bluuebunny/crossref_metadata_2025_split huggingface dataset:
Decomposition of Formic Acid on Silver Catalyst —Adsorption Measurement during Surface Catalysis—
Authors: Fukuda Kenzo , Onishi Takaharu , Tamaru Kenzi 
Published: July 2006

Abstract
The mechanism of the decomposition of formic acid over reduced silver catalyst has been studied by means of the adsorption measurement during surface catalysis. It was found that the decomposition of formic acid on the silver catalyst at 100°C was first order at lower pressures of formic acid, while at medium pressures it was zero order, the reaction rate being independent of the pressures of ambient formic acid; in the first region the amount of adsorbed formic acid was proportional to the pressure of formic acid, and in the second region it was constant, independent of the pressure of formic acid in the ambient gas. The second region corresponds to “saturation” in an ordinary sense. At pressures of formic acid higher than that in the “saturation” region the amount of adsorbed formic acid increases again linearly with the pressure of formic acid. The linear relation between the reaction rate and the amount of formic acid adsorbed during the reaction was observed over the whole range of the pressure of formic acid studied. It is accordingly concluded that a surface unimolecular reaction in terms of the adsorbed formic acid is the ratedetermining step. The exchange reaction of surface formic acid with those in the ambient gas was studied and it was demonstrated all the formic acid in the adsorbed layer accordingly participated in the exchange reaction. The numbers of surface silver atoms occupied by one molecule of adsorbed formic acid at the saturation points at various temperatures are estimated from the number of surface silver atoms and the amount of formic acid adsorbed at the zero-order kinetics. The number of surface silver atoms occupied by one molecule of adsorbed formic acid increases linearly with temperature.
Spectroscopic Studies on Radicals Produced from Acridine and Acridan in γ-Irradiated Rigid Solutions at −196°C
Authors: Shida Tadamasa , Kira Akira 
Published: July 2006

Abstract
Dilute solutions of acridine in ethers and amines were frozen at −196°C to a glassy solid and were γ-irradiated. Electrons ejected by ionization are effectively scavenged by acridine to produce acridine anions which are the sole species having an electronic absorption band in the visible region. In alcohol and ester matrices the anion abstracts a proton from the matrix molecule even at −196°C and yields a semiquinone radical equivalent to the species formed by H-atom abstraction at the 9-position of acridan (dihydroacridine). Acridan in γ-irradiated butyl chloride matrix forms acridan cation which has a characteristic absorption band at 500–750 mμ. Detachment of a proton from the acridan cation produces another semiquinone radical identifiable with the species formed by H-atom abstraction at the 10-position of acridan. Both radicals have a similar yet clearly distinguishable absorption band in the visible region.
The Effects of Organic Additives on the Solubilities and CMC’s of Potassium Alkyl Sulfates in Water. I. The Effects of Several Hydroxy Compounds
Authors: Shirahama Keishiro , Hayashi Makoto , Matuura Ryohei 
Published: July 2006

Abstract
The solubilities and critical micelle concentrations (CMC) of potassium dodecyl sulfate (KDS) and hexadecyl sulfate (KHS) were measured in methanol-, ethanol-, 1-propanol-, ethylene glycol-, 1,2-propanediol-, and glycerol-water mixed solvents over the temperature range from 0 to 40°C. It was found that the higher the hydroxy group density in the solvent, the less the effects on both the solubility and the CMC, and that the presence of an alkyl group in the solvent causes a greater temperature-dependence in the solubility. The solvent effects on the CMC and on the single-ion dispersion were discussed separately. An effect of a net-work structure formed between the hydroxy compound and water on the solubility is suggested. Solvent effects on the alkyl group and the ionic group of a surfactant molecule were separated by considering the difference between the standard free-energy change for the solution process of KHS and that of KDS. The effects on the Krafft point were also discussed in term of the above suggestions.
Paramagnetic Susceptibilities of Some DPPH Derivatives
Authors: Ohigashi Noriko , Inokuchi Hiroo 
Published: July 2006

