bluuebunny/crossref_metadata_2025 huggingface dataset:
LYCODINE, A NEW ALKALOID OF LYCOPODIUM ANNOTINUM
Authors: Anet F. A. L. , Eves C. R.
Published: May 2006

A new alkaloid, lycodine, C17H24N2, m.p. 118°, has been isolated from Lycopodium annotinum. Lycodine is a tetracyclic diacidic base containing a secondary nitrogen atom, a 2,3-disubstituted pyridine ring, and a C-methyl group. The 2,3-disubstitution is in the form of a saturated six-membered ring.
ÉTARD REACTION: II. POLYCYCLIC AROMATIC AND HETEROCYCLIC COMPOUNDS
Authors: Wheeler Owen H.
Published: May 2006

Polycyclic aromatic compounds can, in a number of cases, be oxidized with chromyl chloride, whereas heterocyclic compounds are unaffected.
PHOTOÖXIDATION OF BUTENE-1 AND ISOBUTENE BY NITROGEN DIOXIDE
Authors: Sato S. , Cvetanović R. J.
Published: May 2006

Reactions of oxygen atoms, produced by photolysis of nitrogen dioxide at 3660 Å, with butene-1 and isobutene have been studied at room temperature. In the case of butene-1, α-butene oxide and n-butanal have been identified as the major products, and methyl ethyl ketone, propanal, acetaldehyde, and ethyl nitrate as minor products. With isobutene, isobutanal was recovered as the major product and acetone, methyl ethyl ketone, methyl nitrate, and nitromethane as minor products. The absence of isobutene oxide in the recovered products from the isobutene reaction is due to its rapid reaction with nitrogen dioxide.The following values were obtained for the relative reaction rates of oxygen atoms with nitrogen dioxide (k2), butene-1 (k4a), and isobutene (k4b): k2/k4a = 1.9, k2/k4b = 0.34, k4b/k4a = 5.5.
REACTION OF DEUTERIUM ATOMS WITH ETHANE—MECHANISM OF METHANE EXCHANGE
Authors: Berisford R. , Roy D. J. Le
Published: May 2006

The reaction of deuterium atoms with ethane has been studied at 25 °C. by the method of mercury (3P1) photosensitization. Methane formation takes place by the addition of D atoms to methyl radicals in the presence of a third body. From the dependence of methane exchange on third-body concentration the lifetime of the excited methane molecule is estimated to be of the order of 10−9 sec. The lifetime of the excited ethane molecule formed by the addition of a D atom to an ethyl radical is estimated to be considerably less than 10−9 sec.
THE STRUCTURE OF MITRAPHYLLINE
Authors: Seaton J. C. , Tondeur R. , Marion Léo
Published: May 2006

Mitraphylline (C21H24O4N2) contains a carbomethoxyl group, and on hydrolysis gives rise to mitraphyllic acid. Spectroscopic evidence shows that the alkaloid contains two chromophores, one characteristic of an oxindole and one corresponding to the grouping CH3OOC—Ć==CH.OR. On treatment with dilute mineral acid the alkaloid gives rise to mitraphyllal (C19H24O3N2), which is a hemiacetal that no longer contains the isolated double bond and the carbomethoxyl group originally present in the alkaloid. Reduction of mitraphyllal by the Wolff–Kishner reaction gives mitraphyllane (C19H26O2N2). The dehydrogenation of mitraphyllal produced 3,4-diethylpyridine and 3-ethyloxindole. The action of lithium aluminum hydride on mitraphylline under mild conditions gave rise to mitraphyllol by reduction of the carbomethoxyl group, and under more vigorous conditions to dihydrodesoxy-mitraphyllol by reduction of the oxindole carbonyl as well. This last product has the properties of an aromatic amine. On the basis of the new experimental evidence, a total structure of mitraphylline is derived.
HYDROLYSIS OF SULPHATE ACID ESTER IN UNSTABILIZED CELLULOSE NITRATES
Authors: Gagnon Paul E. , Keirstead Karl F. , Newbold Brian T. , Thomas J.
Published: May 2006

The rate of hydrolysis of the sulphate acid ester in unstabilized cellulose nitrates in acetone/water solution at 25 °C. has been studied. The rate of hydrolysis in 90% acetone/water was too slow to produce a measurable increase in acidity during 24 hours. In 99% acetone/water solution the initial hydrolysis was very rapid and was followed by slower hydrolysis which was complete after 24 hours. Similar results were obtained with wood cellulose nitrates.In the case of cotton cellulose nitrates, there was an indication that hydrolysis of the sulphate acid ester decreased as the nitrogen content increased. The rate of hydrolysis of the sulphate acid ester in both cotton and wood cellulose nitrates was very similar to that of the sulphate acid ester in cellulose acetate sulphate.
THE CRYSTALLIZATION OF CALCIUM SULPHATE DIHYDRATE
Authors: Schierholtz O. J.
Published: May 2006

In this preliminary series of experiments, calcium sulphate dihydrate has been allowed to crystallize spontaneously from solutions of varying degrees of supersaturation, and induction periods and rate constants have been determined. The effect of crystal area, pH, and accelerators and retarders on this process has been examined. The degree of super-saturation has a direct effect on both the induction period and rate constant. Nucleation is affected markedly by pH. Salts having an ion in common with calcium sulphate function as accelerators. Retarders affect the induction period in proportion to their concentration, but show little, if any, effect on the rate of crystallization. The behavior of the various reagents under the conditions prevailing in these experiments is largely in accord with observations on the behavior of commercial plasters.
THE NATURE OF THE CADMIUM IONS IN HYDROXIDE AND CARBONATE SOLUTIONS
Authors: Lake Phyllis E. , Goodings J. M.
Published: May 2006

The nature and concentration of the cadmium–containing ions in potassium hydroxide and potassium carbonate solutions have been studied polarographically. The coordination number for the hydroxide–cadmium complex is 4 and its dissociation constant 2×10−10. The coordination number for the carbonate–cadmium complex is 3 and its dissociation constant 6×10−7.
THE INTERRELATION OF DELPHELINE AND LYCOCTONINE
Authors: Edwards O. E. , Marion Léo , Palmer K. H.
Published: May 2006

