bluuebunny/crossref_metadata_2025 huggingface dataset:
COMPARISON OF EFFECTIVE IONIC RADII IN SOLUTION
Authors: Canady William J.
Published: May 2006

not available
STUDIES IN THE WAGNER–MEERWEIN REARRANGEMENT. PART II
Authors: Anet F. A. L. , Bavin P. M. G.
Published: May 2006

Dibenz[b,f]oxepin and its 10-methyl derivative have been prepared by ring expansion of suitable xanthene derivatives. 2-Flurophenanthrene was synthesized from 2-fluorofluorene.
PREPARATION OF DISTILBENE (1,2,3,4-TETRAPHENYLCYCLOBUTANE)
Authors: Morton J. M. , Flood E. A. , Bright N. F. H.
Published: May 2006

The reaction between benzyl chloride and potassium amide in liquid ammonia has been shown to yield, in addition to stilbene as the main product, considerable quantities of 1,2,3,4-tetraphenylcyclobutane. The isomer of this compound formed in this reaction is believed to be one that has not been reported previously.
AMIDOMYCIN, A NEW ANTIBIOTIC FROM A STREPTOMYCES SPECIES, CHEMICAL STRUCTURE
Authors: Vining L. C. , Taber W. A.
Published: May 2006

Amidomycin, an antibiotic active primarily against yeast, has been isolated from a Streptomyces species. The Compound C10H68O12N4. is neutral, optically active, and shows no unsaturation nor characteristic light absorption maxima. It is composed of 4 moles each of D(−)-valine and D(−)-α-hydroxyisovaleric acid, linked alternately by ester and amide bonds to form a 24-membered ring (I). This structure is assigned from the following observations: on mild alkaline hydrolysis 4 moles of alkali are consumed with formation of a hydroxy acid, C10H19O4N (II). The latter on distillation gave a crystalline lactone, C10H17O3N, considered to be 3,6-diisopropyl-2,5-diketomorpholine (III), which was hydrolyzed to give 1 mole each of D(−)-valine and D(−)-α-hydroxyisovaleric acid.Amidomycin is closely related to valinomycin, an antibiotic isolated from Streptomycesfulvissimus and shown to be a 24-membered ring compound containing D(−)-valine, D(−)-α-hydroxyisovaleric acid, L(+)-valine, and L(−)-lactic acid. It also resembles the enniatins, produced by certain species of Fusarium, but differs from these compounds in the number of units in the ring structure as well as in containing D(−)-valine rather than an N-methyl-L-amino acid.
THE PHOTOLYSIS OF KETENE AT LOW TEMPERATURES
Authors: Paterson W. G. , Gesser H.
Published: May 2006

The photochemical decomposition of ketene at 2700 Å has been investigated at −78 °C. The quantum yield of carbon monoxide is two, indicating that the recombination of methylene radicals does not occur at this low temperature.
ON THE PROTON MAGNETIC RESONANCE SHIFT DUE TO HYDROGEN BONDING
Authors: Korinek G. J. , Schneider W. G.
Published: May 2006

In order to investigate further the nature of the proton resonance shifts accompanying hydrogen bonding, and their relation to the properties of the hydrogen bond, the resonance shift of the acceptor molecule chloroform, interacting in turn with a variety of donor molecules, was measured. The donor liquids chosen were (Et)3N, (Et)2O, PrF, (Me)CO, and EtCN. These are all virtually non-associated in the pure state and may be expected to form simple 1:1 hydrogen-bonded complexes with chloroform, whose existence was confirmed by measuring the binary freezing-point phase diagrams. The difference between the proton shift of chloroform at infinite dilution in each of the donor solvents and at infinite dilution in inert hydrocarbon solvents was taken as the "association" shift representing the difference between chloroform in the hydrogen bonded complex and unassociated chloroform. These shifts correlate well with the expected hydrogen bond strengths in each system and the relative donor strength of the individual solvent molecules. The proton resonance technique appears as a promising method for measuring these properties.
THE VIBRATIONAL SPECTRA OF PYRIDINE, PYRIDINE-4-d, PYRIDINE-2,6-d2, AND PYRIDINE-3,5-d2
Authors: Wilmshurst J. K. , Bernstein H. J.
Published: May 2006

The infrared spectra of pyridine and pyridine-4-d in the vapor state and of pyridine-2,6-d2 and pyridine-3,5-d2 in the liquid and vapor states have been obtained. The Raman spectra of pyridine-4-d, pyridine-2,6-d2, and pyridine-3,5-d2 as liquids have also been obtained together with depolarization ratios. The vapor band contours for pyridine support the assignment of Corrsin, Fax, and Lord in most part in preference to the assignment of McCullough and co-workers but it was found necessary to reassign the b2 frequencies to give agreement between calculated and observed thermodynamic functions. The infrared and Raman data on pyridine-4-d are in agreement with the reported assignment for the a1, a2, and b1 modes but it was found necessary to reassign the b2 frequencies consistent with the present assignment in pyridine. A complete vibrational assignment for pyridine-2,6-d2 and pyridine-3,5-d2 has been made consistent with the present assignment in pyridine.
STIGMASTA-3,5,22-TRIENE AND DISTIGMASTERYL ETHER
Authors: Linburg R. G. , Cox R. H.
Published: May 2006

not available
THE EFFECT OF HYDROGEN CHLORIDE ON THE INFRARED SPECTRUM OF NYLON
Authors: Larose P.
Published: May 2006

The effect of HCl on the infrared spectrum of nylon in the form of Zytel films was studied in the region 3600 cm.−1 to 600 cm.−1. The effect of partial deuteration of the films was also observed. Definite changes in the characteristic bands of the NH—CO group show that HCl interacts with this group. The results indicate that the two NH bands at 3300 cm.−1 and 3030 cm.−1 are associated with different NH bonds. The general effect of the HCl seems best explained by assuming a polar interaction with the peptide linkage. The behavior of several of the bands is readily explained on the basis of the picture given by Fraser and Price for the NH—CO vibration.
CINÉTIQUE DE L'HYDROLYSE DE L'ADÉNOSINE TRIPHOSPHATE EN SOLUTION ALCALINE
Authors: Couture A. M. , Ouellet Ludovic
Published: May 2006

not available
DETERMINATION OF LEAD BY DITHIZONE IN A SINGLE PHASE WATER–ACETONE SYSTEM
Authors: Diaper D. G. M. , Kuksis A.
Published: May 2006

