bluuebunny/crossref_metadata_2025 huggingface dataset:
SURFACE-CATALYZED ATOM RECOMBINATIONS THAT PRODUCE EXCITED MOLECULES
Authors: Harteck Paul , Reeves Robert R. , Mannella Gene
Published: May 2006

Various metal surfaces such as nickel, cobalt, copper, and silver give rise to a reddish luminosity in a stream of N- and O-atoms. Spectroscopic and photographic analysis of these glows indicate the formation of electronically excited molecules on the metal surface which diffuse into the gas phase and radiate. Two parallel processes are involved: the formation of an NO(B2Π), which results in NO β radiation, and the formation of an [Formula: see text] which, in collision, crosses into the N2(B3Π0) state and then radiates back to the [Formula: see text] giving the N2 first positive system. The N2 first positive system observed here shows the strongest bands from v' = 8 and 6; these vibrational levels straddle the [Formula: see text] potential energy curve crossing point. This crossing-over of N2 molecules into the (B3Π0) at this point may explain the observed strong v' = 6 transition in normal N-atom recombination if it is assumed that some of the N-atoms recombine into the [Formula: see text] in addition to the [Formula: see text]state.The N2 second positive system (C3Πu → B3Π0) has also been observed over copper in an N- and O-atom stream. This is most surprising since the N2(C3Πu) has about 1.4 ev more than [Formula: see text]
ELECTROPHILIC CHARACTER OF OXYGEN ATOMS
Authors: Cvetanović R. J.
Published: May 2006

The relative rates of reactions of oxygen atoms with a number of olefins in the vapor phase determined in previous work are summarized and supplemented by some additional results. The uncertainty in the values of the relative rate constants is now believed to be reduced to only a few per cent. A number of simple correlations observed previously have been re-examined on the basis of the more complete and more accurate list of values available at present. These correlations show a distinct electrophilic character of oxygen atoms in their reactions with olefins and their potential significance for the understanding of the finer details of these addition processes is discussed.
A COMBINED FLASH PHOTOLYSIS AND SHOCK WAVE METHOD FOR THE STUDY OF BROMINE ATOM RECOMBINATION OVER A WIDE TEMPERATURE RANGE
Authors: Burns George , Hornig D. F.
Published: May 2006

A combined flash photolysis shock wave experiment is described in which bromine is first flash photolyzed, then compressed and heated by a shock wave, and finally allowed to recombine at the high temperature. Some of the problems connected with working in a shock tube used as a photolysis vessel are analyzed. The apparatus was used to measure recombination rates with argon as a third body at room temperature, to estimate the efficiency of bromine as a third body at room temperature, and to obtain a preliminary measurement of the recombination rate of bromine in the presence of argon at 950 °K.
THE PRODUCT EMITTER DIFFUSION FLAME: THE REACTION OF NITRIC OXIDE WITH OXYGEN ATOMS
Authors: Garvin David , Gwyn Paul P. , Moskowitz Jules W.
Published: May 2006

The use of the Polanyi diffusion flame technique as a diagnostic test for the identification of reactions that lead to light emission is presented. There is developed the mathematical model needed for the interpretation of such flames in which a product is responsible for the emission that is studied. The method is applied to the systems in which oxygen atoms and nitrogen atoms react with nitric oxide. The rate constant of the reaction O + NO + M → NO2 + M at 293 °K was determined as k = 1.4 × 1017 (cc/mole)2 sec−1.
HYDROGEN BONDING IN THE AMINE HYDROHALIDES: III. NEAR-INFRARED SPECTRA OF ALIPHATIC AMINE HYDROHALIDES
Authors: Sauvageau P. , Sandorfy C.
Published: May 2006

The first overtones of the [Formula: see text] stretching fundamentals are very weak and difficult to locate. Binary combinations between [Formula: see text] stretching and [Formula: see text] bending vibrations and also [Formula: see text] stretching–bending combinations fall into the 4600–4400 cm−1 area for primary and secondary amine hydrohalides and are much stronger. The intensity of these combination bands is not due to the anharnionicity of the potential surface but to the electrical anharmonicity of bending vibrations.
SPHERICAL AGGLOMERATION OF BARIUM SULPHATE
Authors: Smith H. M. , Puddington I. E.
Published: May 2006

The mechanical agglomeration of barium sulphate suspended in organic media into essentially spherical masses has been studied. The presence of a small quantity of water is necessary for the phenomenon to occur. This is regarded as a bridging agent that forms liquid lenses between the particles and binds them together. An equilibrium is set up for this water between the surface of the solid and the bulk suspending medium. The methods of formation of the spherical agglomerates are discussed and their properties examined.
ALKALOIDS OF LYCOPODIUM FAWCETTII. PART II
Authors: Burnell R. H. , Mootoo B. S. , Taylor D. R.
Published: May 2006

β-Lofoline and fawcettiine are shown to be identical. Hydrolysis of bases from Lycopodiumfawcettii gave rise to lycofoline and a smaller amount of an α-obscurine like base. Milder extraction procedures afford four new bases, base M, C17H27NO2; base O, C20H31NO5; base K, which is acetylfawcettiine, C20H31NO4; and base, which is diacetyllycofoline, C20H29NO4. The isolation of fawcettiine from LycopodiumclavatumLinn. gathered in Jamaica is also reported.
PROTON MAGNETIC RESONANCE ABSORPTION IN ANHYDROUS POTASSIUM STEARATE
Authors: Grant R. F. , Dunell B. A.
Published: May 2006

The proton magnetic resonance absorption in anhydrous potassium stearate has been measured over the temperature range −190 °C to 182 °C. Abrupt changes in line width have been found between 55 °C and 62 °C, and between 170 °C and 171 °C; these changes correspond approximately to known phase transitions. The reduction in line width and second moment with rising temperature is discussed.
AN IMPROVED PREPARATION OF ω-HYDROXY ALIPHATIC ACIDS AND THEIR ESTERS
Authors: Diaper D. G. M. , Mitchell D. L.
Published: May 2006

Reductive cleavage of the ozonides of aliphatic acids and their esters by sodium borohydride or by hydrogenation produces ω-hydroxy aliphatic acids and ω-hydroxy aliphatic esters, respectively, in high yields.
NUCLEOPHILIC DISPLACEMENT OF METHYL SULPHONIC ESTERS BY HYDROXIDE ION IN WATER
Authors: Hartman S. , Robertson R. E.
Published: May 2006