Lycoctonine has been converted to a derivative of delpheline, thus establishing a common diterpenoid skeleton and identical points of nuclear substitution for the two alkaloids.
VOLTAIC CELLS IN FUSED SALTS: PART IV. ELECTRODE POTENTIALS OF THE SYSTEMS: Tl/TlCl (KCl–NaCl), Cu/CuCl (KCl–NaCl), Cu/CuCl2 (KCl–NaCl), Cr/CrCl2 (KCl–NaCl), AND Cr/CrCl3 (KCl–NaCl). REDOX POTENTIALS OF THE SYSTEMS: Pt/CuCl, CuCl2 (KCl–NaCl), AND Pt/CrCl2, CrCl3 (KCl–NaCl)
Authors: Flengas S. N. , Ingraham T. R.
Published: May 2006

Using a Ag/AgCl (KCl–NaCl) reference electrode, the standard electrode potentials of the systems Tl/TlCl (KCl–NaCl), Cu/CuCl (KCl–NaCl), Cu/CuCl2 (KCl–NaCl), Cr/CrCl2 (KCl–NaCl), and Cr/CrCl3 (KCl–NaCl) were measured and found to be: 0.650 volt at 680 °C, and 0.250, −0.175, 0.755, and 0.423 at 700 °C. respectively. The standard redox potentials of the systems Pt/CuCl2, CuCl (KCl–NaCl), and Pt/CrCl3, CrCl2 (KCl–NaCl) were also measured at 700 °C. and found to be 0.600 and 0.240 volt respectively. The effect of temperature on the electromotive forces of the above cells was measured and the heats of the cell reactions were calculated from the data.
ON THE NATURE OF SULPHUROUS ACID
Authors: Falk Michael , Giguère Paul A.
Published: May 2006

Repeated attempts to detect by infrared spectrometry stable H2SO3 molecules in aqueous solutions of "sulphurous acid" or in frozen mixtures of SO2 and H2O have given only negative results. Sulphur dioxide dissolved in water exists mostly in the molecular state, the HSO3− and HS2O5− ions being formed in small amounts as a result of the equilibria[Formula: see text]There is very little interaction between SO2 and H2O molecules in condensed phases.
PHYSICAL ADSORPTION IN THE BENZENE–POLYSTYRENE SYSTEM
Authors: Barton S. S. , Mason S. G.
Published: May 2006

not available
THE MECHANISM OF THE PYROLYSIS OF PRIMARY ALKYL BROMIDES
Authors: Blades Arthur T.
Published: May 2006

not available
THE EXTENT OF THE ABNORMAL RECOMBINATION OF CYANISOPROPYL FREE RADICALS FROM 2,2′-AZO-BIS-ISOBUTYRONITRILE
Authors: Talât-Erben M. , Isfendiyaroğlu A. N.
Published: May 2006

The extent of the abnormal recombination of cyanisopropyl radicals to yield the ketenimine intermediate has been investigated at 80 °C. in toluene. It is found that 54.4% of the radicals recombine this way. This value is 75% higher than that reported previously. This result makes it possible to estimate a better value for the molar extinction of intermediate, and suggests the possibility that in the decomposition of the latter both free-radical and molecular processes are co-operative.
A MASS SPECTROMETRIC STUDY OF NORMAL OXYGEN AND OXYGEN SUBJECTED TO ELECTRICAL DISCHARGE
Authors: Herron J. T. , Schiff H. I.
Published: May 2006

A mass spectrometric study was made of oxygen activated by microwave and by a-c. glow discharge. Appearance potential curves for normal oxygen at masses 16 and 32 indicated the occurrence of multiple electron impact processes. The change in the curves when the oxygen was activated could be interpreted by assuming the presence of O-atoms in the 3P ground state, and O2 molecules in the 1Δg excited state. No evidence was obtained for the presence of ozone up to pressures of 2 mm. Hg. The recombination coefficient of O-atoms on pyrex was found to be 1.1 × 10−4. Only one oxygen atom in 21 was ionized before recombining in the mass spectrometer ion source. The rate constant for the reaction of O-atoms with N2O is less than 1 × 10−8 cm.3 mole−1 sec.−1, and several orders of magnitude less than this for the reaction O(3P) + N2O → 2NO. The reaction of O-atoms with NO2 was much faster than with NO, but no evidence was found for the formation of NO3.
PREDICTION OF SOME THERMODYNAMIC PROPERTIES EMPLOYING THE ISOELECTRONIC PRINCIPLE
Authors: Smith P. , Rao C. N. R.
Published: May 2006

An empirical method for predicting standard enthalpies and free energies of formation of isoelectronic molecules bearing in turn the groupings —F, —OH, —NH2, and —CH3 is proposed and used. It appears to be accurate to about ±10 kcal. mole−1 or better depending on the procedure employed.
THE SOLUBILITY OF ALUMINUM HYDROXIDE IN ACIDIC AND BASIC MEDIA AT 25 °C
Authors: Gayer K. H. , Thompson L. C. , Zajicek O. T.
Published: May 2006

The solubility of Al(OH)3 was measured in NaOH and HClO4 solutions. Possible reactions of Al(OH)3 in dilute NaOH and HCIO4 solutions are indicated along with the calculated constants. The amphoteric hydroxide was found to be more acidic than basic. The isoelectric point of Al(OH)3 was determined to be pH 7.7.
SOME CHEMISTRY OF 2,6-DIETHYLANILINE
Authors: Bavin P. M. G. , Scott J. M. W.
Published: May 2006

Orientation in the nitration and bromination of amides derived from 2,6-diethylaniline has been shown to be dependent on the acidity of the reaction medium, as found previously for the 2,6-dimethyl homologues.
MICROCALORIMETRY OF THE ADSORPTION OF WATER VAPOR ON SODIUM CHLORIDE
Authors: Papée Henry M. , Laidler Keith J.
Published: May 2006