A modification of the dithizone colorimetric procedure for determination of lead has been developed. By working in an aqueous acetone system (70% acetone by volume) the usual extraction step is avoided. Aqueous ethanol or methanol may also be employed or, under suitable circumstances, water may be omitted from the solvent system. The 70% acetone system proposed is tolerant of cyanide, added to convert interfering ions into non-interfering complex ions, and the interference of copper under the conditions adopted was determined. This system was also found compatible with hydroxylamine, used as stabilizer, and with the barbital buffer. A reproducibility of about 2% was obtained when working with standards in the range from 0 to 10 μg. of lead and the technique was found to be sensitive to 0.1 p.p.m.
THE REACTION OF ACETIC AND TRIFLUOROACETIC ANHYDRIDES WITH SOME SUBSTITUTED GUANIDINE HYDROCHLORIDES
Authors: Cockburn W. F. , Bannard R. A. B.
Published: May 2006

Acetylation of the hydrochlorides of guanidine, cyclohexylguanidine, and 1-guanylpiperidine has been found to yield substituted triazines. Trifluoroacetylation of 1-guanylpiperidine hydrochloride also gives a triazine, whereas guanidine hydrochloride and cyclohexylguanidine hydrochloride are converted to bistrifluoroacetyl derivatives. The same triazines can also be obtained by acylation of the appropriate biguanide.
DIELECTRIC CONSTANTS OF LIQUID SULPHUR DIOXIDE, ETHYL CHLORIDE, AND ETHYLENE OXIDE
Authors: Nickerson J. D. , McIntosh R.
Published: May 2006

Dielectric constants of sulphur dioxide, ethyl chloride, and ethylene oxide have been measured over the frequency range 9 to 92 Mc./second and at temperatures between −35° and +20 °C. Dipole moments computed from the Debye, Onsager, and Kirkwood equations are reported and compared with the moments which are known from measurements on the gaseous substances.
THE SOLUBILITY OF MALACHITE
Authors: Scaife J. F.
Published: May 2006

The solubility at 25 °C. of the sparingly soluble basic copper carbonate malachite has been determined by two methods. The constancy of the calculated value of the solubility product in solutions of varying ionic strength has shown it to be a comparatively well-defined material suitable for the study of the complexing ability of various organic chelating compounds. Evidence is presented for the existence of a cupric ion – carbonate ion complex under appropriate pH conditions.
KINETICS OF THE PHOTOCHLORINATION OF MONOCHLOROMETHYL CHLOROFORMATE IN THE GAS PHASE
Authors: Dignam M. J. , Forbes W. G. , Roy D. J. Le
Published: May 2006

The general features of the mechanism of the over-all process [Formula: see text][Formula: see text] are similar to those for the over-all process [Formula: see text][Formula: see text] studied previously. The reaction is inhibited by HCl. Chains are terminated by two processes, one of which is first order, the other second order in atomic chlorine. The first order process is not entirely diffusion controlled and a theory is advanced to account for its nature; the homogeneous combination of chlorine atoms requires a third body, mono- and di-chloromethyl chloroformate being particularly effective. The activation energy for hydrogen abstraction from monochloromethyl chloroformate by atomic chlorine is 5.2 kcal. per mole. The C—H bond dissociation energy in monochloromethyl chloroformate is estimated to be 99.8 ± 4.5 kcal. per mole.
NUCLEAR MAGNETIC RESONANCE MEASUREMENTS IN SOLUTIONS OF ACETYLACETONE: THE EFFECT OF SOLVENT INTERACTIONS ON THE TAUTOMERIC EQUILIBRIUM
Authors: Reeves L. W.
Published: May 2006

A modified assignment of the PMR signals in acetylacetone is confirmed. The changes in intensity of selected signals with temperature are used to calculate an enthalpy of conversion of 2700 ± 100 cal. between keto and enol forms in pure acetylacetone.Interactions, which perturb the equilibrium between the tautomeric forms in dilute solution by formation of solution complexes, are studied by observing dilution chemical shifts in various solvents. The ratio of keto to enol forms is estimated from measurements of signal intensities at several dilutions in each solvent. The deviations from the correlations of Bernstein and Powling (5) between solvent dielectric constant and molar volume, and the position of the tautomeric equilibrium in dilute solutions, have been used as a criterion of solvent interaction. They are consistent with the present measurements.Typical basic, acidic, amphoteric, and neutral solvents have been chosen to investigate possible types of interaction. Cyclohexane and acetic acid do not perturb the equilibrium by any interactions. Triethylamine forms a hydrogen bonded complex through the enolic—OH group and the nitrogen lone pair, thus converting acetylacetone completely to enol form. Pyrrole forms a weakly hydrogen bonded complex through the carbonyl oxygens of the keto form. Freezing diagrams in the interacting systems are consistent with the complexes suggested by the PMR measurements.
RAMAN SPECTRA AND CONFIGURATION OF SOME α-FURYL AND α-BENZOFURYL KETOXIMES
Authors: Dullien F.
Published: May 2006

Raman spectra of α-furyl and α-benzofuryl ketoximes were taken and analyzed. It was found that the values of the CN frequencies of the isomers display regular differences. By assuming in the syn isomers a weak hydrogen bonding between the OH oxygen and the ring hydrogen, which results in an increased localization of the unbonded electron pair of the OH oxygen and, as a consequence, a decreased resonance with the ring, these differences could be interpreted in agreement with chemical experience.
REVERSIBILITY OF ALKENE OXYMERCURATION
Authors: Rodgman A. , Shearer D. A. , Wright George F
Published: May 2006