Rate data for the reaction between OH− and methyl benzenesulphonate, methyl methanesulphonate, and dimethyl sulphate in water are determined for a series of temperatures. The corresponding [Formula: see text]ratio are found to be 3 to 6 times smaller than those values characterizing the reaction for the methyl halides, and the ratios in all cases are temperature dependent. While the stability of the initial state solvation shell undoubtedly contributes to the difference between the halides and sulphonates in these reactions, it is probable that differences in nucleophilic interaction between the oxygen of the water molecule and the partially empty p orbital of the methyl carbon is a more important factor in determining the characteristic difference.
SOLVENT EFFECTS AS AN AID IN THE ANALYSIS OF THE PROTON MAGNETIC RESONANCE SPECTRUM OF VINYL BROMIDE
Authors: Schaefer T. , Schneider W. G.
Published: May 2006

By making use of specific solvent effects it has been possible to vary the relative chemical shift between the geminal protons of vinyl bromide from about +10 cycles/sec to −4 cycles/sec (at 60 Mc/sec) and to study the resultant changes in the proton resonance spectrum in the limiting region of zero chemical shift. Of particular interest is the growth and displacement of the combination lines, which appear in the resonance signals of the proton bonded to the same carbon atom as the bromine. From the variation of the six possible lines in this region it was confirmed that the cis and trans proton coupling constants must have the same sign. The intensity distribution of the lines in the geminal proton region require the geminal coupling constant to be of opposite sign to the other two.
SOME OBSERVATIONS ON THE STRUCTURE OF ETHYLENETHIURAM MONOSULPHIDE
Authors: Thorn G. D.
Published: May 2006

An attempt has been made to answer several apparent objections to the structure ethylene-thiuram monosulphide assigned to the monomeric material of formula C4H6N2S3 obtained by air oxidation of disodium ethylenebisdithiocarbamate. Comparison of the ultraviolet and infrared absorption spectra, potentiometric titrations, and biological assays of the compound and several heterocyclic and other compounds containing the N–C–S grouping has eliminated two possible alternative structures containing thiadiazolidine and dithiazolidine ring systems and has led to the conclusion that the original assignment of structure was correct.
CONSTITUTION OF AN ACIDIC XYLAN FROM TAMARACK (LARIX LARICINA)
Authors: Adams G. A.
Published: May 2006

An acidic xylan isolated from tamarack wood contained arabinose, xylose, and uronic acid (1:17:3) and was homogeneous on examination by electrophoresis and sedimentation. Molecular weight estimations by four different methods showed a degree of polymerization of 20. Methylation and periodate oxidation showed that the xylan consisted of ca. 16 β-D-xylopyranose units joined by 1 → 4 glycosidic bonds with the possible occurrence of one 1 → 3 linkage. To this unbranched structure were attached as side branches, three single units of 4-O-methyl-D-glucuronic acid through C2 and one unit of L-arabofuranose through C3.
LES SPECTRES INFRAROUGES DE L'ACIDE SULFURIQUE ET DES OLÉUMS
Authors: Giguère Paul A. , Savoie Rodrigue
Published: May 2006

On a mesuré les spectres infrarouges, entre 2 et 30 μ, de l'acide sulfurique et de ses solutions aqueuses à diverses concentrations de même que celui de l'acide deutéré, D2SO4. On a aussi mesuré à l'état solide les spectres de l'acide pur et de ses hydrates à une, deux et quatre molécules d'eau. Les fréquences observées ont pu être attribuées aux différents modes de vibration de la molécule H2SO4. Les résultats confirment et complètent ceux déjà obtenus par d'autres méthodes quant à la nature et l'abondance relative des diverses espèces ioniques (y compris H3O+) et moléculaires présentes dans ces solutions. En particulier, on a vérifié l'auto-dissociation de H2SO4pur et l'ionisation incomplète de l'eau, même dans l'acide très concentré. Enfin on a étudié de la même façon les spectres des oléums contenant jusqu'à 70% de l'anhydride SO3. En augmentant la concentration de ce dernier, on voit apparaître graduellement les bandes de H2S2O7, H2S3O10et enfin SO3.
STRETCHING VIBRATIONS OF THE FREE GROUP
Authors: Chevalier P. , Sandorfy C.
Published: May 2006

not available
NOTE ON THE THERMAL NEUTRON CAPTURE CROSS SECTION OF Cs133
Authors: Baerg A. P. , Bartholomew R. M.
Published: May 2006

not available
CHEMICAL EFFECTS OF THE (n,r) ACTIVATION OF BROMINE IN THE ALKYL BROMIDES: THE HALOMETHANES
Authors: Harris W. E.
Published: May 2006

Techniques for studying the chemical effects accompanying the neutron irradiation of the halomethanes with a neutron flux of only 108 neutrons per square centimeter per second are described. Results are presented from the irradiation of mixtures of bromine with the four bromomethanes and carbon tetrachloride. The formation of organic products which occur as the result of "hot", "hot-spot diffusive", and "thermal" reactions are discussed. The amounts of products resulting from these three types of reactions are estimated. Observations with respect to the formation of bromoethanes are also discussed.
THE KINETICS AND MECHANISM OF THE Cu++-CATALYZED REDUCTION OF CrVI BY HYDROGEN IN AQUEOUS SOLUTIONS
Authors: Hahn E. A. , Peters E.
Published: May 2006

The kinetics of the Cu++-catalyzed reduction of CrVI by H2 in aqueous perchlorate solutions have been investigated between 160° and 200 °C. The mechanism proposed to account for the kinetics gives rise to a rate law of the form[Formula: see text]where[Formula: see text]As a consequence of these studies an important anomaly between the previously published rate law for dichromate reduction and a more recent kinetic study of the cupric-perchlorate-catalyzed hydrogen–oxygen recombination has been resolved.
REARRANGEMENT IN THE REACTION BETWEEN THIONYL CHLORIDE AND 3-METHYL-2-BUTANOL
Authors: Lee C. C. , Finlayson A. J.
Published: May 2006

not available
ORGANOGERMANIUM COMPOUNDS: PART I. THE INTERACTION OF HEXAMETHYLDIGERMOXANE AND TRIMETHYLMETHOXYGERMANE WITH BORON TRIFLUORIDE
Authors: Griffiths J. E. , Onyszchuk M.
Published: May 2006