Using a microcalorimeter of the Calvet type, measurements have been made of the heats of adsorption of water vapor on microcrystals of sodium chloride, the rate of heat production being followed as a function of time. With crystals of surface areas between 1 and 15 square meters per gram it was found that three distinct processes occurred, in the following order: (1) simple adsorption of water on the surface, (2) decrease in the surface area, and (3) penetration of water into the lattice. During the second stage no adsorption could be detected. On crystals with larger surface areas there was considerable overlapping of the three phenomena, but the general mechanisms appear to be the same.
LIGHT ABSORPTION STUDIES: PART XII. ULTRAVIOLET ABSORPTION SPECTRA OF BENZALDEHYDES
Authors: Dearden J. C. , Forbes W. F.
Published: May 2006

The electronic spectra of benzaldehydes in the region 220–360 mμ are recorded and discussed in terms of previously stated hypotheses. The formyl group is shown to endow benzene derivatives with spectral properties similar to those of the acetyl group in acetophenones, except that steric interactions are slightly modified.
LIGHT ABSORPTION STUDIES: PART XIII. THE ELECTRONIC ABSORPTION SPECTRA OF RING-SUBSTITUTED ANILINES
Authors: Forbes W. F. , Leckie I. R.
Published: May 2006

A spectral analysis of benzene derivatives in terms of steric and electronic interactions is extended to ring-substituted anilines.
THE KINETICS OF MOLECULAR SIEVE ACTION. SORPTION OF NITROGEN–METHANE MIXTURES BY LINDE MOLECULAR SIEVE 4A
Authors: Habgood H. W.
Published: May 2006

This system illustrates "partial molecular sieve action". Methane has a higher affinity for the sorbent and hence is preferentially sorbed at equilibrium, while nitrogen diffuses through the crystal more rapidly and thus is preferentially taken up during the early stages of sorption. Measurements were made with the pure gases and with mixtures at 0 °and −79.4 °C. The sorption isotherms fit Langmuir equations and the isosteric heats of sorption are essentially independent of concentration. The sorption rates for the pure gases may be characterized by diffusion coefficients, D, calculated in the usual manner assuming the flux of diffusion to be proportional to the concentration gradient. The resultant values for D increase with increasing sorbate concentration. Diffusion of a mixture may be formally characterized by D's for each component. While that for methane is approximately the same as for methane alone, D for nitrogen in mixtures is much larger than for the pure gas and also varies with composition. This, as well as the existence of a temporary maximum in the amount of nitrogen sorbed, may be explained by considering the driving force for diffusion to be the gradient in chemical potential rather than in concentration.
SYNTHESIS OF N-SUBSTITUTED DIISOPROPANOLAMINES, THEIR SEBACATE POLYESTERS AND POLYURETHANE ELASTOMERS
Authors: Boivin Jean L.
Published: May 2006

Several N-substituted diisopropanolamines were prepared by reacting aqueous solutions of amines with excess propylene oxide at ordinary pressure but higher N-substituted diisopropanolamines had to be prepared in an autoclave at 200 °C. The ionization constants of these bases were measured and recorded as pKa values. Their infrared absorption spectra gave bands common to all diisopropanolamines mainly at 3.04, 7.14, 7.55, 7.85, 9.45, 10.6, and 11.95 microns. Their condensation with sebacic acid gave the corresponding polyesters, which were soluble in strong acids and had molecular weights of about 1500. The hydroxyl-terminated polyesters were cured with a slight excess of 2,4-tolylene diisocyanate at 100 °C for 2 days to yield elastomers of brittle temperatures in the region of −50 °C.
THE SPONTANEOUS PRECIPITATION OF HYDRATED ALUMINA FROM ALUMINATE SOLUTIONS
Authors: Vrbaški T. , Iveković H. , Pavlović D.
Published: May 2006

The rates of spontaneous precipitation of hydrated alumina from unseeded and metastable sodium aluminate solutions of a molar relation for Na2O/Al2O3 (α) ranging from 1.15 to 1.60 have been investigated. All precipitation curves showed autocatalytic characteristics with a pronounced induction period, during which no precipitation occurred, a steady state period, and a period of delayed precipitation. Empirical equations for calculating the maximum precipitation rate, for the time when this precipitation takes place, and for the amount of the precipitate at equilibrium for any of these aluminate solutions have been developed.
AN INTERPRETATION OF THE MOISTURE DESORPTION ISOTHERM OF WHEAT
Authors: Becker H. A.
Published: May 2006

It is shown that the moisture desorption isotherm of wheat can be interpreted in harmony with Cassie's theoretical assumptions regarding adsorption on localized sites by the equation[Formula: see text]where N is the number of adsorbed molecules per gram of wheat and S is the number of localized sites. Kf/(1 + Kf) is a Langmuir-type factor for adsorption of the low energy fraction of molecules, and K′fn is a factor for adsorption of the normally condensed fraction of molecules. In agreement with theory K′,n,and S are independent of temperature. The dependence of K on temperature gives a value of −6.27 kcal/mole for the partial molal enthalpy of dilution of the low energy fraction of molecules, which is in the order of magnitude of a hydrogen bond. The analysis also illuminates the practice of the drying of wheat. An exact correspondence appears to exist between the calculated values of S and the apparent surface (or equilibrium) moistures observed in studying the diffusion of moisture out of wheat. The theoretical relation[Formula: see text]is therefore given for predicting apparent surface moisture contents in the vacuum drying of wheat, where[Formula: see text]
NEUTRON CAPTURE CROSS SECTION OF I129 AND I130
Authors: Roy J. C. , Wuschke D.
Published: May 2006

The capture cross section of I129 for 2200 m/sec neutrons and its resonance capture integral were determined by counting the beta rays emitted by the 12.5-hour I130 formed by an (n, γ) reaction on I129. The σ2200 was found to be 26.7 ± 2.0 barns and the resonance capture integral 36 ± 4.0 barns. The effective capture cross section of I130 for reactor neutrons was measured to be 18.0 ± 3.0 barns by counting the beta rays emitted by the 8.1-day I131 produced by successive neutron capture in I129. The neutron fluxes were measured with cobalt monitors; the thermal cross section and the resonance capture integral of Co59 were taken to be 36.5 and 48.6 barns.
ON THE PREPARATION AND SINTERING OF CLOUD PRECIPITATING AGENTS. LEAD DI-IODIDE MICROCRYSTALS
Authors: Papée Henry M.
Published: May 2006

not available
DONOR ACCEPTOR REACTIONS OF TITANIUM TETRACHLORIDE WITH FORMAMIDE AND N,N-DIMETHYL FORMAMIDE
Authors: Archambault Jacques , Rivest Roland
Published: May 2006