It has been shown that deoxymercuration (conversion of an α-oxyorganomercurial to the alkene) is a second-order reaction dependent on concentration of the mercurial and of the deoxymercurating acid. Moreover the rate of deoxymercuration increases with basic strength of the alkoxy substituent in the mercurial. This tendency would indicate that the rate was dependent on the strength of the acid used for deoxymercuration. The supposition has been proved by use of trifluoroacetic acid which decomposes α-2-methoxycyclohexylmercuric trifluoroacetate more slowly than does hydrochloric acid. The trifluoroacetoxymercurial decomposes to the extent of 35% whereas its synthesis is effected in 60% maximum yield from cyclohexene and mercuric trifluoroacetate. A measurable equilibrium is thus attained in this oxymercuration, though not necessarily because of a simple reversible reaction.
A RECORDING SPOON GAUGE
Authors: Hooley J. G.
Published: May 2006

The movement of the tip of a glass spoon gauge is followed by means of a linear variable differential transformer with a sensitivity of 2.2 mv. per micron. For a spoon that will stand a differential pressure of one atmosphere this amounts to 5 mv. per mm. of mercury. There is no hysteresis, the temperature coefficient is 0.1 mm. per °C, and there is a null point drift of about 0.05 mm. per hour. The over-all accuracy is 0.2 mm. in the range 0 to 760 mm.
REARRANGEMENT STUDIES WITH C14: V. THE SOLVOLYSIS OF 2-PHENYLETHYL-1-C14p-TOLUENESULPHONATE
Authors: Lee C. C. , Slater G. P. , Spinks J. W. T.
Published: May 2006

The solvolysis of 2-phenylethyl-1-C14p-toluenesulphonate in absolute ethanol, glacial acetic acid, 90% formic acid, and anhydrous formic acid gave rise to products which showed rearrangements of the C14-labeled atoms from the C-1 to the C-2 positions to the extent of 0.3%, 5.5%, 40%, and 45%, respectively. The results constitute an unequivocal proof that phenyl participation occurs in the reactions studied. The different degrees of rearrangement found for the different solvent systems are in agreement with the concept that the solvolysis process may have a range of mechanisms between the two extremes of the nucleophilic or SN2 type and the limiting or SN1 type. In the solvolysis in absolute ethanol, a small amount of "unreacted" 2-phenylethyl p-toluenesulphonate recovered from the reaction mixture was found to show isotope position rearrangement of almost the same degree as the ethanolysis product. This finding is tentatively attributed to the phenomenon of internal return involving an ethyl-phenonium p-toluenesulphonate ion-pair.
STUDY OF HALOGENATED HYDROXYPHENAZINES
Authors: Gagnon Paul E. , Keirstead Karl F. , Newbold Brian T.
Published: May 2006

The properties of chlorotrihydroxydihydrophenazine were thoroughly investigated. Oxidations with sodium perborate or hydrogen peroxide in glacial acetic acid gave chloro-trihydroxyphenazine-5,10-dioxide. Methylation gave a monomethyl derivative and acetylation yielded mono-, di-, and tri-acetyl derivatives. Benzoylation gave a tetrabenzoyl compound. Bromination gave a monobromo derivative. Nitrosation produced a mononitroso and nitration a mononitro compound. Degradation by zinc dust distillation and thermal decomposition yielded phenazine. Molecular weight and absorption spectra determinations supported the chemical evidence that the compound was 1-chloro-2(or 3),6,8-trihydroxydihydrophenazine. 1,4,9-Trichloro-2(or 3),6,8-trihydroxydihydrophenazine, 1,4,9-trichloro-2(or 3, or 8),6-dihy-droxydihydrophenazine, and 1-bromo-2(or 3),6,8-trihydroxydihydrophenazine were similarly identified.
PREPARATION AND CHEMISTRY OF Δ8-HEXAHYDRO-1,4,8-PYRIMIDAZOLE, Δ9-1,5,9-TRIAZABICYCLO(4.4.0)DECENE, AND Δ9-1,4,9-TRIAZABICYGLO(5.3.0)DECENE
Authors: Mckay A. F. , Kreling M.-E.
Published: May 2006

The preparations of Δ8-hexahydro-1,4,8-pyrimidazole, Δ9-1,5,9-triazabicyclo(4.4.0)decene, and Δ9-1,4,9-triazabicyclo(5.3.0)decene from the corresponding 2-(ω-hydroxyalkylamino)-Δ2-1,3-diazacycloalkenes by chlorination and dehydrohalogenation are described. The nitro derivatives of these bicyclic compounds are more stable towards refluxing ethanol than 1-nitro-2,3,5,6-tetrahydro-1-imidaz(1,2-a)imidazole.
THE HEAT CAPACITIES OF THE CRYSTALLINE AND VACUUM DEHYDRATED FORM OF MAGNESIUM SULPHATE MONOHYDRATE
Authors: Frost G. B. , Breck W. G. , Clayton R. N. , Reddoch A. H. , Miller C. G.
Published: May 2006

Dehydration, under vacuum, of magnesium sulphate heptahydrate yields a product of monohydrate composition which does not give a diffraction pattern on X-ray examination and therefore has no evident crystalline structure. The heat capacity of this product has been determined over the temperature range from 90°K. to room temperature, and has been found to be substantially higher than that of the normal crystalline monohydrate. Consideration of these differences in heat capacity in conjunction with surface area data indicates that vacuum dehydration does not result in the formation of microcrystals the surfaces of which are available for gas adsorption. It is possible that aggregates of closely packed crystallites are formed in localized regions, these being interspersed with capillaries. Alternatively, it is possible that vacuum dehydration results in an intermediate state of ionic disorder.
THE ANALYSIS OF NUCLEAR MAGNETIC RESONANCE SPECTRA: III. PYRIDINE AND DEUTERATED PYRIDINES
Authors: Schneider W. G. , Bernstein H. J. , Pople J. A.
Published: May 2006