Boron trifiuoride does not form a stable adduct with hexamethyldigermoxane. Instead, cleavage of the Ge—O—Ge linkage occurs with quantitative formation of trimethylfluorogermane and boron trioxide. Trimethylmethoxygermane and boron trifiuoride form a 1:1 addition compound which sublimes without decomposition. Dative dπ–pπ bonding, if present in the Ge—O linkage of trimethylmethoxygermane, does not appear to affect appreciably the electron-donor activity of the oxygen atom toward boron trifiuoride. The preparation and some properties of CH3GeH2Br, CH3GeHCl2, (CH3)3GeCl, (CH3)3GeF, [(CH3)3Ge]2O, and (CH3)3GeOCH3 are described.
IMPROVEMENTS IN THE ACIDOLYSIS PROCEDURE FOR LIGNIN ISOLATION AND IN THE PROCEDURE FOR THE ANALYSIS OF LIGNIN OXIDATION PRODUCTS
Authors: Pepper J. M. , Siddiqueullah M.
Published: May 2006

not available
EXCHANGE REACTIONS BETWEEN ZINC AND ITS IONS
Authors: Sandor J. E.
Published: May 2006

The exchange reaction between zinc metal and zinc ions in solution has been studied by means of radioactive zinc-65. Polycrystalline zinc and bicrystals of zinc were used under conditions where the radioactive material was incorporated either in the solid or the liquid phase. Strain-free clean surfaces were obtained and autoradiographs taken.The results of the experiments using bicrystals were interpreted on the basis that a local cell action sets up an electrochemical potential between liquid and solid at the beginning of the reaction. Exchange was found to take place in both directions, but the reaction did not follow a simple logarithmic law.
THE REACTION OF ALKYL IODIDES WITH IODO-ARSINES IN THE PRESENCE OF MERCURY
Authors: Baig M. M. , Cullen W. R.
Published: May 2006

The reaction of alkyl iodides with iodo-arsines in the presence of mercury generally gives arsonium derivatives of triiodomercury (II). Thus tetramethylarsonium triiodomercury (II) is obtained from the reactions of methyl iodide with the compounds (CH3)3−nAsIn (n = 1,2,3). Phenyl-iodo-arsines give the new compounds C6H5AsR3HgI3 and (C6H5)2AsR2HgI3 (R = CH3 or C2H5) from similar reactions. However, the reaction of iododimethylarsine with ethyl iodide gives the 1:1 arsine complex (CH3)2AsC2H5.HgI2. The compounds (C2H5)4AsI and (C2H5)4 AsHgI3 were reinvestigated, and used to prepare the compound ((C2H5)4As)2HgI4.
THE ALUMINUM REDUCTION OF MAGNESIUM OXIDE: I. THE VAPOR PRESSURE OF MAGNESIUM OVER THE SYSTEM Al–MgO
Authors: Grjotheim K. , Herstad O. , Toguri J. M.
Published: May 2006

The equilibrium vapor pressure of magnesium over the reaction between magnesium oxide and aluminum was measured by means of the transportation method. In the temperature range 850–1150 °C the results can be expressed by the equation log Pmm of Hg = −9617/T + 8.93. From X-ray diffraction analysis this reaction proceeds according to the equilibrium[Formula: see text]
HIGH-TEMPERATURE STUDIES OF METALLURGICAL PROCESSES: PART I. THE THERMAL REDUCTION OF MAGNESIUM OXIDE WITH SILICON
Authors: Toguri J. M. , Pidgeon L. M.
Published: May 2006

The rate of reaction (a) has been studied over the temperature range 1140–1460 °C, by following the loss in weight of the reactants in high vacuum.[Formula: see text]The loss in weight of the reactants was found to be greater than that which can be accounted for by the above reaction. The excess weight loss was found to be due to a brownish, glassy deposit which appeared outside the reaction zone. This material was analyzed by X-ray diffraction and found to be an intimate mixture of Mg2SiO4 and Si. Experiments conducted showed that both of these materials are not appreciably volatile at 1350 °C. This transfer of silicon and silicate is postulated to occur by the formation of gaseous SiO formed from the reaction mixture. Based on this assumption a possible mechanism for this reaction is postulated.
THE THERMAL NEUTRON FISSION YIELDS OF U233
Authors: Bidinosti D. R. , Irish D. E. , Tomlinson R. H.
Published: May 2006

Using the mass spectrometer and isotope dilution technique, 27 cumulative fission yields from the thermal neutron fission of U233 along with 13 other fission product chains relative to each other have been determined. After normalization of the latter, values are obtained for all but seven fission decay chains whose yields are in excess of 0.5%.
DISTRIBUTION OF NUCLEAR CHARGE IN THE PROTON-INDUCED FISSION OF Th232: PART II
Authors: Kjelberg A. , Taniguchi H. , Yaffe L.
Published: May 2006

The fractional chain yields of Ga72, Br82, Ag112, and La140, formed in the proton-induced fission of Th232, have been measured at proton energies ranging between 12.8 and 82.4 Mev. The yields are compared with data previously obtained by others from uranium and thorium fission, and with predictions made by Coryell.During the course of this investigation, the half-life of Zn72 was checked and found to be 46.5 ± 0.1 hours, rather than 49 hours as previously reported.
REACTIONS OF ALUMINUM ALKOXIDES WITH ACETYLACETONE, BENZOYLACETONE, AND ETHYL ACETOACETATE
Authors: Mehrotra R. K. , Mehrotra R. C.
Published: May 2006

The observed stability of stable bridge structure, [Formula: see text] in aluminum alkoxides has been explained on the powerful tendency of aluminum to attain co-ordination number 4. This would predict the monomeric nature of the derivatives of the type, (OR)2Al(lig), where ligand (lig) is a diketone like acetylacetone (acac), benzoylacetone (bzac), or ketoester like ethyl acetoacetate (etac). This has been confirmed by actual synthesis of these compounds by reactions between aluminum alkoxides (ethoxide and isopropoxide) and acetylacetone, benzoylacetone, and ethyl acetoacetate in equimolecular ratios. These and also (OR)Al(lig)2 as well as Al(lig)3 have been shown to be monomeric in boiling benzene. The volatility of the derivatives was found in the order [(OPri)3Al]2 > (OPri)2Al(acac) > (OPri)Al(acac)2. This leads to the conclusion that chelation lowers the volatility and the direct relationship between volatility and molecular complexity, observed in the case of simple alkoxides, is not applicable in these derivatives. Further mixed derivatives of the type Al(acac)(etac)2 and Al(etac)(acac)2 have also been synthesized during the course of the above work.
THE MECHANISM OF THE ALCOHOLYSIS OF ALIPHATIC NITRITES: II. ACID-CATALYZED ALCOHOLYSIS OF 1-METHYLHEPTYL NITRITE
Authors: Allen A. D. , Schonbaum G. R.
Published: May 2006