Abstract
The static magnetic susceptibilities of poly crystalline samples of 1,1-bis(p-chlorophenyl)-2-picrylhydrazyl (Cl-DPPH), 1,1-bis(p-bromophenyl)-2-picrylhydrazyl (Br-DPPH), and 1,1-bis (p-methoxyphenyl)-2-picrylhydrazyl (CH3O-DPPH) were measured in the temperature range from 10°K to 300°K. These three substances showed strong paramagnetism comparable to that of DPPH, having relatively weak interaction energies between their unpaired electrons. Of these, the paramagnetic susceptibility of CH3O-DPPH was analysed on the basis of the singlet-triplet model with the energy separation of 2J/k=33.8°K.
Electrophoretic Behavior of Micelles of a Polyether-sulfate Type Surfactant
Authors: Tokiwa Fumikatsu , Ohki Kenji 
Published: July 2006

Abstract
The electrophoretic properties of the micelle of sodium dodecyltrioxyethylene sulfate have been studied in the presence of various types of inorganic z+-z− electrolytes and in the presence of organic electrolytes (RNH3Cl and RCOONa) of various sizes. The effect of the type of electrolytes on the zeta potential of the micelle, ζ, is similar in tendency to the effect to be expected on the basis of the Gouy-Chapman equation for spherical colloid particles. The valence of counterions has a considerable effect on ζ, but that of the co-ions has only a slight effect. With respect to the size of ions, counter-ions (RNH+) appreciably influence the potential of the micelle, whereas co-ions (RCOO−) influence the potential almost not at all. The value of ζ slightly increases, and then steeply decreases, with an increase in the size of the cations through a maximum value.
Reactions of Singlet Oxygen and Half-reduced Oxygen which are Produced Simultaneously by the Interaction of Triplet Dye and Oxygen
Authors: Usui Yoshiharu , Iwanaga Chieko , Koizumi Masao 
Published: July 2006

Abstract
Under experimental conditions in which the interaction between triplet dye and oxygen is an initiating process (D–O mechanism), the photosensitized oxidation of leucofluorescein in the aqueous solution (reaction (1)) has been found to decrease in rate with the increasing oxygen concentration and that the magnitude of the retarding effect of oxygen is almost the same independent of sensitizing dye. This is in sharp contrast to the kinetic feature of the oxidative photobleaching of dye (reaction (2)), where the rate becomes constant beyond a certain small oxygen concentration. On the basis of these findings, it has been proposed that in reaction (1), 1O2 plays a dominant role and it is deactivated by process 1O2+3O2→23O2. As to reaction (2), strong evidence has been presented for the view that the interaction of triplet dye and oxygen in the aqueous solution produces a rather stable D+···O2− of which only a small portion decomposes irreversibly. The principal evidence is as follows; 1) the free half-oxidized dye (produced by the reaction between triplet dye and [Co(Ox)3]3− was found to oxidize FH2 with a high rate and its decay was found to be accelerated by the addition of FH2; 2) the decay of the half-oxidized species (first order decay!) produced in the aerated aqueous solution, on the other hand, was not affected by FH2 under otherwise similar conditions as in (1).
An MO-Theoretical Study of the E2 Reaction of Ethyl Chloride
Authors: Hao Hideyuki , Fujimoto Hiroshi , Fukui Kenichi 
Published: July 2006

Abstract
The change in the electronic state in the course of the E2 reaction of ethyl chloride was followed by means of the extended Hückel calculation. A model is adopted in which the nucleophilic reagent approaches the trans-β-hydrogen atom. The valence-inactive population of the trans-β-hydrogen atom in the lowest unoccupied (LU) molecular orbital (MO) was employed as a theoretical reactivity index. The theoretical conclusion derived was consistent with the experimental results.
On the Order of Isotopic Exchange Reactions
Authors: Takaishi Tetsuo 
Published: July 2006