The proton resonance spectra of pyridine, 2,6-pyridine-d2, 3-pyridine-d1, and 4-pyridine-d1 have been obtained for the pure liquids under conditions of high resolution. The spectra have been analyzed as proton groupings of AB2X2, AB2, perturbed ABX, and B2X2 respectively. The spin-coupling constants obtained from analysis of the simpler spectra of the deuterated molecules were used to suggest trial solutions for the analysis of the complicated AB2X2 spectrum of pyridine. A final set of chemical shifts and spin-coupling constants derived for pyridine give satisfactory agreement between the observed and calculated spectrum.
THE NON-ENZYMATIC HYDROLYSIS OF ADENOSINE DIPHOSPHATE
Authors: Holbrook K. A. , Ouellet Ludovic
Published: May 2006

The kinetics of the non-enzymatic hydrolysis of adenosine diphosphate in aqueous solution have been studied at pH 3.5 to 10.5 and temperatures from 80° to 95 °C. The reaction has been followed by measuring colorimetrically the inorganic phosphate liberated according to the over-all reaction[Formula: see text]The reaction has been found to be first order with respect to ADP concentration and to be catalyzed by hydrogen ions. From rate studies at pH 8.0 an activation energy of 24.2 kcal./mole was derived. A mechanism is proposed to account for the observed facts and the mechanism for the hydrolysis of adenosine triphosphate is also discussed.
THE TEMPERATURE DEPENDENCE OF APPARENT DIELECTRIC CONSTANTS OF ADSORBATES ON NON-POROUS TITANIUM DIOXIDE
Authors: Petrie S. E. , McIntosh R. , Channen E. W.
Published: May 2006

The temperature dependence of the apparent dielectric constants of various adsorbed polar gases on finely divided, non-porous titanium dioxide has been determined. Within the experimental error, the apparent dielectric constant of the material adsorbed in the monolayer is independent of temperature. The effect of temperature on the dielectric constant for gas adsorbed beyond the monolayer depends on the adsorbate. These results have been interpreted as indicating that molecules initially adsorbed are oscillators, while those adsorbed in later stages of the adsorption process may be rotators or oscillators.
A REPORT ON A SYMPOSIUM HELD BY THE PHYSICAL CHEMISTRY DIVISION OF THE CHEMICAL INSTITUTE OF CANADA
Authors: Laidler K. J. , Ramsay D. A.
Published: May 2006

not available
EQUIVALENT ORBITALS AND THE SHAPES OF EXCITED SPECIES
Authors: Linnett J. W.
Published: May 2006

The electron distributions in the ground states of C2H2, HCO, and NH2, and in one excited state of each species, have been considered by transforming the simple molecular orbitals into equivalent ones. In the light of these considerations, the shapes and dimensions of the above species in these states have been discussed. It is found that a considerable degree of understanding can be achieved though there is uncertainty in the interpretation in some cases.
DIABATIC REACTIONS
Authors: Eyring Henry , Stewart George , Parlin Ransom B.
Published: May 2006

The fundamentals of diabatic reactions are briefly reviewed. The two important types of radiationless transitions at the crossover region of two potential surfaces are considered kinetically and rate formulations are given. The first type involves an appreciable activation energy in excess of the heat of reaction. The second does not. The reaction velocity is formulated using the absolute rate theory where the transmission coefficient is interpreted in terms of the Landau–Zener probability approximation. The over-all rate of a sequence of reactions is treated in accordance with the principle that resistances in series are additive. If the second in a sequence of two reaction steps involves a negative activation energy and is slow because of failure to cross to the new surface the resultant repeated passage through the crossover region requires a special formulation of the transmission coefficient, which is given. Whether this transmission coefficient influences the over-all rate or not depends on whether or not it belongs to the rate-determining step.Quenching reactions are classified in terms of the number of free valences involved, an electron being excited from a saturated molecule conferring radical-like properties on the excited molecule. Excited odd-electron molecules will attract at considerable distances without appreciable activation energy.The transmission coefficient is discussed in terms of recruitment factors for cases in which the products of a reaction are out of equilibrium.Hot positive ions resulting from mass spectrographic reactions are indicated as another example of diabatic reactions, and a procedure for treating these by the activated complex theory is briefly mentioned.
REACTIONS INVOLVING ELECTRONICALLY-EXCITED OXYGEN
Authors: Gill E. Kerry , Laidler K. J.
Published: May 2006

The various electronically-excited states of oxygen atoms and molecules are briefly considered. Certain reactions involving some of these electronically-excited species are then discussed with reference to the experimental evidence and to the potential-energy surfaces on which they occur. In the case of the mercury-photosensitized formation of ozone from oxygen it is concluded that both experimental evidence and theoretical arguments point to the fact that the oxygen molecule initially formed is in an excited [Formula: see text] state. Consideration is also given to the mechanism of formation of O2* in the carbon monoxide flame and in other flames. The reactions[Formula: see text]and[Formula: see text]are also discussed briefly.
PRIMARY PROCESSES IN REACTIONS INITIATED BY PHOTOEXCITED MERCURY ISOTOPES
Authors: Gunning Harry E.
Published: May 2006

A study has been made of the reaction of Hg2026(3P1) atoms, photoexcited in natural mercury vapor; with a number of substrates which form solid mercury compounds in mercury photo-sensitization. Some data are also given for reactions initiated by Hg1986(3P1) atoms. The solid mercury compounds formed were examined for enrichment in the isotope initiating the reaction. Such enrichment would be evidence for the primary formation of the mercury compound.Three HgO-forming substrates were studied: water vapor, nitrous oxide, and oxygen. The Hg2Cl2-forming substrates studied included hydrogen chloride, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, isopropyl chloride, and boron trichloride. One Hg2Br2-forming substrate was examined—isopropyl bromide.Among the HgO-forming substrates only water vapor gave enrichment in Hg202 in the HgO product. The Hg202 content of the oxide was found to vary from 32 to 35%, depending on reaction conditions, compared to a natural abundance of 29.6%. With water vapor – butadiene mixtures, oxides containing as high as 90% Hg202 were obtained. Similar enrichment factors were obtained for Hg1986(3P1) reactions.Hydrogen chloride and the alkyl chlorides yielded calomels containing a maximum of 45% Hg202. Methyl chloride gave similar enrichment factors in Hg198 for the Hg1986(3P1) reaction. The calomel formed in the boron trichloride reaction showed no enrichment.Addends such as butadiene and benzene, when added to hydrogen chloride, increased the Hg202 enrichment from 45% to 60%.For those reactions which yield mercury compounds enriched in the initiating mercury isotope, evidence is presented for a single primary process. Failure to obtain pure isotopes is attributed to exchange reactions with adsorbed natural mercury during recovery of the enriched mercury from the product. It is postulated that the addends react with the mercury product and reduce chemisorption of natural mercury on the product.The significance of these findings in the mechanisms of the reactions studied is discussed.
STUDIES OF CHEMICAL REACTIONS OF EXCITED SPECIES USING INTENSE LIGHT SOURCES
Authors: Marcus R. A.
Published: May 2006