The acid-catalyzed alcoholysis of 1-methylheptyl nitrite has been studied kinetically. The reaction rate is first order with respect to both the nitrite and the hydrogen ion concentration, and the reaction does not involve the asymmetric carbon center. Addition of lithium salts (chloride and perchlorate) indicates catalysis by chloride ion. Addition of water in low concentrations inhibits the reaction strongly. These results and the mechanism of the reactions are discussed in terms of the properties of the alcohols and the dissociation of the acid catalysts in the alcohols used.
ARYLATION OF QUINONES BY DIAZONIUM SALTS: VII. SYNTHESIS AND STRUCTURE OF SOME ARYL-CHLORO-p-BENZOQUINONES
Authors: Bagli Jehanbux F. , L'Écuyer Ph.
Published: May 2006

A careful re-examination of the arylation (P. Brassard and P. L'Écuyer. Can. J. Chem. 36, 814(1958)). reaction with chlorobenzoquinone has revealed in its products the presence of all the three possible disubstituted isomeric quinones. Arylation using diazotized p-nitro-aniline has resulted in the isolation of the three new isomeric quinones, whose structures are assigned, based on chemical and spectral evidences. Mechanistic implications in the arylation and halogenation of benzoquinones are discussed.
PRESSURE EFFECT AND MECHANISM IN ACID CATALYSIS: VII. HYDROLYSIS OF METHYL, ETHYL, AND t-BUTYL ACETATES
Authors: Osborn A. R. , Whalley E.
Published: May 2006

The effect of pressures up to 3 kbar on the rate of the acid-catalyzed hydrolysis of methyl, ethyl, and t-butyl acetates in dilute aqueous acid and of ethyl acetate in concentrated hydrochloric acid has been measured. The volume of activation for t-butyl acetate is zero within experimental error, showing that the mechanism is unimolecular. Those for methyl and ethyl acetates are near –9 cm3mole−1 in both dilute and concentrated acid. We deduce from this that the mechanism is the same in 9.2-M hydrochloric acid as in dilute acid, that the transition state is not highly polar, and that if the proton in the reactive protonated ester is on the carbonyl oxygen then the attacking water molecule adds, and if the proton is on the ether oxygen then the attacking water molecule substitutes.
A STUDY OF THE EMISSION INTENSITIES OF Cr LINES FROM SHOCKED GASES CONTAINING Cr(CO)6
Authors: Bauer S. H. , Kiefer John H. , Loader Brian E.
Published: May 2006

Argon–nitrogen mixtures (9/1) were inoculated with traces of Cr(CO)6 (0.026%) and shocked to temperatures in the range 3500 °K to 5700 °K. The intensities of a violet line (7P2 → 7S3) and a triplet of green lines (5P3,2,1 → 5S2) were measured concurrently, with a dual-channel spectrograph. Exclusive of runs for which T > 5000 °K, the variation of intensity with temperature was brought to agreement with theoretical predictions under the assumption that the N2 vibrations, the dissociation of Cr(CO)6, and the ionization of Cr attained their equilibrium states, but allowance had to be made for self-absorption. The dependence of the rise times on temperature suggest that the excitation and ionization of Cr is predominantly due to collisions with electrons. The over-all shapes of the recorded light pulses were qualitatively accounted for. It is suggested that extraneous background radiation contributed to the measured intensities for samples shocked to temperatures above 5000 °K.
OLIGOSACCHARIDES FROM THE SAP OF SUGAR MAPLE (ACER SACCHARUM MARSH)
Authors: Haq S. , Adams G. A.
Published: May 2006

From the sap of the sugar maple (Acersaccharum Marsh) two trisaccharides have been isolated by column and paper chromatography. One was identified as O-β-D-fructofuranosyl-(2 → 6)α-D-glucopyranosyl(1 → 2)β-D-fructofuranoside (6G-fructosylsucrose), the other was tentatively established as either 6F-fructosylsucrose or 1F-fructosylsucrose. These trisaccharides are not related in either composition or structure to the polysaccharides present in the sap and wood.
RECOMBINATION OF ATOMS AT THE SURFACE OF THERMOCOUPLE PROBES
Authors: Tsu Kin , Boudart M.
Published: May 2006

When atoms produced by a discharge at one end of a closed cylindrical tube diffuse down the tube, their rate of recombination on the walls of the tube can be determined by measuring the temperature of a probe traveling along the axis of the tube. However, the catalytic activity of the probe may, under specified conditions, appear to be the same whatever the catalytic activity of the probe material. This effect is offered as a possible explanation of the findings of Wood and Wise, who recently reported essentially the same recombination probability for hydrogen atoms on 12 different metals.
PHOSPHATASE ALCALINE INTESTINALE: CINÉTIQUE DE L'HYDROLYSE DU PHOSPHATE DE p-NITROPHÉNYLE
Authors: Lazdunski Michel , Ouellet Ludovic
Published: May 2006

The Michaelis constants and the rates at high substrate concentration for the system p-nitrophenyl phosphate – intestinal alkaline phosphatase have been measured at 15.3 °C and 24.4 °C from pH 7.5 to pH 10.4.The experimental data can be interpreted as indicating the presence of three acid groups in the active center of the enzyme. The observed pK of ionization of these groups are 9.02, 8.39, and 7.65 at 15.3 °C, and 9.75, 8.42, and 7.62 at 24.4 °C.These data stress the importance of electrostatic interactions between the groups in the active center and the rest of the enzyme molecule. A heat of ionization of 6 to 7 kcal/mole is attributed to each of these groups. At least one active group of the enzyme would be a thiol function and the other ones imidazole or thiol.
ADSORPTION OF BENZENE AND ETHANOL UP TO HIGH RELATIVE PRESSURES ON FINELY DIVIDED SODIUM CHLORIDE: PART I. PARTICLE SIZE EFFECTS AND THE ADSORPTION OF BENZENE: PART II. THE LOWERING OF SURFACE FREE ENERGY BY ETHANOL
Authors: Weiler R. R. , Beeckmans J. , McIntosh R.
Published: May 2006