Abstract
The conditions for the applicability of the McKay law were studied. It was concluded that the first order kinetics no longer holds when the concentrations of intermediates cannot be disregarded when compared with those of reactants and products and when the rate determining step cannot be specified. Some reactions were illustrated in which McKay’s law cannot be applied.
On the Presence of Tetrafluoroborate Ions in Natural Waters
Authors: Onishi Tomio 
Published: July 2006

Abstract
Tetrafluoroborate ions (BF4−) can be formed only in a strongly acid solution. Certain acid thermal waters and volcanic gases in the active volcanic zone can be expected to be the media of BF4− formation. When BF4− is supplied to natural waters, its rate of hydrolysis is relatively low, suggesting the possibility of the occurrence of BF4− in natural waters. The contents of BF4− have been determined in various thermal water samples from a volcano in Satsuma Iwo-jima, and the presence of BF4− confirmed. The BF4− content in the condensed water of volcanic gas from a fumarole with the high temperature of 745°C is 304 mg/l, which is 26% of the total F, and 79% of the total B content. The BF4− content in a sample of water from Kitabira Spa (pH 1.1) is 8.0 mg/l, which is about 50% of the total F or B. However, the presence of BF4− can not be confirmed in ordinary natural waters such as land and sea waters.
Gas Chromatography of Rare Earth Chelates of Pivaloyltrifluoroacetone
Authors: Shigematsu Tsunenobu , Matsui Masakazu , Utsunomiya Kei 
Published: July 2006

Abstract
The gas chromatographic behavior of Sc, Y, and rare earth chelates of a new β-diketone, pivaroyltrifluoroacetone (PTA), was investigated. PTA was synthesized by a Claisen condensation from pinacolin and ethyltrifluoroacetone. Sc, Y, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, and Lu PTA chelates were prepared. Their elemental analyses and infrared spectra indicated that they were anhydrous tris chelates, and the TGA curves of the chelates proved their good volatile characteristics, showing approximately a 100% weight loss. Gas chromatograms of all the chelates and of mixtures of Sc, Y, and several rare earth chelates were obtained. Some relationships were observed between the retention time, the volatilization temperature, and the ionic radius of the central metal: With the decrease in the ionic radius, the retention time of the chelate decreased and the volatilization temperature became lower.
Crystal Growth of the Phosphate Coating on Iron and Steel
Authors: Umegaki Takao , Okabe Taijiro , Omori Keiichi 
Published: July 2006

Abstract
Crystal growth of the phosphate coating on steel and pure iron was investigated by microscopic observation and X-ray diffraction. β-Hopeite was recognized as a main constituent of the phosphate coating. From the experimental results obtained in this investigation and the crystal structure of β-hopeite proposed by Gamidov and Galovachev (Dokl. Akad. Nank, SSSR, 150, 2, 381, (1963)), it was concluded that the bonding of the (010) plane of β-hopeite to the (100) plane of iron is most favorable for atomic arrangement of the phosphate coating.
Nickel(II) and Copper(II) Complexes of C,N-Disubstituted Salicylideneimines with Steric Hindrance
Authors: Yamada Shoichiro , Takeuchi Akira , Yamanouchi Kuniko , Iwasaki Katsumoto 
Published: July 2006

Abstract
Many new nickel(II) and copper(II) complexes (abbreviated as M(X-sal.R)2) of Schiff bases were obtained from C-substituted salicylaldehydes and 2,6-dimethyl- and 2,6-diethyl-aniline, where X denotes 5-Br, 5-Cl, 5,6-benzo, 5-NO2 and 3-CH3O. For X=5-Cl, the corresponding nickel(II) complex with R=2,6-dichlorophenyl was also synthesized. All these nickel(II) complexes consist of square-planar molecules in the solid state and in non-donor solvents. The nickel (II) complexes, when dissolved in pyridine, either take up two pyridine molecules to form six-coordinated complexes or retain the original planar configuration. The configuration in pyridine depends upon the nature of X, demonstrating that the effect of X on the electronic state of the ligand may also be important, besides the steric factor, in determining the configuration of the nickel(II) complexes. The corresponding copper (II) complexes, which are square-planar in the solid state and in non-donor solvents, combine with one or two pyridine molecules, when dissolved in pyridine.
Reaction of Salicylamine with α-Dicarbonyl Compounds. I. Transamination Reaction
Authors: Kanatomi Hajime , Murase Ichiro 
Published: July 2006

