bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Study of the Surface Heterogeneity of Nickel Oxide Catalysts by the Flash Desorption Method
Authors: Kondo Junko , Uchijima Toshio , Yoneda Yukio 
Published: July 2006

Abstract
The flash desorption method was applied to the carbon dioxide - nickel oxide system in order to investigate the surface heterogeneity of nickel oxide catalysts. It was found that there were two peaks in flash desorption chromatograms. The Arrhenius plots for carbon monoxide oxidation on nickel oxide were found to be composed of two straight lines. It was shown that the inflection of the Arrhenius plots was due to the existence of two kinds of active sites which differ in activation energy for the oxidation reaction and in the strength of interaction with carbon dioxide. The numbers of active sites for carbon monoxide oxidation were determined by the measurement of the amounts of desorbed carbon dioxide.
Studies of the Photochemistry of Aromatic Diazo Compounds. II. The Electronic Structures of Some p-Substituted Benzenediazonium Cations
Authors: Sukigara Mitsunori , Kikuchi Shin-ichi 
Published: July 2006

Abstract
The electronic structures and electronic absorption spectra of p-fluoro-, p-chloro-, p-bromo-, p-iodo, p-methoxy-, and p-dimethylaminobenzenediazonium cations were studied by making molecular orbital calculations and by measuring the visible and near-ultraviolet absorption spectra. From the calculations it is understood that when an electron-donating group is introduced at the p-position of the benzenediazonium cation, the 1A1-1A1 transition shows a very large shift to longer wavelengths, while the 1A1-1B1 transition is not so much affected; at the same time, the N–N bond order in the ground state decreases. It is shown that there is a linear relationship between the N–N bond order and the wave number of the N–N stretching of the p-substituted benzenediazonium salt. It is concluded from the calculations that the electron affinity of the nonsubstituted benzenediazonium cation has a large value, such as 2.40 eV.
The Concentrations and the Reactivity of the Adsorbed Species during Surface Catalysis on a Ternary-component Methanol Synthesis Catalyst
Authors: Tsuchiya Susumu , Shiba Tadao 
Published: July 2006

Abstract
The relative reactivity of the adsorbed species during a catalytic methanol synthesis reaction on a ternary-component catalyst was investigated. Abrupt changes in the ambient pressure of a component in the gas phase, at a nearly equilibrium condition, were correlated with the corresponding changes in the amounts of the adsorption and in the total ambient pressure. The data collected from such dynamical treatments indicate that the species adsorbed on the catalyst surface, in a nearly equilibrated system of the simultaneous adsorption of hydrogen and carbon monoxide, is mostly the surface intermediate complex formed from both of them. Furthermore, the results obtained suggest an order for the reaction speed of each elementary step in the methanol synthesis reaction.
Internal Rotation of Propane from the Microwave Spectrum
Authors: Hirota Eizi , Matsumura Chi , Morino Yonezo 
Published: July 2006

Abstract
The microwave spectrum of propane was observed in the first-excited states of the CH3torsion. Each transition was split into a symmetric triplet; the splittings were 14–19% larger for the (−) state than for the (+) state. The top-top interaction and its effect on the rotational spectra were treated by the perturbation theory, and the results were applied to the analysis of the triplet splittings. The two barrier parameters, V3 and V3″, were thus determined to be 3325±20 and −170±30 cal/mol respectively.
Investigations of Solvent Effects on Paper Chromatography
Authors: Paul Agnes , Janardhan Pandarinath B 
Published: July 2006

Abstract
The mechanism of paper chromatography consists of three stages: i) adsorption; ii) desorption; iii) migration due to solvation. Solvation depends on the physical properties of the solvent. The present paper will attempt to correlate the Rf values of metal ions with such physical properties of the solvent as (a) surface tension, (b) viscosity, (c) solubilisation, and (d) the dielectric constant. Experiments have been conducted with pure and mixed solvents of the aliphatic alcohol series. As a result, it may be reported that the Rf values of cations (silver, copper, nickel and ferric ions) bear almost a linear relationship to the dielectric constant/viscosity quotient.
A Spectrophotometric Study on the Thorium Complex of o-Hydroxyphenyl-azo-chromotropic Acid
Authors: Toei Kyoji , Miyata Haruo , Nakashima Susumu , Kiguchi Sachiaki 
Published: July 2006