Co-ordination complexes of titanium tetrachloride with formamide and N,N-dimethyl formamide have been prepared. All the complexes found are explained through a co-ordination number of 6 for titanium (IV).The infrared spectra of these compounds were measured; a negative shift observed for the carbonyl frequency and a positive shift observed for what is thought to be the C—N frequency are explained by a co-ordination through the oxygen of these molecules. Structural formulas are proposed for the compounds obtained.
RECIPROCAL SALT PAIRS, INVOLVING THE CATIONS Li2, Na2, AND K2, THE ANIONS SO4, AND Cl2, AND WATER, AT 25 °C
Authors: Campbell A. N. , Kartzmark E. M. , Lovering E. G.
Published: May 2006

In the reciprocal salt pair Li2, K2, Cl2, SO4, and water, at 25 °C there are large areas in which potassium sulphate and potassium lithium sulphate (KLiSO4) are separately in equilibrium with solution. Two incongruent invariant points exist. At one of these the composition of the solution is 0.917 mole fraction chloride, 0.437 mole fraction lithium, and 19.4 moles of water per total mole of salt, the equilibrium solid phases being potassium chloride, potassium sulphate, and the double salt. At the second, the composition of the solution is 0.967 mole fraction chloride, 0.870 mole fraction lithium, and 13.8 moles of water per mole of salt, the solid phases being potassium chloride, double salt, and lithium sulphate monohydrate. One congruent invariant point exists, at which the composition of the solution is 1.00 mole fraction chloride, 0.960 mole fraction lithium, and 9.6 moles of water per mole of salt, the solid phases being lithium sulphate monohydrate, lithium chloride monohydrate, and potassium chloride.In the reciprocal salt pair Li2, Na2, Cl2, SO4, and water, at 25 °C there is an incongruent invariant point at which the composition of the solution is 0.873 mole fraction chloride, 0.668 mole fraction lithium, and 15.1 moles water per total mole of salt, the solid phases being sodium chloride, solid solution of sodium and lithium sulphates, and lithium sulphate monohydrate. A congruent invariant point exists, at which the composition of the solution is practically entirely lithium chloride, the solid phases present being lithium chloride monohydrate, lithium sulphate monohydrate, and sodium chloride.
THE ELECTRICAL POLARIZATIONS OF BIS-MERCURIALS
Authors: Sawatzky Henry , Wright George F
Published: May 2006

Very dilute solutions of diphenylmercury in carbon tetrachloride have been found not to have orientation polarization, but in not-so-dilute carbon tetrachloride or in dioxane and benzene at any concentration there is evidence of moment. Moreover, these moments vary negatively in carbon tetrachloride and dioxane and positively in benzene with respect to temperature. The angular C—Hg—C linkage responsible for orientation polarization is also demonstrated by appreciable moments for para methylmercuri-bis-benzene and the homologous durene. Magnitudes comparable with the aryl analogues are found for several alkyl-bis-mercurials, but the similarity in the moments of trifluoromethyl and methyl-bis-mercury as well as a temperature coefficient for moment of the latter compound indicates that the C—Hg—C linkage may vary widely and easily. However, a lower limit may be set by the moments of mercuracyclohexane and mercuracycloheptane in which the mercury angle is fixed by the cyclic structure.
THE CONDENSATION OF RHODANINE WITH AROMATIC DIALDEHYDES AND SOME RELATED COMPOUNDS
Authors: Allan Frederick J. , Allan G. Graham , Thomson J. B.
Published: May 2006

The condensation of rhodanine and its 3-ethyl and 3-phenyl derivatives with terephthaldehyde, pyridine-2,6-dicarboxaldehyde, and phthaldehyde has been investigated. Twenty-nine 5-arylidene-rhodanines containing an electrophilic substituent in the aromatic ring have been prepared.
POTATO X VIRUS: PART I. THE SIZE AND SIZE DISTRIBUTION OF POTATO X VIRUS IN TOBACCO SAP
Authors: Reichmann M. E.
Published: May 2006

Assuming an irreversible, random, end-to-end aggregation of a small percentage of potato X virus in tobacco sap, the flow birefringence parameters of such polydisperse systems have been calculated. The extinction angles χ were evaluated for different values of the ratio G/θ1(G gradient θ1, rotary diffusion constant of non-aggregated virus) for preparations containing between 0 and 15% by weight of aggregated material. A particle length of 6200 Å for the non-aggregated virus particle was derived and an amount of 13–15% aggregated material was estimated.A partially purified and fractionated preparation of potato X virus was also investigated and an average particle length of 5400 Å was derived. Because of the possible contribution of small fragments, this length was taken as the lower limit.The flow birefringence – gradient curve indicated that the potato X virus behaves like a rigid particle. No evidence of flexibility was obtained from extinction angle – gradient measurements in the range 0.1–0 M phosphate buffer concentrations at pH 7.2.
OCCURRENCE OF β-DOLABRIN (4-ISOPROPENYLTROPOLONE) IN WESTERN RED CEDAR (THUJA PLICATA DONN.)
Authors: Gardner J. A. F. , Barton G. M.
Published: May 2006

The steam-volatile oil of western red cedar contains traces of a fifth tropolone, β-dolabrin (4-isopropenyltropolone), in addition to α-, β-, and γ-thujaplicin and 7-hydroxy-4-isopropyltropolone. The presence of β-dolabrin, previously obtained from Japanese "Hiba" wood by Nozoe, was detected by paper chromatography and proved by isolation of a sample from the steam-volatile oil by a combination of sodium salt precipitation, fractional crystallization, and preparative paper chromatography. The approximate composition of the steam-volatile oil from butt heartwood is given.
DISTRIBUTION OF NUCLEAR CHARGE IN THE PROTON-INDUCED FISSION OF Th232
Authors: Pate B. D. , Foster J. S. , Yaffe L.
Published: May 2006