The use of measurements of the products of flash photolysis as a means for studying the reactions of electronically-excited molecules is discussed. With intense light sources the problem of isolating these reactions from others involving free radicals is simplified. The flash sources also have their limitations, and misleading information which can result from the presence of inert gases is noted. A diagnostic test is proposed for detecting the effects (if any) of a possible adiabatic temperature rise of the flash.Some recent studies in the author's laboratory are summarized. Evidence is presented that in the flash photolysis of acetone acetyl radicals arise from an excited molecule. Several deactivation processes are described and compared with results from fluorescence studies.
CHEMILUMINESCENCE IN THE SYSTEM ATOMIC SODIUM PLUS ATOMIC HYDROGEN
Authors: McKinley Jr. J. D. , Polanyi J. C.
Published: May 2006

When atomic sodium is diffused into a mixture of atomic and molecular hydrogen, a weak chemiluminescence is observed in the gas phase. Visible emission consists of the sodium D lines. The total intensity of the emission, ~5 × 1011 photons/second, indicates that only one in 5 × 104 of the sodium atoms entering the reaction vessel is involved in luminescent reaction. In order to account for the rapid fall-off in intensity of the flame away from the nozzle it is necessary to suppose that some non-luminescent reaction is removing sodium atoms in the gas phase. Preliminary experiments suggest that the non-luminescent reaction is Na + H + H2 → NaH + H2, and the luminescent reaction either Na + Na + H → NaH + Na* with collision yield 4 × 10−3 or Na + H + H → H2 + Na* with collision yield 1 × 10−5.
THE INFRARED SPECTRA OF MALONATE ESTERS
Authors: Abramovitch R. A.
Published: May 2006

The infrared spectra of a number of malonate esters have been examined. Most of them exhibit two ester carbonyl stretching bands which have been shown not to be due to enolization and conjugate chelation or to association. The influence of α-substituents is discussed, as well as the reason for the splitting of the band.
PHOTOLYSIS OF ACETONE IN THE PRESENCE OF METHYL-d3 ACETATE
Authors: Wijnen M. H. J.
Published: May 2006

The photolysis of acetone in the presence of CH3COOCD3 has been carried out over the temperature range 151° to 274 °C, at different ratios of acetone to methyl acetate and at different light intensities. As activation energies for the abstraction reactions[Formula: see text]and[Formula: see text]were obtained E2 = 10 ± 0.5 kcal. and E3 = 14 ± 1 kcal.
THE RELATION BETWEEN THE SULPHATE AND NITROGEN CONTENT OF UNSTABILIZED CELLULOSE NITRATE
Authors: Gagnon Paul E. , Keirstead Karl F. , Newbold Brian T.
Published: May 2006

The sulphate and nitrogen contents of cellulose nitrates prepared from mixed acids containing different amounts of sulphuric acid were compared. The sulphate content showed a tendency to decrease with increasing nitrogen, for instance it was 1.96% for 10.54% and 0.44% for 13.31%. Similar results were obtained with a series of wood cellulose nitrates, for instance 2.40% for 11.01% and 0.91% for 12.47%. With practically the same amount of sulphuric acid in the mixed acid, cellulose nitrates were prepared and the sulphate and nitrogen contents were compared. For unstabilized cotton cellulose nitrates, the sulphate content decreased steadily with increasing nitrogen content. Similar results were obtained with wood cellulose nitrates.
A CONTRIBUTION TO THE CHEMISTRY OF UNSTABILIZED CELLULOSE NITRATE
Authors: Gagnon Paul E. , Keirstead Karl F. , Newbold Brian T.
Published: May 2006

Cotton linters and wood cellulose were nitrated in parallel experiments with a series of mixed acids and the products examined for nitrogen and sulphate content. A higher degree of nitration was obtained with the cotton cellulose, and the sulphate content of the nitrated cotton increased steadily with increasing concentration of sulphuric acid in the nitration medium while the sulphate content of the wood cellulose passed through a maximum value which depended on the degree of nitration. The sulphate content of the cotton cellulose nitrates was higher than that of the wood cellulose nitrates when the nitrations were performed under similar conditions.
THE INFRARED AND RAMAN SPECTRUM OF DIMETHOXYMETHANE
Authors: Wilmshurst J. K.
Published: May 2006

not available
DETERMINATION OF SULPHATE ACID ESTER IN UNSTABILIZED CELLULOSE NITRATE BY THE HYDROLYSIS METHOD
Authors: Gagnon Paul E. , Keirstead Karl F. , Newbold Brian T.
Published: May 2006

The method of determining sulphate acid ester in unstabilized cellulose nitrates by hydrolysis in acetone/water solution was evaluated. The precision of duplicate determinations for cotton and wood cellulose nitrates containing about 100% sulphate ester was −0.1 to +5.9% and +0.4 to +9.2%, respectively. With cellulose nitrates containing 69–43% and 69–47% sulphate ester, it was +1.8 to +13.4% and +0.4 to +21.0%. The sulphate acid ester content of both unstabilized cotton and wood cellulose nitrates increased with decreasing nitrogen content.
BLOCK AND GRAFT POLYMERS: II. BLOCK POLYMERS FROM ACRYLAMIDE AND ACRYLONITRILE AND ACRYLAMIDE AND ACRYLIC ACID
Authors: Miller M. L.
Published: May 2006