Abstract
o-Hydroxyphenyl-azo-chromotropic acid was used as a colorimetrie reagent for thorium. The acid dissociation constants of the reagent have been determined by the pH titration method. The pK1 (for the dissociation of the phenolic hydroxyl group) and pK2 (for that of the naphtholic hydroxyl group) were found to be 7.60 and 10.60 respectively at 25°C and μ=0.1. The reagent forms a violet 1 : 1 complex in an acidic solution, and its apparent stability constant is measured spectrophotometrically.
The Spectrophotometric Determination of Scandium(III) with Chromazurol S
Authors: Ishida Ryoei , Hasegawa Norio 
Published: July 2006

Abstract
Chromazurol S reacts with scandium(III) in a weakly acidic medium to form one of two kinds of complexes according to the pH value of the medium. Their compositions were confirmed; one had a 1 : 2 combining ratio of scandium (III) and chromazurol S at pH 5.2 or higher, and the other, a 1 : 1 ratio at pH below 4.0. The color development of the 1 : 2 complex is more sensitive than the other. Therefore, it was applied to the determination of scandium(III). Several conditions for the color development were investigated, a calibration curve was made under the optimum conditions, and the influences of coexisting ions were investigated. The maximum absorption wavelength of the complex is 550 mμ against the reagent blank. The optimum pH for the color development is about 5.6. By adding a reagent in an amount four times the scandium concentration, the maximum color intensity is given. The color intensity decreases gradually during the first 1.5 hr, and then it remains constant for several hours. A linear relationship between the absorbance and the scandium concentration is obtained in the concentration range from 4 to 27 μg per 10 ml. The value of the molar extinction coefficient of the complex at 550 mμ is 27000, and the sensitivity of the color reaction is 0.0017 μg/cm2 for log I0/I=0.001. The formation constant, K, of the complex is calculated to be 9.5×1011 under these conditions. Anions such as fluoride, phosphate, oxalate, tartrate, citrate, and EDTA interfere with the color development of the complex. Cations such as Al(III), Be(II), U(VI), Fe(II), Th(IV), Cu(II), Y(III), Fe(III), Zr(IV), and W(VI) interfere, too.
Isotopic Exchange Reaction between Bis(α-benzildioximato)nickel(II) and Nickel Ions in Pyridine and Pyridine-Water Solutions
Authors: Hirota Reiko , Saito Nobufusa 
Published: July 2006

Abstract
The rate of isotopic exchange reaction between bis(α-benzildioximato)nickel(II) and nickel ions in pyridine greatly increases in the presence of water. When the water content in pyridine is lower than 3 m, the reaction takes place according to the rate equation:
Rate=k1(complex)+k2(complex)(Ni2+)(H2O)
For the catalyzed step, a mechanism is proposed.
Copper(II) Complexes with Phthalic Acid
Authors: Shimizu Ichiro , Tsuchiya Ryokichi , Kyuno Eishin 
Published: July 2006

Abstract
Three copper(II) complexes with phthalic acid, [Cuph(H2O)] (I) (ph=C6H4(COO)2), [Cu(Hph)2(H2O)2] (II), and [Cuph]2 (III), were prepared. Compound I was prepared from an aqueous solution of copper sulfate and phthalic acid within the temperature range of 60–79°C. It was a light blue crystal forming a hexagonal unit, the parameters being a=13.07 Å and c=13.98 Å and with the chemical unit Z equalling 8. II was prepared at a temperature below 60°C. It was a blue crystal having a hexagonal unit of a=11.42 Å, c=13.68 Å, and Z=4. The magnetic moments of I and II were 1.87 B. M. and 1.96 B. M. (both 21.5°C) respectively, showing I and II to have a monomer structure with respect to the two copper atoms. III could be prepared at temperatures above 79°C. It was a bluish-green crystal containing a hexagonal unit of a=12.77 Å, c=13.02 Å, and Z=4. The magnetic moment of III was found to be 1.54 B. M. (18.4°C), suggesting that complex III consisted of a dimer structure with respect to the copper atoms. The appearance of a shoulder near 370 mμ. in the reflection spectra of the copper complex III in the powdered crystalline state confirmed the suggestion of a dimer structure.
Interaction of Excited Aromatic Hydrocarbons with Aromatic Amines
Authors: Mataga Noboru , Ezumi Kiyoshi 
Published: July 2006