Adsorption of benzene has been studied using four samples of fine sodium chloride. The range of relative pressures employed extended to 0.99. The data were employed to show that a correction to the relative pressure should be applied because of the curvature of the surface. The correction was made in the form of a reduction of the apparent relative pressure by application of the Kelvin equation, since the relative pressure over a convex surface would be less than over a plane surface. The adsorption data at high relative pressures for several samples of salt could then be represented by a common curve. It was further concluded that the thick-layer theory of adsorption due to Frenkel, Halsey, and Hill was applicable to adsorption on salt. Adsorption data for ethanol were then obtained and the reduction of surface free energy of the salt by the saturated vapor was evaluated. This figure was then combined with van Zeggeren's and Benson's value of the solid–liquid interfacial free energy for salt and ethanol to provide a provisional value of the surface free energy of sodium chloride of 227 ergs cm−2.
THE CONDENSATION OF RHODANINE AND DERIVATIVES WITH 4-ANTIPYRINALDEHYDE
Authors: Allan Frederick J. , Allan G. Graham
Published: May 2006

not available
THE MERCURY-PHOTOSENSITIZED OXIDATIONS OF HYDROCARBONS: PART I. INTERACTION OF MERCURY WITH PRODUCTS FORMED IN THE REACTING MIXTURE
Authors: Bell K. M. , McDowell C. A.
Published: May 2006

The interaction of mercury with two hydrocarbon oxidation systems, namely those of oxygen and cyclohexene, and oxygen and isobutane, has been studied at 30 °C in a conventional static photochemical apparatus. The removal of mercury from the gas phase in the mercury-photosensitized oxidation of isobutane is attributed to a reaction with ozone,[Formula: see text]whilst interaction with an intermediate of the oxidation chain is responsible for mercury removal in the cyclohexane oxidation reaction:[Formula: see text]
MERCURY-PHOTOSENSITIZED OXIDATIONS OF HYDROCARBONS: PART II. THE MERCURY-PHOTOSENSITIZED OXIDATION OF ISOBUTANE
Authors: Bell K. M. , McDowell C. A.
Published: May 2006

The mercury-photosensitized oxidation of isobutane has been studied over a wide range of pressures of the hydrocarbon and oxygen, in a conventional static photochemical apparatus at the temperatures of 30 °C and 100 °C. The main products of the reaction are tertiary butyl hydroperoxide, together with tertiary butyl alcohol, acetone, and corresponding small quantities of formaldehyde and methyl alcohol. Isobutyraldehyde was also detected; ditertiary butyl peroxide being notably absent. Peroxide yields suggest that a reaction between an excited isobutane molecule and oxygen is important in the initiation processes and that peroxide is formed in the reaction[Formula: see text]
THE INFLUENCE OF HYDROGEN ION CONCENTRATION ON THE MYOSIN-CATALYZED HYDROLYSIS OF ADENOSINE TRIPHOSPHATE
Authors: Pelletier Gérard E. , Ouellet Ludovic
Published: May 2006

The Michaelis constants for the system myosin–ATP have been measured at 5 °C and 15 °C from pH 7.0 to pH 10.5, in the presence of 0.4 M potassium chloride and 0.005 M calcium chloride. The experimental data point to the presence, in the active center, of two ionizable groups, with experimental acid pK of 7.35 and 8.6 respectively at 15 °C. The apparent heats of ionization of these groups are about 9 kcal/mole for the first one and close to zero for the second. These data are interpreted as indication of the presence in the active center of myosin of a histidyl and a sulphydryl residue. A mechanism is proposed for the hydrolysis of ATP in the presence of myosin.
EFFECT OF AMBIENT OXYGEN ON THE SEMICONDUCTIVITIES OF EVAPORATED FILMS OF MESONAPHTHODIANTHRENE AND MESONAPHTHODIANTHRONE
Authors: Kuroda H. , Flood E. A.
Published: May 2006

The electrical conductivity of an "evaporated" film of mesonaphthodianthrene increases when the film is exposed to oxygen. The increase in conductivity is associated with changes in the semiconductivity activation energies. The activation energy for the oxygen-free anthrene (bulk conduction) is 0.74 ev while that associated with oxygen adsorption (surface conduction) is 0.40 ev. In marked contrast, the conductivity of an evaporated film of mesonaphthodianthrone decreases when exposed to oxygen. An oxygen-free film of the anthrone has different activation energies in different temperature regions, the activation energies being 0.73 ev and 0.43 ev in the higher and lower temperature regions, respectively. The conduction associated with the lower activation energy decreases when the film is exposed to oxygen.The effect of oxygen on the semiconductivities of mesonaphthodianthrene and mesonaphthodianthrone are compared with the effect of oxygen on their electron spin resonance spectra.
BACTERIOSTATS: V. THE PREPARATION AND BACTERIOSTATIC PROPERTIES OF AMIDINE DERIVATIVES
Authors: Garmaise D. L. , Kay R. W. , Gaudry R. , Baker H. A. , McKay A. F.
Published: May 2006

A number of polyamidines, N-substituted amidines, and diamidines were prepared for evaluation as bacteriostats. N,N′-Bis-(3,4-dichlorobenzyl)-sebacamidine dihydrochloride was the most active compound prepared in this investigation.
CYCLOHEXANE COMPOUNDS: III. THE 1-METHOXY- AND 1-ETHOXY-2-HYDROXY-3-BROMOCYCLOHEXANES
Authors: Bannard R. A. B. , Hawkins L. R.
Published: May 2006