Block polymers of acrylamide and acrylonitrile and of acrylamide and acrylic acid have been prepared by photolysis of polymers with end groups that contained bromine. The intrinsic viscosities and softening points of these polymers have been measured and compared with the viscosities and softening points of random copolymers having the same composition and molecular weight.
THE PHOTOLYSIS OF AZOETHANE
Authors: Cerfontain H. , Kutschke K. O.
Published: May 2006

The photolysis of azoethane at λ 3660 Å has been reinvestigated. The quantum yield of nitrogen formation was found to be dependent on the azoethane pressure and the temperature, indicating collisional deactivation of excited azoethane molecules.The results confirm the mechanism proposed by Ausloos and Steacie (1). For the activation energy of the addition reaction C2H5 + C2H5N2C2H5 a value of 6.0 ± 0.3 kcal./mole has been obtained, assuming a negligible activation energy for the combination reaction of two ethyl radicals.
SYNTHESIS OF GUANIDINE FROM UREA, AMMONIUM BENZENESULPHONATE, AND AMMONIUM SULPHAMATE
Authors: Boivin Jean L. , Tremblay Meude
Published: May 2006

Guanidine benzenesulphonate has been obtained in yields exceeding 70% by heating urea, ammonium sulphamate, and ammonium benzenesulphonate in respective molar ratios of 1:1:0.75. The effects of temperature, proportion of reactants, and reaction time were studied batchwise. Then the process was operated on a continuous basis in a four-flask cascade reactor at temperatures between 240° and 260 °C.
THE HEMICELLULOSE OF WHITE ELM (ULMUS AMERICANA): I. IDENTIFICATION OF 2-O-(4-O-METHYL-D-GLUCOPYRANOSYLURONIC ACID)-D-XYLOPYRANOSE
Authors: Gillham J. K. , Timell T. E.
Published: May 2006

Alkaline extraction of wood meal from white elm (Ulmus americana) has yielded a hemicellulose which on hydrolysis gave a sugar mixture containing xylose together with traces of galactose, glucose, mannose, and rhamnose in addition to two monouronic acids and one aldobiouronic acid. The latter was identified as 2-O-(4-O-methyl-D-glucopyranosyluronic acid)-D-xylopyranose.
RADIOCHEMICAL ANALYSIS FOR LONG-LIVED FISSION PRODUCTS IN ENVIRONMENTAL MATERIALS
Authors: Merritt W. F.
Published: May 2006

A method is described whereby radiochemical analysis for the long-lived fission products Ru106, Sr90, Cs137, and Ce144 may be performed on the same sample of soil, water, or biological material. Carriers are added and the material is fused at 550 °C. with KOH, KNO3, and K2CO3. Ruthenium and cesium are extracted with water, strontium and cerium remaining in the melt. Ruthenium is extracted into carbon tetrachloride as ruthenium tetroxide, cesium is absorbed on Duolite C-3 cation-exchange resin from alkaline solution, strontium and cerium are extracted from the melt with acid, cerium is precipitated as the hydroxide and strontium as the carbonate. The elements are precipitated, weighed, and counted according to standard procedures.
ELECTROLYTIC CONDUCTANCE IN HYDROGEN PEROXIDE–WATER MIXTURES: PART I. THE ALKALI CHLORIDES
Authors: Thomas D. K. , Maass O.
Published: May 2006

The equivalent conductance of a series of alkali chlorides has been measured in water–hydrogen peroxide mixtures over the whole range of solvent composition. The measurements were made by a simple direct-current method, and the results obtained are interpreted in terms of the viscosity of the solvent.
LYCOPODIUM ALKALOIDS: VI. REACTIONS OF THE DIPHENYL DERIVATIVE OF DESOXODIHYDROANNOTININE
Authors: Betts E. E. , MacLean David B.
Published: May 2006

Desoxodihydroannotinine reacted with phenyl lithium to yield a diphenyl derivative, C28H35O2N (III). This compound yielded a ketone, C28H33O2N (V), upon oxidation by the Oppenauer procedure and a dihydroxyketone, C28H33O3N (VI), upon oxidation with chromic acid. A ketone VIII, epimeric with V, was obtained by treatment of III with potassium tertiary butoxide in cyclohexanone. Both V and VIII underwent elimination of their diphenyl carbinol groups upon treatment with potassium tertiary butoxide to yield an unsaturated ketone, C15H21ON (IX), and benzohydrol. These reactions are discussed in relation to the recently proposed structures for the parent alkaloid, annotinine.
THE COMPOUND CaO.Ti2O3
Authors: Bright Norman F. H. , Rowland John F. , Wurm Joseph G.
Published: May 2006

By electrolyzing baths of molten CaCl2 containing perovskite(CaO.TiO2), a compound within the ternary Ca–Ti–O system, namely CaO.Ti2O3, has been obtained. The compound has been identified by chemical analysis, and its crystallographic data have been determined by X-ray means. Attempts to synthesize the compound apart from the electrolytic cell have, so far, failed.
PHOTOCONDUCTIVITY AND ABSORPTION AND FLUORESCENCE SPECTRA OF 9,10-DICHLOROANTHRACENE
Authors: Bock E. , Ferguson J. , Schneider W. G.
Published: May 2006

The spectral response, voltage, light intensity, and temperature dependences of the photocurrent generated in crystals of 9,10-dichloroanthracene have been studied as well as the absorption and fluorescence spectra. The magnitude of the measured photocurrent was 102–103 times larger than that observed in anthracene under similar conditions. The spectral response of the photocurrent in the surface cell arrangement was found to depend on the direction of the incident light relative to the electrodes. Above a certain value of the applied voltage the photocurrent was found to be ohmic. The photocurrent increased as the 0.7 or 0.8 power of the light intensity depending on whether the light was incident on the same side or opposite sides of the crystal face containing the electrodes. When the crystal was cooled the photocurrent passed through a maximum between 20° and 0 °C.The absorption edge of crystalline 9,10-dichloroanthracene as well as the absorption spectrum in chloroform solution were determined. When the crystals were cooled the fluorescence spectrum was observed to shift to longer wavelengths and the intensity increased between two and three times.
THE CHANGE OF PHOTOCONDUCTION AND SEMICONDUCTION IN AROMATIC HYDROCARBONS ON MELTING
Authors: Kommandeur J. , Korinek G. J. , Schneider W. G.
Published: May 2006