Abstract
It has been established that many aromatic hydrocarbons in N,N-dimethyl aromatic amine solvents show their fluorescence spectra at much longer wavelengths than in such inactive solvents as n-hexane and toluene. Because the absorption spectra of the hydrocarbons in the amines do not show any essential change, it is confirmed that specific interaction between a hydrocarbon and an amine occurs only in the excited electronic state (the fluorescent state). It has been clearly demonstrated, from the relation between the frequencies of the long-wavelength fluorescence and the electron affinities of the excited aromatic hydrocarbons, the ionization potentials of the amines, etc., that this interaction can be ascribed to the charge transfer from the amine to the excited hydrocarbon, and that the long-wavelength fluorescence is a kind of charge-transfer fluorescence. At the temperature of liquid nitrogen, the interaction becomes much weaker because the rearrangement motions of molecules during the lifetime of the excited state, which are necessary for the charge-transfer complex formation, are more or less hindered in a rigid solvent at low temperatures. It has been confirmed that the interaction is still weaker in the phosphorescent state. This phenomenon has been explained by reference to the electronic processes in the complex.
The Autoxidation of Toluene Catalyzed by Metal Ions in Aqueous Solutions. I
Authors: Suzuki Nobutake , Hotta Hiroshi 
Published: July 2006

Abstract
The yield of benzaldehyde, which was the main product, depended on the kind of metal ions between 100°C and 200°C. The yield was high in a ferrous sulfate solution, even at lower temperatures, while it was extremely low in a ferric sulfate solution, even above 180°C. The yield in a cupric sulfate solution was appreciable at 180°C only with γ-radiation, while it was high near 200°C even without γ-radiation. All the yields were a little higher with γ-radiation than without γ-radiation. The rate-constant ratio of toluene to toluene-d8 was about 1.4 for the benzaldehyde and benzyl alcohol produced by using Fenton’s reagent at 70°C, respectively. It may be concluded from the experiments using the oxygen-18 enriched water that the oxygen of the benzaldehyde produced is transferred from the dissolved molecular oxygen, while that of benzyl alcohol is transferred partly from water. On the basis of these facts, a whole reaction scheme is proposed for the present system. The difference between toluene and benzene is also discussed in the present paper.
A New Spectrophotometric Method for the Determination of Micro Amounts of Sulfite
Authors: Okutani Tadao , Utsumi Satori 
Published: July 2006

Abstract
A new spectrophotometric method for the determination of a minute quantity of sulfite was studied. When a definite amount of aqueous solution of mercuric nitrate mixed with potassium bromide and an ethanol solution of diphenylcarbazone are added to the sample solution kept at pH 7.0, sulfite reacts with mercuric reagent and the excess of the mercuric reagent forms the reddish-violet complex with diphenylcarbazone which may be easily extracted by benzene. Sulfite is determined by measuring the absorbancy of the benzene phase which decreases upon an increase in the concentration of sulfite, at the wavelength of 562 mμ, The method which is applicable to the determination of both sulfite and sulfide has also been established, because sulfide as well as sulfite reacts with mercuric reagent. By this proposed method, sulfite (0.1—2.5 ppm) and sulfide (0.01—0.5 ppm) could be determined at the same time rapidly and accurately. The composition of the complex formed between mercury(II) and sulfite was also studied.
The Liquid Phase Oxidation of Acrolein. II. Solvent Effects in the Liquid Phase Oxidation of Acrolein and the Decomposition of Peracrylic Acid
Authors: Ohkatsu Yasukazu , Takeda Makoto , Hara Takao , Osa Tetsuo , Misono Akira 
Published: July 2006

Abstract
The liquid phase oxidation of acrolein and the decomposition of peracrylic acid with Co-(acac)3 in various solvents were investigated. The solvents of butyric and valeric acids gave the most desirable results with respect to the selective oxidation; for example, in butyric acid with 5×10−4mol/l of Co(acac)3 for 4 hr at 35°C, the conversion of acrolein and the selectivity of acrylic acid were 45.1% and 86.0%, respectively. The preferable solvent effects of C4 and C5 carboxylic acids were discussed in terms of the acidity and dielectric constant of the solvents, the oxygen solubility in the solvents and the interaction of the solvents with acrolein. Further more, from the comparison of solvent effects in the oxidation of acrolein with those in the decomposition of peracrylic acid, one of the rate determining steps in the oxidation was elucidated to be much concerned with the decomposition of peracrylic acid formed during the reaction.
An MO Interpretation of the Methylation of Olefins by the Methylsulfinyl Carbanion
Authors: Yamamoto Osamu , Kato Hiroshi , Yonezawa Teijiro 
Published: July 2006