1α-Methoxy- 2β - hydroxy- 3α-bromocyclohexane and 1α-methoxy-2α-hydroxy-3β-bromocyclohexane have been prepared by the action of hydrobromic acid on 1β-methoxy-2α,3α-epoxycyclohexane and 1α-methoxy-2α,3α-epoxycyclohexane respectively. Assignment of stereochemical configuration to 1α-methoxy-2β-hydroxy-3α-bromocyclohexane was made by catalytic denomination of the phenyl- and 1-naphthyl-urethanes to derivatives of 2β-methoxy-1α-cyclohexanol. An alternative proof of structure was obtained by de-etherification of the bromohydrin to 3α-bromo-1α,2β-cyclohexanediol, which was catalytically debrominated to 1α,2β-cyclohexanediol and oxidized via periodate to 2-bromoadipaldehyde, isolated as the bis-2,4-dinitrophenylhydrazone. The structure of 1α-methoxy-2α-hydroxy-3β-bromocyclohexane was established by de-etherification to 3β-bromo-1α,2α-cyclohexanediol, which was oxidized by periodate 10 times more rapidly than its isomer. The corresponding ethoxy compounds were prepared and their structures were elucidated in a completely analogous manner.
THE EPIMERIZATION OF DELCOSINE
Authors: Skarić Vinko , Marion Léo
Published: May 2006

Delcosine has been assigned tentatively the same C—N skeleton as lycoctonine. In lycoctonine, ring A carries at C-1 a methoxyl group which is directed away from the nitrogen ring. In delcosine, C-1 carries a hydroxyl group which has the opposite configuration and is directed towards the nitrogen. An attempt to correlate the two structures first involves epimerization at C-1 in delcosine. This has been carried out by oxidation of desethyldelcosine to an azomethine, the ethiodide of which, by the action of methanolic potassium hydroxide, is converted to oxo-1-epidelcosine in two steps. Oxo-1-epidelcosine in an acid-catalyzed rearrangement is transformed to a pinacone which, after methylation, gives O,O-dimethyl-anhydro-oxo-1-epidelcosine. This compound was compared with O-methylanhydro-oxolycoctonine, prepared from oxolycoctonine, but was not identical. Removal of a methoxyl, which in each compound is ortho to a carbonyl, by the action of sodium amalgam, produced O,O-dimethyl-6-desmethoxy-anhydro-oxo-1-epidelcosine and O-methyl-6-desmethoxy-anhydro-oxolycoctonine, which are not identical, but show in their infrared spectra much less dissimilarity than the spectra of the pair of compounds from which they were derived. These results are discussed in terms of the structure of delcosine.
INTERMOLECULAR FORCES AND LIQUID STRUCTURE IN SOME METAL ALKOXIDES
Authors: Bradley D. C. , Prevedorou Calliope C. A. , Wardlaw W.
Published: May 2006

The viscosities of some alkoxides of titanium, zirconium, cerium (IV), thorium, and tin (IV) have been measured in the temperature range 25–40 °C. The liquid structure in these compounds is discussed in terms of the activation energy, free energy, and entropy of activation for viscous flow, and the energies of cohesion and vaporization.
INFRARED SPECTRA AND THE STRUCTURES OF XANTHATES AND DIXANTHOGENS
Authors: Shankaranarayana M. L. , Patel C. C.
Published: May 2006

The infrared spectra of representative dialkyl dixanthogens and a few xanthates have been examined. All these compounds have two strong absorption bands in the regions 1140–1265 and 1010–1080 cm−1. On the basis of the shift of the bands with the changes in the substituents in the xanthic acid, the former band is assigned to the C=S group, while the latter to the CO group. Except in the ionic compounds, the canonical structure [Formula: see text] contributes very little to the structures of dixanthogens and covalent metal complexes.
HYDROGEN BONDING IN SOLUTIONS OF SUBSTITUTED ACETIC ACIDS
Authors: Reeves Leonard W.
Published: May 2006

The changes in chemical shift of the acid proton in some simple carboxylic acids on dilution in four solvents has been studied. The existence of chainlike hydrogen-bonded polymers in solution is suggested by the results. The association of the monomer molecules in dilute solution with donor centers in the solvent molecules is suggested from a study of the —O—H monomer stretching bond in the vapor and in two solvents. There is a difference in the behavior of acetic and trifluoroacetic acid in N-methyl and N,N-dimethyl formamide, which has been explained in terms of protonation of the amides in trifluoroacetic acid solutions.
THE RADIOLYSIS OF ETHANOL: I. VAPOR PHASE
Authors: Ramaradhya J. M. , Freeman G. R.
Published: May 2006

The alpha radiolysis of ethanol vapor at 108 °C produced hydrogen as the major single product, with smaller amounts of methane, carbon monoxide, ethylene, ethane, acetaldehyde, formaldehyde, water, 2,3-butanediol, 1,2-propanediol, propanol, and butanol. The initial yield of hydrogen was G(H2) = 8.9 ± 0.4, which is much higher than the values reported for the liquid phase (G(H2) ≈ 4).A mechanism is proposed to account for the formation of the products. However, the observed value of G(H2O) = 5.4 is over four times larger than can be explained by the mechanism.There is a good material balance in the observed reaction products, which indicates that little polymerization occurred during the radiolysis. This is in marked contrast with the vapor phase radiolysis of cyclohexane.
CARBONIUM PERCHLORATES IN CHLOROFORM SOLUTION
Authors: Gatzke A. L. , Stewart Ross
Published: May 2006

not available
THE GAS–LIQUID PARTITION CHROMATOGRAPHY OF CARBOHYDRATE DERIVATIVES: PART I THE SEPARATION OF GLYCITOL AND GLYCOSE ACETATES
Authors: Gunner S. W. , Jones J. K. N. , Perry M. B.
Published: May 2006

Gas–liquid partition chromatography has been used to separate the fully acetylated derivatives of tetritols, pentitols, hexitols, heptitols, octitols, and anomeric glycoses.
THE EFFECT OF THE AMBIENT OXYGEN ON THE ELECTRICAL PROPERTIES OF AN EVAPORATED FILM OF PENTACENE
Authors: Kuroda Haruo , Flood E. A.
Published: May 2006

The "oxygen effect" on the dark current as well as that on the photocurrent was investigated using thin evaporated films of pentacene, 1,2-benzpentacene, 1,2,8,9-dibenzpentacene, 6,13-diphenylpentacene, and 5,7,12,14-tetraphenylpentacene. No oxygen effect could be detected in the dark current.From the photocurrent dependence on oxygen pressure and from the rate of photocurrent decay, it is concluded that additional charge carriers are produced on illumination by photoexcitation of a surface complex.
ALIPHATIC CHEMISTRY OF FLUORENE: PART VII. SPIROLACTONES
Authors: Bavin P. M. G.
Published: May 2006