The variation of the photocurrent and dark current on melting naphthalene and biphenyl was studied. A large increase in the value of the photocurrent was observed. This change is very similar to that of the dark current. It is concluded that the increased mobilities of the charge carriers in the melt are mainly responsible for the change in both cases. The existence of photoconduction in the non-crystalline state is discussed.
THE CONDENSATION OF FURAN WITH CARBONYL COMPOUNDS
Authors: Brown William H. , French Warren N.
Published: May 2006

A homologous series of substituted quaterenes has been synthesized by the condensation of 2,2-isopropylidenebis[5-(dimethylfurfuryl)furan] with keto acids and their esters. Substituted quaterenes containing chlorine have also been prepared. Only one out of the theoretically possible four geometrical isomeric quaterenes which could arise from the condensation of furan with butanone has been isolated. In all instances where more than one geometrical isomeric quaterene would be theoretically possible, only one has been isolated. Two new dinitro compounds have been prepared by the nitration of 2,2-difurylbutane and 3,3-difurylpentane.
THE MOLECULAR WEIGHT OF POLYVINYL ACETATE
Authors: Sirianni A. F. , Tremblay R. , Puddington I. E.
Published: May 2006

The molecular weights of a series of unfractionated polyvinyl acetates of low degrees of polymerization have been measured by determining the lowering of the vapor pressure of their solutions. An approximate molecular-weight range of 5000–40,000 was examined. While most of the determinations were made in benzene solutions at 55 °C., other solvents and temperatures were used. Anomalous results were obtained with one sample of fractionated material.
THE REDUCTION OF SOME HALOGENATED COMPOUNDS BY CHROMOUS CHLORIDE
Authors: Anet F. A. L. , Isabelle Elaine
Published: May 2006

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GAS–LIQUID PARTITION CHROMATOGRAPHY OF ORGANIC SULPHUR COMPOUNDS
Authors: Amberg C. H.
Published: May 2006

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ARSENATES OF THE TRANSITION METALS: THE ARSENATES OF COBALT AND NICKEL
Authors: Taylor J. B. , Heyding R. D.
Published: May 2006

Complex oxides occurring in the systems CoO/AS2O5 and NiO/As2O5 have been studied using Debye–Sherrer diagrams. The compounds were prepared either by high-temperature reaction of the oxides and subsequent pyrolysis of the products or by aqueous precipitation of arsenates followed by thermal dehydration.The existence of compounds having metal oxide to arsenic pentoxide ratios of 1:1, 2:1, and 3:1 has been clearly demonstrated and the thermal stabilities of each in vacuo and in air have been studied. Corresponding compounds in the cobalt and nickel series are isostructural and unit-cell dimensions have been determined. The compounds with a 2:1 ratio could not be isolated readily although their existence is indisputable and tentative figures for the unit-cell dimensions have been obtained.Another compound, probably with a metal oxide to arsenic pentoxide ratio of 6:1, has been observed during the pyrolysis of the 3:1 compounds. Apparently the cobalt and nickel compounds are isostructural and represent the only phase existing between the 3:1 compounds and the metal oxides.
SOME NEW FLUORIDE COMPLEXES OF TRIVALENT TITANIUM
Authors: Bright Norman F. H. , Wurm Joseph G.
Published: May 2006

Three new complex fluorides of trivalent titanium have been isolated from the products of electrolysis, under an inert atmosphere, of molten baths of KC1, NaCl, or mixtures of KCl and NaCl, containing either K2TiF6 or Na2TiF6. Electrolytic baths containing a mixture of KCl and NaCl with either K2TiF6 or Na2TiF6 yielded a violet-colored, face-centered cubic compound identified as K2NaTiF6, which was virtually insoluble in water and amenable to electrostatic separation from the metallic titanium also produced in the electrolysis. Baths containing molten mixtures of K2TiF6 and KCl gave a pale violet compound K3TiF6, which was slightly soluble in water. Baths containing Na2TiF6 and NaCl gave a deep violet-colored compound Na3TiF6 which was almost insoluble in water. The compounds K3TiF6 and Na3TiF6 have structures which approximate to cubic. The compounds K2NaTiF6 and Na3TiF6 are more stable to atmospheric oxidation than is K3TiF6. X-Ray diffraction patterns have been recorded for these compounds and some of their physical and chemical properties determined.
A NEW SPOT TEST FOR NITRATE ION
Authors: Coldwell B. B. , McLean S. R.
Published: May 2006

Under the influence of short ultraviolet radiation, diphenylamine and nitrate salts react to produce a yellow-colored product. The reaction appears specific and makes it possible to detect 1 μg. of nitrate ion in 0.01 ml. of solution.
HYDROGENOLYSIS OF CARBOHYDRATES: IV. 1,2-O-ISOPROPYLIDENE-D-GLUCOFURANOSE
Authors: Gorin P. A. J. , Perlin A. S.
Published: May 2006

1,2-O-isopropylidene-D-glucofuranose was treated with hydrogen at 180 °C. and 2900 p.s.i. using copper chromium oxide catalyst and dioxane as solvent. The major isolated products were a hexanediol (2.4%), a mixture of hexanetriols (6.5%), a hexanetetrol (4.3%), and an isopropylidene-aldohexose (4.2%) which differed from the starting material. The latter product yielded L-idose on hydrolysis, showing clearly that isomerization of carbon 5 of monoacetone-D-glucose occurs under the reaction conditions used.The diol and the major components of the triol mixture were found to possess a 1,2-glycol group which was derived mainly from the 5,6-glycol group of the original monoacetone-D-glucose. Thus, hydrogenolysis of 1,2-O-isopropylidene-D-glucofuranose-l-C14 afforded the 1,2-hexanediol and mixed triols containing only about 30% of the total specific activity in carbon 1. The tetrol was shown to be 1,2,5,6-hexanetetrol. The results suggest that the carbon–oxygen bonds at carbons 5 and 6 of isopropylidene-D-glucose are least prone to hydrogenolysis and that those at carbons 3 and 4 are most readily cleaved.
PHOTOLYSIS OF n- AND i-PROPYL PROPIONATE
Authors: Wijnen M. H. J.
Published: May 2006