Abstract
The reactions of salicylamine with α-dicarbonyl compounds were examined in the hope of obtaining 2,2′-bibenzoxazine derivatives I or Schiff bases II as two-to-one condensation products; however, salicylidenesalicylamine was isolated in every case. It was found that the reaction proceeded through transamination, followed by trans-Schiffization between salicylamine and α-dicarbonyl compounds. The mechanism and the conditions under which the reactions take place were investigated.
Trimethylenediamine Complexes. I. Some Trimethylenediamine Complexes Derived from trans-[CoCl2tn2]Cl in Methanol
Authors: Kawaguchi Hiroshi , Yano Naomichi , Kawaguchi Shinichi 
Published: July 2006

Abstract
Several diacidobis(trimethylenediamine)cobalt(III) complexes including nitrate, nitrite and thiocyanate ions as ligands have been prepared by ligand substitution reactions of trans-dichlorobis(trimethylenediamine)cobalt(III) chloride in methanol. All these compounds were assumed to have the trans configuration according to the Baldwin’s criterion based on the CH2 rocking vibration. Isomeric pairs of chloronitro and chloronitrito complexes were also characterized by means of infrared data.
Solvent Effect in a Partial Asymmetric Synthesis. II
Authors: Inamasu Shuji , Horiike Michio , Inouye Yuzo 
Published: July 2006

Abstract
Further evidence for the unambiguous solvent polarity dependence of the stereochemistry in the base-catalyzed Michael type condensation was provided by the systems involving (−)-menthyl chloroacetate and methyl acrylate, and (−)-menthyl chloroacetate and (−)-menthyl acrylate with a modification of the work-up. The electrostatic control of the stereoselectivity was interpreted by the same theorem developed in the previous study and some novel features found for the present systems were discussed.
Nonequilibrium Thermodynamics of the Relaxing System Subject to Multinomial Distribution
Authors: Ishida Kenji 
Published: July 2006

Abstract
It has been shown that the relaxation process in a system of noninteracting particles in contact with a heat bath, on the assumption that the system is in local equilibrium, can be described by the Markov process homogeneous in time, and that the solution of the Markov process is a multinomial distribution. The nonequilibrium thermodynamics for such a relaxing system was formulated by means of the stochastic entropy production which can be derived by the probabilistic version of classical entropy production. As a special case, the stochastic nonequilibrium thermodynamics for the relaxing system of identical harmonic oscillators was discussed.
Spectroscopic Behavior of Würster’s Blue Perchlorate and N-Ethylphenazyl Crystals
Authors: Sakata Tadayoshi , Nagakura Saburo 
Published: July 2006

Abstract
The electronic absorption spectra of Würster’s Blue perchlorate and N-ethylphenazyl in solid were measured at various temperatures ranging from 48°K to 300°K. In both cases, strong bands due to the charge-transfer between the half occupied orbitals of respective component radicals were observed in near infrared region. This assignment of these bands was supported by the polarized absorption measurement carried out with the Würster’s blue perchlorate single crystal. The charge-transfer band of solid Würster’s blue perchlorate was found to increase its intensity with decreasing temperatures; in particular, the increasing tendency became predominant below the phase transition point (186°K). The similar tendency was also observed for solid N-ethylphenazyl. The temperature dependence of the band was found to be closely related with the population of triplet excitons determined from the measurement of magnetic susceptibility or paramagnetic resonance. The separation J between the ground singlet state and the thermally accessible triplet state was determined from the analysis of the temperature dependence of the charge-transfer band to be 235 cm−1 and 320 cm−1 for Würster’s blue perchlorate and N-ethylphenazyl, respectively.
The Molecular and Crystal Structure of Bis(2-hydroxyethylimino-pyruvato)copper(II) Tetrahydrate
Authors: Iijima Kinya , Oonishi Isao , Muto Fumio , Nakahara Akitsugu , Komiyama Yoshimichi 
Published: July 2006