A number of spirolactones have been prepared from fluorene-9-carboxylic acid, either by the halolactonization reaction or by alkylation of the methyl ester with hydroxyalkyl halides.
THE CLEAVAGE OF ETHERS BY t-BUTYLMAGNESIUM BROMIDE AND COBALTOUS CHLORIDE
Authors: Eisenbraun E. , Purves C. B.
Published: May 2006

not available
THE RAMAN SPECTRA OF SOME POLYSULPHURYL CHLORIDES AND FLUORIDES
Authors: Gillespie R. J. , Robinson E. A.
Published: May 2006

The Raman spectrum of disulphuryl chloride, S2O5Cl2, has been reinvestigated and the Raman spectra of S2O5F2, S2O5ClF, S3O8Cl2, S3O8F2, and the new compound S3O8ClF are reported for the first time. The vibrational spectra of these polysulphuryl halides are interpreted in terms of characteristic group frequencies by comparison with the vibrational spectra of simple sulphuryl compounds. The spectra are consistent with acyclic structures for the polysulphuryl halides.
THEORETICAL STUDIES ON THE ELECTRONIC SPECTRA OF SUBSTITUTED AROMATIC MOLECULES: PART I. THE INTRAMOLECULAR ELECTRON TRANSFER MODEL
Authors: Bloor J. E.
Published: May 2006

A simple empirical model, based on molecular orbital theory without configuration interaction, is used to interpret the K band transitions of substituted aromatic molecules as involving intramolecular electron transfer between substituent and hydrocarbon. For electron-donating substituents, such as amino, methoxyl, chloro, bromo, and iodo, the transfer is from substituent to hydrocarbon, while for electron-attracting substituents, such as nitro, formyl, acetyl, and cyano, the charge transfer is from hydrocarbon to substituent. Such a treatment is successful for "long field molecules" (benzene, diphenyl, terphenyl, styrene, and stilbene), but for "round field" molecules agreement between experiment and theory was achieved only for electron-donating substituents. The theory, like less empirical theories, overestimates the relative effect of a substituent in the 2-position compared with substitution in the 1-position.
PROTON RESONANCE SPECTRA OF 8-HYDROXY AND 8-METHYL QUINOLINE
Authors: Reeves L. W. , Strømme K. O.
Published: May 2006

not available
THE SEPARATION OF SMALL AMOUNTS OF THE PLATINUM METALS: 1. THE COLORIMETRIC DETERMINATION OF RHODIUM AND ITS SEPARATION FROM IRIDIUM
Authors: Ryan D. E.
Published: May 2006

A method for separating small amounts of rhodium from iridium is described. In 3 to 9 M hydrochloric acid solutions, the amber-to-red complex of bivalent rhodium with 4,5-dimethyl-2-mercaptothiazole is formed after reduction of tervalent rhodium with chromous or stannous chloride. Rhodium is quantitatively separated from iridium by chloroform extraction of this product; separation can be made in solutions that have been fumed with sulphuric acid if chromous chloride is used for the prior reduction of the rhodium. The complex, after removal of the chloroform, is dissolved in dilute hydrochloric acid, and the optical density of the resulting colored solution is measured.
THE EFFECT OF HYDROGEN CHLORIDE ON THE NEAR-INFRARED SPECTRUM OF NYLON
Authors: Larose P.
Published: May 2006

Samples of oriented nylon film and filament were treated with anhydrous HCl and examined in the near-infrared region of 9000 to 3700 cm−1 with polarized light. The results are in agreement with previous observations made in the 3600–600 cm−1 region, and corroborate earlier evidence that HCl interacts with the peptide linkage. The disorienting effect of the HCl is also reflected in the spectrum of the treated specimens.
PERFLUOROALKYL ARSENICALS: PART III. THE PREPARATION AND PROPERTIES OF SOME NEW TRIFLUOROMETHYL AND HEPTAFLUOROPROPYL ARSINES
Authors: Cullen W. R.
Published: May 2006

The reaction of heptafluoroiodopropane with the appropriate phenyl-iodo-arsine in the presence of mercury yields the compounds C3F7As(C6H5)2, (C3F7)2AsC6H5, and C3F7(CH3)AsC6H5. However, the compounds (CF3)2AsR (R = C2H5, C4H9) are obtained from the reaction of the compounds R2AsI with mercury and trifluoroiodomethane. The ultraviolet spectra of the heptafluoropropyl-arsines are discussed.
β-AROYL-α- AND -β-ARYLPROPIONIC ACIDS: PART I. THEIR PREPARATION AND LACTONIZATION
Authors: Sherif Sayed
Published: May 2006

Bromobenzene reacts with phenyl- and p-methoxyphenyl-succinic anhydride in the presence of anhydrous aluminum chloride to give a mixture of β-p-bromobenzoyl-α- and -β-phenyl-propionic acid, and a mixture of β-p-bromobenzoyl-α- and -β-p-hydroxyphenylpropionic acid, respectively.Similarly, iodobenzene reacts with the same anhydrides to give a mixture of β-p-iodobenzoyl-α- and -β-phenylpropionic acid and β-benzoyl-α- and -β-phenylpropionic acid, and a mixture of β-benzoyl- and β-p-iodobenzoyl-α-p-methoxyphenylpropionic acid, respectively.Phenyl- and diphenyl-succinic anhydride are cyclized by aluminum chloride to 1-ketoindane- and 1-keto-2-phenylindane-3-carboxylic acid, respectively.The above keto acids are converted by boiling acetic anhydride into β,γ-unsaturated γ-lactones.
THE ELECTRONIC ABSORPTION SPECTRA OF DIXANTHOGENS
Authors: Shankaranarayana M. L. , Patel C. C.
Published: May 2006

The electronic absorption spectra of diethyl, diisopropyl, di-n-butyl, and diisoamyl dixanthogens have been studied in polar and non-polar solvents. The compounds exhibit a low-intensity band around 365 mµ and two high-intensity bands around 285 and 242 mµ. The 365 mµ band is assigned, as a result of the solvent studies, to n → π* transition and the 285 mµ band to π → π* transition. The band around 242 mµ may be due to the n → σ* transition, since in polar solvents it shows mainly a blue shift.
CORRELATIONS OF ETHYLENIC PROTON COUPLING CONSTANTS WITH ELECTRONEGATIVITY
Authors: Schaefer T.
Published: May 2006