The photolysis of n- and i-propyl propionate has been studied in the temperature range of 30° to 170 °C. The results strongly indicate that the following three primary processes may occur:[Formula: see text][Formula: see text]Based on these primary steps a qualitative explanation may be given for the formation of all reaction products.
REACTOR NEUTRON-CAPTURE CROSS SECTION OF 18-MINUTE Rb88
Authors: Roy J. C. , Berry P. J. , Roy L. P.
Published: May 2006

The reactor neutron-capture cross section of 18-minute Rb88 has been determined by an activation method. The yield of Rb89 formed by successive neutron capture in Rb87 was determined by counting the beta rays emitted by its daughter, 51-day Sr89. In these experiments Sr89 is also produced by the Sr88(n, γ)Sr89 reaction from the Sr88 contamination in the rubidium target and from Sr88 formed by the beta decay of Rb88. Corrections for the contributions from these sources to the yield of Sr89 have been measured experimentally. The reactor neutron-capture cross section of Sr88 has been measured to be 5.8 mb. for the conditions of the experiment. Taking 0.12 ± 0.3 barn for the thermal cross section of Rb87, the cross section of Rb88 was found to be 1.0 ± 0.3 barn for reactor neutrons.
ALKYLGUANIDINE NITRATES AND ALKYLNITROGUANIDINES
Authors: Gagnon Paul E. , Boivin Jean L. , Boivin Paul A. , Dickson John H.
Published: May 2006

The fusion of mixtures of alkylamine nitrates, RR'NH.HNO3 (R' = H when R = methyl, isopropyl, isobutyl, n-amyl, and phenyl, and R' = C2H5 when R = ethyl), and dicyandiamide, or calcium cyanamide, or calcium cyanamide and urea, yielded alkylguanidine nitrates. The latter were also obtained by heating solutions of alkylamine nitrates and calcium cyanamide. By treatment of the alkylguanidine nitrates with sulphuric acid, alkylnitroguanidines were prepared in good yields. A study of the effect of temperature on the yield of n-amyl and of time and temperature on the yields of methyl, isopropyl, and isobutyl nitroguanidine was made. The solubility of methyl, isopropyl, isobutyl, and n-amyl nitroguanidine in water and 10% and 20% sulphuric acid solutions at 0 °C. was determined.
STUDIES IN THE WAGNER–MEERWEIN REARRANGEMENT. PART III
Authors: Anet F. A. L. , Bavin P. M. G.
Published: May 2006

2-(9-Methyl-9-fluorenyl)-propan-2-ol and 3-(9-ethyl-9-fluorenyl)-pentan-3-ol have been prepared and shown to give 9,10-dimethyl- and 9-10-diethylphenanthrene, respectively, when heated with polyphosphoric acid.
VOLTAIC CELLS IN FUSED SALTS: PART III. THE SYSTEM SILVER – SILVER CHLORIDE, CADMIUM – CADMIUM CHLORIDE
Authors: Flengas S. N. , Ingraham T. R.
Published: May 2006

Using a silver–silver chloride reference electrode, the standard electrode potential his been established for the equilibrium Cd|Cd++ in melts containing equimolar quantities of KCl and NaCl. The experimentally obtained standard potential was greater than that calculated from theoretical thermodynamic data. This difference was attributed to the formation of a cadmium complex in the melt. A dissociation constant for the complex was calculated.The effect of temperature on the electromotive force of the silver–cadmium voltaic cell was also measured, and the heat of the cell reaction was calculated from the data. To extend the temperature range of the cadmium data, a cadmium–lead alloy was used in the higher temperature experiments. To correlate these data with those for the pure cadmium system, the activity coefficients of cadmium in the alloy were determined electrometrically using the silver–silver chloride electrode as a reference. It was found that the activity coefficients were in agreement with previously published data obtained at lower temperatures using a pure cadmium reference electrode. The activity coefficients were virtually independent of temperature but showed large positive deviations from unity when the mole fraction of cadmium was decreased below about 0.8.
THE EFFECT OF THE AMBIENT GASES ON THE SURFACE PHOTOCURRENT IN ANTHRACENE
Authors: Waddington T. C. , Schneider W. G.
Published: May 2006

Following the observation that the photocurrent in anthracene is markedly affected by an atmosphere of oxygen over the system, the behavior of anthracene in the presence of atmospheres of other gases has been investigated. The effect has been shown to be confined to the surface photocurrent, and the active gases have been shown to fall into two classes: (1) gases which are electron acceptors, e.g. BF3, HCl, O2, and NO, which all increase the photocurrent markedly; (2) gases and vapors which are electron donors, e.g. NH3, (CH3)2O, and (CH3)3N, which all decrease the photocurrent markedly. The effect of the pressure of the ambient gas and of the temperature of the system on the photocurrent has also been investigated.
LIGHT-ABSORPTION STUDIES: PART X. ULTRAVIOLET SPECTRA IN ACID AND BASIC MEDIA–—SOME FURTHER OBSERVATIONS ON THE ORTHO EFFECT
Authors: Forbes W. F. , Ralph Audrey S. , Gosine Rosemarie
Published: May 2006

The spectra of acetophenones and related compounds are obtained in acid and basic solution and are compared with previously reported spectra of substituted benzene derivatives. Evidence is adduced that the B-bands, not only in neutral solution, but also in acid or basic solution, are determined primarily by steric and mesomeric interactions.Following previous work, the main cause of the ortho effect in the B-band of electronic spectra is ascribed to steric interactions between the vicinal substituents, and in this way, steric interactions explain the frequent similarity in the spectra of meta and ortho isomers. Other factors also play a part, and one of these, a short-range interaction between the substituent and the benzene ring, is discussed.
2-BENZHYDRYLIMINO-4-THIAZOLIDONES AND RELATED COMPOUNDS
Authors: Winthrop Stanley O. , Gavin Gregory
Published: May 2006

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