The cross sections for the independent formation of I130, I131, Te131, I132, and I134 and for the cumulative formation of Te132, I133, and I135 in the proton-induced fission of Th232 have been measured at nine proton energies between 8 and 87 Mev. From these data and from published total chain yield data, charge distribution curves have been obtained. These are compared with published charge distribution curves for uranium fission at energies up to 480 Mev and together they show a shift of the most probable fission product charge toward stability and a widening of the distribution with increasing bombarding energy. These phenomena are interpreted in terms of current models for nuclear reactions.
DISSOCIATION CONSTANTS OF THE CYANOHYDRINS OF SOME TRITERPENE KETONES
Authors: Wheeler Owen H. , Gaind V. S.
Published: May 2006

The reactivity of a number of triterpene ketones towards cyanohydrin formation is influenced by groups present in rings remote from the keto group. The results are interpreted as evidence of "conformational transmission" of the effects of the substituents.
THE CONFIGURATION OF GLYCOSIDIC LINKAGES IN OLIGOSACCHARIDES: VII. 4-O-β-D-GALACTOPYRANOSYL-D-GALACTOSE FROM WHITE BIRCH WOOD
Authors: Gillham J. K. , Perlin A. S. , Timell T. E.
Published: May 2006

not available
ADDITION OF PYRROLES TO 1,4-BENZOQUINONE
Authors: Bullock E.
Published: May 2006

not available
THE N- AND C-TERMINAL END GROUPS OF HAIR KERATIN
Authors: Kerr M. F. , Godin C.
Published: May 2006

The N-terminal and the C-terminal residues of human and horse hair and partially reduced hair have been determined. Aspartic acid, glutamic acid, glycine, serine, threonine, alanine, and valine were identified as N-terminal groups. Aspartic acid, glutamic acid, glycine, serine, threonine, and alanine were identified as C-terminal groups. These are the same N-terminal and C-terminal amino acids as have been found previously for wool and feather keratin.
DETERMINATION OF URANIUM IN FLOTATION CONCENTRATES AND IN LEACH LIQUORS BY X-RAY FLUORESCENCE
Authors: Smithson G. L. , Eager R. L. , VanCleave A. B.
Published: May 2006

X-Ray fluorescence has been applied to the analysis of flotation concentrates obtained from pegmatitic uranium ores occurring in Northern Saskatchewan. Approximate uranium analyses can be obtained by direct measurement on flotation concentrates but more accurate results are obtained by using an internal standard such as strontium or yttrium. The time required for an analysis, as compared to that of conventional chemical or fluorimetric methods, is considerably reduced and flotation pilot plant operations can therefore be more effectively controlled. The method has been extended to include the analysis of sulphate leach liquors obtained from the leaching of pegmatitic ores and their flotation concentrates. Organic phases obtained in liquid – liquid extraction studies can also be rapidly analyzed for uranium by X-ray fluorescence.
FUSED HETEROCYCLICS: PART III. SYNTHESIS OF QUINOLINO-(2′:3′:3:4)-QUINOLINE
Authors: Anet Ragini
Published: May 2006

Quinolino-(2′:3′:3:4)-quinoline has been synthesized from 3-aminoquinoline-4-carboxylic acid via 4′-hydroxyquinolino-(2′:3′:3:4)-quinoline.
THE INTERACTION OF FRIEDEL–CRAFTS CATALYSTS WITH ORGANIC MOLECULES: I. THE CH3COCl:AlCl3 SYSTEM
Authors: Cook Denys
Published: May 2006

An infrared study of the liquid complex of aluminum chloride with acetyl chloride has been undertaken. The results indicate that the pure liquid complex is not a simple mixture, but consists of (1) the donor–acceptor complex [Formula: see text] and (2) the ions [CH3CO]+ and [AlCl4]−. A solution of the liquid complex in a solvent of high dielectric constant like nitrobenzene (ε = 36.1) contains both these species, but in a low dielectric constant solvent like chloroform (ε = 5.05) only (1) is present. The carbon–chlorine bond in (1) is modified. The mechanism of Friedel–Crafts ketone synthesis is briefly examined in the light of these results.
BRIDGING AND NON-BRIDGING LIGAND EFFECTS IN REDOX REACTIONS OF METAL IONS
Authors: Taube Henry
Published: May 2006

not available
SOME THEORETICAL ASPECTS OF ELECTRON-TRANSFER PROCESSES IN AQUEOUS SOLUTION
Authors: Laidler Keith J.
Published: May 2006

A theoretical treatment has been developed for the rates of electron-transfer reactions in aqueous solution, with particular reference to the ferric–ferrous system. The reactions are considered to be diffusion-controlled processes, the approach of the ions being hindered by the electrostatic repulsion between them. Calculations have been made of the free energy of the diffusion process and for the repulsion, account being taken of the variation in dielectric constant with the electric field. The form of the potential-energy barrier between the ions is calculated for various separations, and the transmission coefficient calculated using the quantum-mechanical expression corresponding to a rectangular barrier. The total free energy of activation for the reaction, which is the sum of the contributions due to diffusion, repulsion, and tunnelling, is found to pass through a minimum at a separation of about 4 Å. The calculated free energy of activation for the reaction is 15.4 kcal, in good agreement with the experimental value of 16.8 kcal. The energy and entropy of activation for the reaction are also briefly discussed.
ON THE THEORY OF ELECTROCHEMICAL AND CHEMICAL ELECTRON TRANSFER PROCESSES
Authors: Marcus R. A.
Published: May 2006

Kinetic studies of simple electron transfer systems in solution and at electrodes have revealed a number of interesting and simplifying features. The chemical reactions also represent one of the very few cases in kinetics where it has been possible to make reasonable calculations of the absolute rate constant without introducing adjustable parameters or arbitrary assumptions. Because of their comparative simplicity, these processes also serve as a useful kinetic tool for investigating ion–solvent–electrode interactions.In the present paper the writer's recent theoretical investigations are summarized and used to interpret data obtained from both solution and electrode studies. Various phenomena are discussed in the light of this theory and several predictions of behavior are made. The topics considered include effects of changing the overpotential or the standard free energy of reaction, the ionic structure, temperature, salt concentration, solvent, and electrode material. Both the parallelism between chemical and electrochemical transfers and the role played by the electrostatic image in the latter case are discussed. A classification of reactants is employed throughout, based in part on differences in the theoretical treatment.
LIMITING CONDUCTANCE OF LYONIUM AND LYATE IONS
Authors: Kilpatrick Martin
Published: May 2006

