-O-β-D-glucopyranosyl-D-erythritol and 4-O-β-D-galactopyranosyl-D-erythritol. In turn, 2-O-β-D-glucopyranosyl-D-erythritol is degraded to 2-O-β-D-glucopyranosyl-glycerol.
THE REACTIVE COMPONENTS IN ACTIVE NITROGEN AND THE ROLE OF SPIN CONSERVATION IN ACTIVE NITROGEN REACTIONS
Authors: Evans H. G. V. , Winkler C. A.
Published: May 2006

Critical examination of the available experimental information provides rather convincing evidence that atomic nitrogen is the main reactive species in active nitrogen. It appears quite unlikely that a significant contribution to the activity is made by electronically excited molecules, metastable atoms, ions, or triatomic radicals. Evidence exists, however, for the presence of more than one active species, and a plausible suggestion would seem to be that the second species is vibrationally excited molecules. Consideration of the role of spin conservation in reactions of active nitrogen leads to the conclusion that reactions that conserve spin occur more readily than those in which spin is not conserved.
CONDUCTANCES OF LITHIUM NITRATE SOLUTIONS IN ETHYL ALCOHOL AND ETHYL ALCOHOL - WATER MIXTURES AT 25.0 °C.
Authors: Campbell A. N. , Debus G. H.
Published: May 2006

The conductances of solutions of lithium nitrate in 30, 70, and 100 weight per cent ethyl alcohol have been determined at concentrations ranging from 0.01 molar up to saturation, at 25 °C. The densities and viscosities of these solutions have also been determined. The data have been compared with the calculated conductances obtained from the Wishaw–Stokes equation. The agreement is fairly good up to, say, 2 M, for all solvents except absolute alcohol. In the latter solvent there is no value of å, the distance of closest approach, which will give consistent values of the equivalent conductance. In passing from pure water to pure alcohol, the value of å increases progressively and this we attribute to a change in the solvation of the lithium ion from water molecules to alcohol molecules. Some further calculations incline us to the view that the nitrate ion, as well as the lithium ion, is solvated to some extent, at least in alcohol.
THE EFFECT OF ELECTROLYTES ON THE RATE OF CHLORIDE LOSS FROM CHLOROPENTAMMINE CHROMIUM (III) ION IN AQUEOUS SOLUTION
Authors: Ikuta M. , McAdie H. G. , Smith W. MacF.
Published: May 2006

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THE INFRARED ABSORPTION SPECTRA OF DEUTERATED ESTERS: II. ETHYL ACETATE
Authors: Nolin B. , Jones R. Norman
Published: May 2006

The infrared absorption spectrum of ethyl acetate has been compared with the spectra of seven derivatives deuterated in the methyl and methylene groups. In the region 3500–1300 cm.−1 most of the bands can be assigned to vibrations localized in the individual groups. Absorption characteristic of the trideuteromethyl and dideuteromethylene groups can be recognized between 2300 and 2000 cm.−1. The C=O stretching vibration shows progressive displacement to lower frequency with increasing deuteration. The spectra in the range 1300–700 cm.−1 are also reported.