Abstract
Recently the reaction of the methylsulfinyl carbanion with a number of olefins (quinoline, acridine, anthracene, butadiene, etc.) has been reported on by several authors. The superdelocalizability for the nucleophilic attack, Sr(N), is used as a theoretical index for discussing the intermolecular reactivity. It is pointed out that the calculated values of Sr(N) are useful in predicting the relative reactivity as well as the orientation in the nucleophilic aromatic methylation. In addition, the mechanism of the ring-opening reaction taking place with regard to benzofuran is discussed briefly.
Magnetic Properties of Aromatic Hydrocarbon-Alkali Metal Ion-Pair Salts. I
Authors: Nishiguchi Hiroaki 
Published: July 2006

Abstract
Measurements of magnetic susceptibility and electron paramagnetic resonance absorptions have been carried out on biphenyl (Bp)-potassium (K), -rubidium (Rb), and -cesium (Cs) ion-pair salts. These powder salts were prepared by the evaporation of the solvent from the corresponding anion radical solutions in vacuo. The magnetic susceptibility of the Bp-K system is paramagnetic and exhibits a maximum at 130±4°K. This susceptibility can be fitted approximately to the expression:
χM=\frac2Ng2β2kT·\frac13+eδ⁄kT,
which leads to a singlet-triplet dimer model consisting of a singlet ground state and a triplet state lying slightly above the ground state. The line width of the electron paramagnetic resonance (EPR) spectrum is also temperature-dependent and becomes broader as the temperature decreases. The Bp-Rb and Bp-Cs systems also exhibit susceptibilities which monotonously increase as the temperature decreases. These can be fitted to the higher temperature range (kT⁄δ&gt;1) of the above equation rather than to the Curie-Weiss law. For these compounds single absorption lines have also been observed at g=2.002 in the EPR spectra at room temperature. The results suggest that these salts may be interpreted generally by means of the singlet-triplet dimer model proposed for the organic salts based on the anion radical of tetracyanoquinodimethane (TCNQ). However, one marked difference is that the singlet-triplet separations of these compounds are very small in comparison with those of the TCNQ radical salts.
Krafft Temperatures of Perfluoro-Octanoic Acid and of Its Salts
Authors: Nakayama Haruo 
Published: July 2006

Abstract
The Krafft temperatures of perfluoro-octanoic acid and of its alkali metal and ammonium salts have been determined from the solubility measurements. The heats of solution and of wetting of dry solid surfactants have also been measured. The solubility decreases in the order; Li-salt&gt;Na-salt&gt;K-salt, and then increases in the sequence; Rb-salt&lt;Cs-salt. Ammonium salt is more soluble than sodium salt. Acid is least soluble. The heats of wetting depend markedly on the kind of counterions, but the heats of solution of hydrated solids, which are calculated from the temperature-dependence of single-dispersion solubility, are almost independent of the counterions. The order of Krafft temperatures for alkali metal salts is; Li&lt;Na&lt;K&gt;Rb&gt;Cs, just the reverse of that of the solubility. It is concluded that the Krafft temperature of each substance is mainly determined by the magnitude of the non-micellar solubility, and that the increasing order of the solubilities of salts can reasonably be estimated by comparing it with the solubility order of ordinary organic or inorganic salts which have the same chemical properties as the surfactants. This sequence of solubility is markedly determined by the strength of the acids from which the salts are derived.
The Structure of Mo7O246− Ion in the Crystal of Ammonium Heptamolybdate Tetrahydrate
Authors: Shimao Eikoh 
Published: July 2006

Abstract
The structure of a discrete polyanion, Mo7O246−, in the crystal of ammonium heptamolybdate tetrahydrate, previously determined by Lindqvist, has been redetermined and refined by a two-dimensional, single crystal X-ray diffraction study. The positional parameters of the oxygen atoms, which were left undetermined in the previous investigation, have been determined. Lindqvist’s description of the structure still applies. However, the distortion of the polyanion has been found to be more pronounced than was previously assumed. Comparisons with molybdenum oxides and oxyacids are discussed with regard to the structure, the Mo–Mo distances and Mo–O distances.
The Indirect Gas Ghromatographic Determination of Palladium in an Aqueous Solution
Authors: Hara Tadashi , Koga Tadashi , Takeda Hajime 
Published: July 2006