The problem of proton mobility has been considered in H2O–CH3OH, H2O–D2O, and H2O–H2O2 solvents from the current viewpoint of the mechanism of proton mobility for aqueous solutions. Mixed solvents are more complicated in that one must consider the relative basicity and acidity of the species competing for the protons. It is concluded that for dilute solutions of HClO4, where water is replaced by hydrogen peroxide, the decrease in equivalent conductance relative to that of KCl in the same solvent mixture is due to the partial elimination of the proton transfer process.For highly acidic non-aqueous solvents of high dielectric constants such as HF, HCN, and HCOOH, the problem of the weakness of the usual "strong" acids of aqueous solution makes a direct determination of the limiting equivalent conductances difficult. In the case of anhydrous hydrogen fluoride the available experimental evidence indicates that the limiting conductance of the lyonium ion is approximately the same as that of the potassium ion but the lyate ion has a higher limiting conductance than other stable anions.The higher proton mobility in ice leads one to expect that hydrogen-bonded systems may be found where the conductivity may approach that of electronic semiconductors.
EXCHANGE BETWEEN METALS AND THEIR IONS IN SOLUTION
Authors: King Cecil V. , McKinney Nancy E.
Published: May 2006

The mechanisms by which a metal specimen can acquire radioactivity when immersed in a tracer solution of its own ions are discussed. Consideration is given to the roles of exchange current, adsorption, local cell electrolysis, corrosion, and self-diffusion within the metal. It is shown that exchange current cannot be measured by the tracer method unless conditions are unusually favorable, and that too little attention has been paid to the role of internal diffusion. Some experimental results with silver are presented and the importance of internal diffusion is shown.
THE DETERMINATION OF KINETIC PARAMETERS OF REDOX REACTIONS FROM CURRENT–POTENTIAL CURVES
Authors: Randles J. E. B.
Published: May 2006

Methods are suggested for calculating kinetic parameters of moderately rapid redox reactions from current–potential curves obtained with (a) rotating electrodes or stationary electrodes in stirred solutions, (b) dropping mercury electrodes. Experimental results for the V2+/V3+ reaction at a dropping mercury electrode are presented and compared with a-c. impedance measurements on the same system. It is found that there is a good agreement between the kinetic parameters obtained by the two methods when the current–potential curves are interpreted with the aid of Koutecky's theory of diffusion to a dropping mercury electrode.
CATHODIC ORGANIC PROCESSES
Authors: Allen M. J.
Published: May 2006

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THE THEORY OF FORMATION OF HIGH RESISTANCE ANODIC OXIDE FILMS
Authors: Young L.
Published: May 2006

Various models are considered for the growth of anodic oxide films (metal ions mobile). In general, a transition is expected, as the thickness of the film is increased, from control by the metal/oxide interface (Cabrera and Mott) with very thin films to control by the movement of ions through the body of the film (Verwey), with the concentration of mobile ions taking up the value (p, say) which gives electroneutrality. The field strength only varies with thickness in the transition region of thickness. Dewald's theory is the special case of p zero, which gives a field increasing continuously to infinite thickness. The high field production of Frenkel defects (with the vacant cation sites immobile and the interstitial ions mobile) as postulated by Bean, Fisher, and Vermilyea, and a slight mobility of oxygen ions are two processes which would allow p to vary with the field strength, and which would, therefore, give rise to "overshoot" in the transients in the field strength which occur when the applied current is suddenly changed. However, if the field strength is sufficiently great to produce Frenkel defects it would be expected to be sufficiently great to cause the vacancies to be mobile. This case is considered. Finally, it is noted that in an amorphous oxide it is difficult to maintain a distinction between lattice and interstitial ions, and, in fact, a range of site energies and jump distances would be expected. Some of the observed features (including "overshoot", and Tafel slope anomalies) of the kinetics for tantalum may, therefore, be due simply to the fact that the oxide is amorphous.
THE FORMATION AND PROPERTIES OF PASSIVE FILMS ON IRON
Authors: Cohen Morris
Published: May 2006

A unified mechanism for the formation of passive films on iron in aqueous solutions is presented. The effects of water, oxygen, and oxidizing and non-oxidizing ions are considered. The γ-Fe2O3 film is formed first by the oxidation of water-formed magnetite and further thickening of the film takes place by the oxidation of diffusing Fe++ ion at the water surface of the oxide film. The main force leading to diffusion is the field set up by the adsorbed negative ion and the positive Fe++ ions at the surface of the metal. Some of the properties of the protective γ-Fe2O3 film and factors leading to its destruction are discussed.
THE ELECTROCHEMICAL BEHAVIOR OF THE NICKEL – NICKEL OXIDE ELECTRODE: PART I. KINETICS OF SELF-DISCHARGE
Authors: Conway B. E. , Bourgault P. L.
Published: May 2006

The nickel – nickel oxide electrode forms the positive plate in the charged nickel–cadmium battery. After "charging" the electrode to a chemical state represented by the non-structural formula NiOx, where x can vary from about 1.4 to 1.8 depending on the current density and temperature, loss of oxygen and a fall of potential on open circuit occurs. In the present work this "self-discharge" effect has been examined by study of (i) the rate of decay of e.m.f. on open circuit, (ii) rate of oxygen evolution on open circuit, (iii) the electrochemical capacity of the electrode, and (iv) the build-up or charging curves for the electrode. The decay behavior has been studied in aqueous KOH solutions from 0.0015 to 15 M. Tafel slopes are obtained from the plots of e.m.f. vs. log (time of decay), and abrupt changes occur at certain electrode potentials which indicate changes of rate-determining mechanism in the self-discharge process. The slopes observed are interpreted in terms of a new scheme of consecutive reactions for anodic oxygen evolution by deducing, by means of the Christiansen method, the relevant Tafel slopes. It is shown that the scheme proposed uniquely accounts for the experimental behavior and that the change of mechanism observed in the self-discharge can only be explained if two consecutive and not alternative processes are involved. The dependence of the rates of self-discharge upon OH− ion and water activity is deduced and the significance of these results is discussed.
THE SYNTHESIS OF 4-O-β-D-GALACTOSYL-D-GLUCOSE (LACTOSE)
Authors: Curtis E. J. C. , Jones J. K. N.
Published: May 2006