A strong correlation is found between the electronegativity, Ex, and the three proton coupling constant of the vinyl group in over a hundred compounds of the type CH2 = CHX. This correlation extends over the range Ex = 4 to 1 and over the range Jgem + Jcis + Jtrans = 14 to 50 c.p.s. Simple implications and some useful applications of this correlation are discussed.
ACID-CATALYZED REACTIONS OF VINYL COMPOUNDS: PART I. PRELIMINARY STUDIES ON VINYL ESTERS AND BENZENE
Authors: Pepper J. M. , Robinson B. P. , Schwanbeck G. W.
Published: May 2006

A detailed study of the nature, and the mechanism of formation, of the products of the aluminum chloride catalyzed reaction of vinyl esters and benzene has been initiated. Using vinyl acetate the formation of the previously reported acetophenone, 1,1-diphenylethane, and 9,10-dimethylanthracene has been confirmed. By means of both column chromatography and thermal distillation, a similar carbonyl-containing fraction was obtained which, as a result of a gas chromatographic study, has been shown to be a mixture of six compounds. Of these, the two major components have been identified as acetophenone and p-ethylacetophenone, the latter previously unreported as a product of this reaction.The reaction of vinyl formate and benzene has been studied for the first time. High yields of 9,10-dimethylanthracene were obtained but no carbonyl-containing compounds. A study of the effect of a variation in molar ratio of benzene to vinyl acetate indicated that a maximum yield of 9,10-dimethylanthracene was obtained using a 6:1 molar ratio.The significance of these results is discussed.A method has been devised for an improved synthesis of 9,10-dimethylanthracene. The generality of this procedure for the synthesis of other substituted polynuclear compounds is indicated.
SYNTHESIS OF POTENTIALLY PHYSIOLOGICALLY ACTIVE β-PHENYLETHYLAMINES: PART II. 3,4-METHYLENEDIOXY-α-AMINOMETHYLBENZYL ALCOHOL DERIVATIVES
Authors: Heacock R. A. , Hutzinger O. , Nerenberg C.
Published: May 2006

The preparation of 3,4-methylenedioxy-α-aminomethylbenzyl alcohol and a number of its N-alkyl and N,N-dialkyl derivatives by the reduction or reductive alkylation of 3,4-methylenedioxy-α-nitromethylbenzyl alcohol is described.
CIS–TRANS ISOMERS OF ASARONE, THEIR LIQUID–GAS CHROMATOGRAPHIC BEHAVIOR AND THAT OF CERTAIN OTHER PROPENYLPHENOLETHERS
Authors: Baxter R. M. , Fan M. C. , Kandel S. I.
Published: May 2006

not available
FLUORINE PERCHLORATE, INFRARED AND NUCLEAR MAGNETIC RESONANCE SPECTRA
Authors: Agahigian H. , Gray A. P. , Vickers G. D.
Published: May 2006

not available
STUDIES OF CHLOROBIUM CHLOROPHYLLS: IV. PREPARATIVE LIQUID–LIQUID PARTITION CHROMATOGRAPHY OF PORPHYRINS AND CHLOROPHYLL DERIVATIVES AND ITS USE TO RESOLVE CHLOROBIUM PHEOPHORBIDE (650) INTO SIX COMPONENTS
Authors: Hughes D. W. , Holt A. S.
Published: May 2006

Various porphyrins and chlorophyll derivatives have been purified on a preparative scale by distribution between hydrochloric acid and ether on Celite columns. By this technique crude Chlorobium pheophorbide (650) was resolved into six components, which possessed almost identical visible absorption spectra, but slightly different acid distribution numbers. Chromic acid oxidation and subsequent gas–liquid partition chromatography of the neutral fractions indicate the presence of more than one Chlorobium chlorophyll (650) in the original pigment preparation.
THE OBJECTIVE EVALUATION OF THE POSITIONS OF INFRARED ABSORPTION MAXIMA
Authors: Jones R. Norman , Seshadri K. S. , Hopkins J. W.
Published: May 2006

The fit of polynomial series of varying degree to infrared absorption bands in the neighborhood of the maxima has been investigated, and, in the instances considered, an acceptable graduation was usually possible with a quartic equation. By differentiation of the polynomial an objective, and independently reproducible, numerical value can be obtained for the band maximum. The abscissal positions computed for the maximum converged as the degree of the polynomial was raised, provided the experimental points did not exhibit gross departures from a smooth distribution. The convergence of the roots of the quadratic, cubic, and quartic functions was employed to check the applicability of the technique in individual cases. A Lorentz curve can be fitted exactly by a parabola if the reciprocal of the absorbance is plotted as ordinate, but in practice no improvement in the fit of power series to real absorption bands was achieved by using the reciprocal ordinates.Frequency shifts in the infrared spectra of benzene, acetone, and nitromethane on solution in carbon tetrachloride have been measured by this method. The finite displacements observed contradict a recent statement in the literature that the peak frequencies of the bands in the spectra of these and other substances are uninfluenced by solution in non-polar solvents.
THERMODYNAMIC PROPERTIES AND GEOCHEMISTRY OF ISOTOPIC COMPOUNDS OF SELENIUM
Authors: Krouse H. R. , Thode H. G.
Published: May 2006

Using "normal vibration equations" and statistical mechanics, the isotopic vibrational frequencies and the partition function ratios for various Se76- and Se82-containing compounds have been calculated. The equilibrium constants for selenium isotope exchange reactions derived from these partition function ratios indicate that noticeable fractionation of selenium isotopes can be expected in the laboratory and in naturally occurring processes.The Se82/Se76 ratios for 16 natural samples have been compared mass spectrometrically. Variations of up to 1.5% found in this ratio are discussed.A kinetic isotope effect of 1.5% found in a chemical reduction of selenite ion to elemental selenium is also discussed.
FURANOCOUMARINS OF PHELLOPTERUS LITTORALIS
Authors: Yang Chao-Hwa , Brown Stewart A.
Published: May 2006

not available
NUCLEAR MAGNETIC RESONANCE STUDIES OF HYDROGEN BONDING IN ETHANOL AND 2,2,2-TRIFLUOROETHANOL
Authors: Rao B. D. Nageswara , Venkateswarlu Putcha , Murthy A. S. N. , Rao C. N. R.
Published: May 2006

not available