Abstract
An indirect method has been proposed for the gas-chromatographic determination of palladium in an aqueous solution. After a mixture of propylene and propane has come in contact with a palladium sample solution, the amount of propylene in the remaining gas is estimated, propane being used as an internal standard. An apparatus consisting of a gas sampler, a gas tank, etc. was devised. The reaction between propylene and palladium ions in less than 3.0 N perchloric acid goes to completion within 15 min. According to the present method, the calibration curve is straight for Pd up to 500 ppm and for Hg up to 1500 ppm. The following ions in concentrations less than that of Pd2+ are tolerable; Co2+, Mg2+, Mn2+, Li+, Sn4+, Ni2+, Cu2+, Cd2+, Zn2+, Pb2+, Al3+, ClO4−, Cl−, NO3−, CH3COO−, and SO42−, while Fe3+, Ag+, Hg2+, Pt2+ and Pt4+ interfere seriously. The interference of ferric, silver, and mercuric ions can be avoided by chloride or bromide precipitation, followed by passing the substances through a cation exchanger column. The behavior of the mercuric ion in the presence of the palladium ion, which is quite different from that of the mercuric ion alone, has also been discussed.
The Alkaline Hydrolyses of Chlorophenyl Phenyl Sulfoxides and Sulfones
Authors: Oae Shigeru , Khim Yong He 
Published: July 2006

Abstract
Both phenylsulfonyl and phenylsulfinyl group have been shown to activate the nucleophilic substitution of aromatic chloride from ortho- and para-positions, however, the effect of phenylsulfonyl group was substantially larger than that of phenylsulfinyl group. The activation by these sulfur groups is presumably due to the conjugative stabilization by the phenylsulfonyl or -sulfmyl groups through expansion of the sulfur valence shell. The addition complex is presumed to retain its configuration, since the stereo-integrity of the sulfoxide group has been shown to be maintained throughout the experiment.
Thermochemical Evidence of OH–π Type Intermolecular Hydrogen Bonds
Authors: Murakami Sachio , Fujishiro Ryoichi 
Published: July 2006

Abstract
A calorimeter for measuring the heat of mixing was constructed. Using the calorimeter, the heats of mixing were measured at 25.0±0.01°C for binary mixtures of benzyl alcohol with ethyl benzene or cyclohexane and ethyl benzene with cyclohexane, and at 35.0±0.01°C for binary mixtures of m-cresol with m-xylene or cyclohexane and m-xylene with cyclohexane. By plotting the values of the heats of mixing, ΔHx1M against the mole fraction of component 1, x1 and by extrapolating the curve to an infinite dilution (x1→0) for each system, the heats of mixing at an infinite dilution (\undersetx1→0limΔHx1M) were obtained graphically. By using the values of \undersetx1→0limΔHx1M obtained for these systems and by applying an enthalpy cycle, the OH–π type intermolecular hydrogen bond energies were estimated to be ΔH=−6.2 kJ for the benzyl alcohol-ethyl benzene - cyclohexane system and ΔH=−13.1 kJ for the m-cresol - m-xylene - cyclohexane system. The results obtained have been discussed from two points of view, that is, the proton-donating power of alcohols and the proton-accepting power of aromatic hydrocarbons.
Radiation Chemistry of Dicarboxylic Acids in the Solid State. II. C-13 Isotope Effects in the Radiation-induced Decarboxylation of Malonic and Several Aliphatic Dicarboxylic Acids
Authors: Hosaka Akio , Sugimori Akira , Tsuchihashi Gen-ichi 
Published: July 2006

Abstract
The C-13 isotope effects in the radiation-induced decarboxylation of several dicarboxylic acids were investigated. Malonic acid showed a C-13 isotope effect of about 2%; this is much greater than those of monocarboxylic acids. The greater isotope effect of malonic acid is attributed to the intramolecular competition of the C-carboxyl bond rupture. Succinic, adipic, and pimeric acid, in which the intramolecular interaction of two carboxyl groups can be expected, gave large isotope-effect values, whereas glutaric and sebatic acid, in which such an effect may be expected to be small, showed lower isotope effects. Analogously, maleic acid (cis isomer) showed a larger isotope effect than did fumaric acid (trans isomer).
Secondary Electrons in the Radiolysis of Cyclohexane
Authors: Sato Shin , Terao Terumi , Kono Michiyuki , Shida Shoji 
Published: July 2006

Abstract
Carbon dioxide and sulfur hexafluoride have been used as electron scavengers in the γ-radiolysis of cyclohexane. The dependence of G(H2) on the concentrations of additives can be interpreted satisfactorily in terms of diffusion-controlled reactions between electrons and the additives. A simple calculation was made using a function proportional to r2exp(−αr2) for the initial distribution of secondary electrons. The distribution constant α and the value of G(electrons) were adjusted to make the calculated curve of G(H2) vs- scanvenger concentration coincide with the observed one. The average initial separation of the secondary electron from the parent positive ion was found to be about 50 Å, and G(electrons) = 3.