4-O-β-D-Galactosyl-D-glucose (lactose) has been synthesized using a modification of the Koenigs–Knorr reaction.
PERACETIC ACID OXIDATION OF HALOGENATED AZOBENZENES
Authors: Gagnon Paul E. , Newbold Brian T.
Published: May 2006

A series of dihalogenated and five tetrachloroazobenzenes were oxidized to the corresponding azoxy compounds by means of 30% hydrogen peroxide in glacial acetic acid, the reaction being carried out at about 60–70 °C, for 24 hoursAs expected, the yields, in general, obtained from azobenzenes containing substituents in the 2,2′-positions were lower than those from compounds having substituents in the 3,3′- and 4,4′-positions, which gave very good results.
A NEW SPECTROPHOTOMETRIC PROCEDURE FOR PLATINUM WITH TIN (II) CHLORIDE
Authors: Berman S. S. , Goodhue E. C.
Published: May 2006

A spectrophotometric procedure has been developed for microgram quantities of platinum utilizing an absorption peak at 310 mμ formed when platinum salts react with tin (II) chloride. The method offers a 5-fold increase in sensitivity over the conventional platinum – tin (II) chloride procedure. Several factors influencing the intensity and stability of the absorbing species, whose nature is unknown, are described. Palladium and rhodium produce gross interferences, but small quantities of iridium, iron, copper, and chromium can be tolerated. The procedure is applicable to fumed sulphuric acid solutions of platinum and to solutions of platinum in nitric acid. The recommended concentration range is 0.4 to 6 p.p.m. when measurements are made in 1.0- cm cells.
MICROCALORIMETRY OF ADSORPTION OF WATER VAPOR ON LEAD DI-IODIDE
Authors: Papée Henry M.
Published: May 2006

Using a microcalorimeter of the Calvet type, measurements of the total heat of adsorption of water vapor on microcrystals of lead di-iodide have been made. By comparing the results obtained with those relating to the kinetic process of surface sintering by water vapor, heats for the process of sintering were calculated. The same sintering characteristics were found for preheated and unheated samples, but it was found that the heated product adsorbs more water than the original salt. Qualitative experiments on lead mono-iodide show a different pattern of heat evolution with time, and the over-all process requires more water to reach completion than in the case of di-iodide. The heats evolved are much greater, probably partly due to the reaction of water with the surface.
POTATO X VIRUS: PART III. LIGHT SCATTERING STUDIES
Authors: Reichmann M. E.
Published: May 2006

Light scattering studies were made on a non-aggregated potato X virus preparation. The data are consistent with a cylindrical model 5400 Å long having a molecular weight of 35 × 106. The weight average length of 4700 Å was determined from the high angle measurements. The low value of the weight average length, as compared with the length of the most frequent particle from electron microscopy, is interpreted in terms of a slight tendency to aggregate side-by-side. The insignificant extent of this aggregation is demonstrated by a direct evaluation of the weight average diameter. The value of 109 Å obtained is only 9% higher than the number average diameter reported in the literature.
DÉRIVÉS DU TRIMÉTHYL-1,8,8 BICYCLO[3,2,1]OCTANE: III. SYNTHÈSE DES TRIMÉTHYL-1,8,8 BICYCLO[3,2,1]OCTANOLS-2α ET -2β ET DES TRIMÉTHYL-5,8,8 BICYCLO[3,2,1]OCTANOLS-2α ET -2β
Authors: Favre H. , Lefebvre M. , Richer J-C.
Published: May 2006

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DÉRIVÉS DU TRIMÉTHYL-1,8,8 BICYCLO[3,2,1]OCTANE: IV. DÉTERMINATION DES CONFIGURATIONS DES DEUX DIMÉTHYL-5,5 CYCLOHEXANEDIOLS-1,3
Authors: Favre H. , Richer J-C.
Published: May 2006

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A NEW MOLECULAR REARRANGEMENT: IV. FURTHER OBSERVATIONS ON THE CHEMISTRY OF 1-NITRO-2,3,5,6-TETRAHYDRO-1(H)-IMIDAZ(1,2-a)IMIDAZOLE AND 1-(β-CHLOROETHYL)-2-IMIDAZOLIDONE
Authors: McKay A. F. , Kreling M.-E.
Published: May 2006

Chlorination of 1-(β-hydroxyethyl)-2-nitrimioimidazolidine gives a mixture of 1-(β-chloroethyI)-2-nitriminoimidazolidine and 1-nitro-2,3,5,6-tetrahydro-1(H)-imidaz(1,2-a)imidazole hydrochloride. The other products, 1-(β-aminoethyl)-3-nitro-2-imidazolidone hydrochloride and 1-(β-nitraminoethyl)-2-imidazolidone, isolated during the original study of the chlorination of 1-(β-hydroxyethyl)-2-nitriminoimidazolidine are formed by the action of ethanol on 1-nitro-2,3,5,6-tetrahydro-1(H)-imidaz(1,2-a)imidazole hydrochloride. Amines add to 1-nitro-2,3,5,6-tetrahydro-1(H)-imidaz(1,2-a)imidazole nitrate to give the corresponding 1-(β-nitraminoethyl)-2-substituted amino-2-imidazoline nitrates. These reactions and the aminolysis of 1-(β-chloroethyl)-2-imidazolidone are described in detail.
INTERPRETATION OF LIGHT SCATTERING DATA OBTAINED FROM SOLUTIONS OF LARGE ROD-LIKE PARTICLES
Authors: Reichmann M. E.
Published: May 2006

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CYCLIZATION OF 1,3-BIS-(β-CHLOROETHYL)-UREA
Authors: Kreling M. -E , McKay A. F.
Published: May 2006

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PREPARATION OF 1,5-DIPHENYLNAPHTHALENE
Authors: Bailey A. S.
Published: May 2006

The transformation of 1,5-dioxodecalin into 1,5-diphenylnaphthalene is described.
PREPARATION AND CHEMISTRY OF TRANS 1-CYANO-4-CHLORO-2-BUTENE
Authors: Daessle Cl. , Tarlton E. J. , McKay A. F.
Published: May 2006

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INFRARED SPECTRUM OF CRYSTALLINE H2S2
Authors: Zengin Numan , Giguère Paul A.
Published: May 2006

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THE REACTION OF ACTIVE NITROGEN WITH HYDROGEN BROMIDE
Authors: Dunford H. B. , Melanson Bernadine E.
Published: May 2006

The reaction of active nitrogen with hydrogen bromide was found to produce bromine and ammonium bromide as the main products, along with traces of compounds tentatively identified as bromamine, NH2Br, and bromimine, NHBr2. Hydrogen abstraction from hydrogen bromide by nitrogen atoms, imine and amine radicals can account for ammonia formation. Considerable catalysis of nitrogen atom recombination by hydrogen bromide appears to occur. A resonance transfer of the electronic energy responsible for the nitrogen afterglow to bromine with a resultant bromine emission spectrum is proposed to account for the orange reaction flame.
MEASUREMENT OF Ni63 WITH A 2π PROPORTIONAL COUNTER
Authors: MacEwan J. R. , MacEwan J. U. , Yaffe L.
Published: May 2006

Measurement of Ni63, a β−emitter with very low maximum energy, is described. External absorption curves were determined in aluminum and a range 8.5 ± 0.5 mg/cm2 was found. This corresponds to a maximum energy of the β radiation of 72.7 ± 2.5 kev, in reasonably good agreement with values obtained by other methods. Self-absorption curves of electrolytically deposited samples were obtained and attempts made to compare these with the theoretical predictions of Gora and Hickey.
PROTONATION OF THE CARBONYL GROUP: II. THE BASICITIES OF SUBSTITUTED BENZALDEHYDES
Authors: Yates K. , Stewart Ross
Published: May 2006

The basicities of seven meta- and para-substituted benzaldehydes have been determined by a spectrophotometric method in sulphuric acid media. The simple Hammett relation does not hold for these bases but a good correlation exists between [Formula: see text] and σ+. The effects of substitution on the wavelengths of maximal ultraviolet absorption in benzaldehyde are compared with those in acetophenone.The basicity of o-tolualdehyde was determined in an attempt to estimate the steric effects of ortho substitution. The effects of symmetrical trisubstitution on the basicity of benzaldehyde and acetophenone are compared and discussed.
QUANTITATIVE GAS CHROMATOGRAPHY OF REACTION PRODUCTS FROM THE CATALYTIC OXIDATION OF ETHYLENE
Authors: Amberg C. H. , Echigoya E. , Kulawic D.
Published: May 2006

A simple two-stage gas chromatograph is described which employs only one detector for both effluent streams. It was designed specifically for the routine quantitative analysis of mixtures of ethylene oxide, carbon dioxide, and ethylene in the presence of water vapor and a large excess of air, and for concentrations down to 0.2% by volume of individual components.
THE STEREOCHEMISTRY OF THE PIMARIC ACIDS
Authors: Edwards O. E. , Howe R.
Published: May 2006

Isodextropimaric and dextropimaric acids have been shown to have the same stereochemistry at C1, C11, and C12, but to be epimeric at C7. A critical survey is made of the present evidence with regard to the stereochemistry at C13 in these acids. Preliminary experiments on the action of formic acid on isodextropimaric acid are reported.
APPLICATIONS OF PROTON MAGNETIC RESONANCE SPECTRA IN FATTY ACID CHEMISTRY
Authors: Hopkins C. Y. , Bernstein H. J.
Published: May 2006

An introductory study has been made of the proton magnetic resonance spectra of fatty acids, fatty acid esters, and natural glyceride oils. Characteristic signals were recorded for the hydrogens of such groupings as hydroxy, acetoxy, and epoxy; isolated, conjugated, and methylene-interrupted double bonds; and others. Examples are given of the application of this technique in identifying the fatty acids of natural glyceride oils. Semiquantitative estimations are shown to be feasible. Evidence for Nunn's formula for sterculic acid is discussed on the basis of the spectra of the acid and its derivatives.
A SURVEY OF THERMODYNAMIC PARAMETERS FOR SOLVOLYSIS IN WATER
Authors: Robertson R. E. , Heppolette R. L. , Scott J. M. W.
Published: May 2006

A method is suggested for determining the standard state entropies [Formula: see text] of the transition state for the neutral hydrolysis of esters in water. This has required the development of methods for approximating initial state parameters where experimental data are lacking.Characteristic linear correlations between the entropy and enthalpy of activation are observed for hydrolysis in water, as well as for the bimolecular halide exchange reaction in acetone and for acid–base equilibria. Explanations are advanced to explain the observed trends.From the derived standard state entropies, a method for estimating the charge development in the transition state for the methyl and isopropyl halides is proposed. With this further detailed knowledge of the transition state in the methyl halide series, reasonable values of the activation enthalpy can be calculated from available thermochemical data.
ABSOLUTE CONFIGURATION OF (−)-HOMOSTACHYDRINE
Authors: Robertson A. V. , Marion Léo
Published: May 2006

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SEPARATION OF NICKEL AND COBALT BY PAPER CHROMATOGRAPHY
Authors: Weidmann Gerhard R.
Published: May 2006

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PYRIDINIUM BETAINES OF 1,3-INDANDIONE SERIES
Authors: Frangatos Gerassimos , Taurins Alfred
Published: May 2006

2-Bromo- (II) and 2,2-dibromo-1,3-indandione (III) react with pyridine, 3- and 4-methylpyridine, and 2-, 3-, and 4-pyridinecarboxylic acids to give 1-(3-hydroxy-1-oxo-2-indenyl)-pyridinium hydroxide betaines. In the betaines derived from pyridinecarboxylic acids the negative charge is located not in the carboxylic group but on the carbonyl oxygen atoms.