Abstract
A new copper(II) chelate of the Schiff base derived from pyruvic acid and ethanolamine has been prepared. The crystal structure of this complex, [Cu(pyv=etham)2]·4H2O, has been determined from three dimensional X-ray diffraction data. The dimensions of monoclinic cell are a=6.50Å, b=19.75Å, c=7.26Å, β=113.0° and Z=2. The space group is P21⁄n. The structure has been refined by three dimensional difference syntheses to R=0.126. It has been disclosed that copper (II) links to the 2-hydroxyethyliminopyruvate anion through the terminal carboxylate group, and the nitrogen of the Schiff base linkage. Having a center of symmetry, the complex molecule is in the trans-configuration and has normal bond distances and angles. The coordination around copper(II) is square planar; the Cu–O and Cu–N distances are 1.92 and 2.00Å, respectively. Two additional oxygen atoms of the water molecules at 2.57Å complete a distorted octahedron around copper(II). The complex molecules are held together in the crystal by the O–H···O hydrogen bonds, forming a three dimensional network.
Preparation of Star-Type Graft Copolymer through the Polymerization of Methyl Methacrylate with Use of the Potassium Complexes of Polystyrene having a Benzophenone Unit
Authors: Nobutoki Koji , Sumitomo Hiroshi 
Published: July 2006

Abstract
Polystyrene ketone possessing a benzophenone structural unit in the middle part of the chain was synthesized by the coupling reaction of one-ended living polystyrene with 2,4′-dichlorobenzophenone. Polystyrene ketone potassium ketyl was prepared by the reaction of polystyrene ketone with an equivalent amount of potassium naphthalene complex in tetrahydrofuran. Polystyrene ketone potassium dianion was also formed with excess potassium in the solvent. These polystyrene ketone potassium adducts induced a quantitative polymerization of metyl methacrylate. Gross polymer from each of the reaction systems was elution-fractionated into four fractions in which a new class of star-type graft copolymer was included together with polystyrene and polymethyl methacrylate. Each fraction was characterized by means of the measurements of the yield, molecular weight and styrene content. Consideration was also made on a possible mechanism of the polymerization.
Thermodynamic Properties of Galvinoxyl Radical and Its Phenol Derivative; Mechanism of the Phase Transition
Authors: Kosaki Akio , Suga Hiroshi , Seki Syûzô , Mukai Kazuo , Deguchi Yasuo 
Published: July 2006

Abstract
Measurements of heat capacity of Galvinoxyl radical and its phenol derivative were carried out in the temperature region from 12 to 300°K. Galvinoxyl radical exhibits a phase transition of first-order nature at 81.5°K which corresponds to the susceptibility anomaly already measured. The enthalpy and entropy of transition amount to 1504.6 J/mol and 18.67 J/(°K·mol), respectively. The entropy change, which corresponds formally to R In 9.45, cannot be explained by taking only the magnetic contribution. On the other hand, its phenol derivative, the corresponding diamagnetic substance, has not thermal anomaly in the above temperature region. X-Ray diffraction patterns at room temperature for both substances agree well with each other in their diffraction angles. From these experimental findings, it seems to be plausible that a kind of transformation of the crystal structure of Galvinoxyl radical takes place at the transition point which may be induced by a pairing of magnetic spins between neighboring molecules.
Influence of Impurities on Phosphate Coating Formation
Authors: Umegaki Takao , Ito Hiroshi , Okabe Taijiro 
Published: July 2006

Abstract
The applicability of wet-process phosphoric acid containing such impurities as Al3+, Ca2+, Fe3+ and SO42− was examined. From the viewpoint of the corrosion resistivity of the phosphate coating, Al3+ ion was found to be the most undesirable contaminator. NaF was recognized as the most effective masking reagent for an elimination of Al3+ hindrance. SO42− also affected the phosphate coating formation, but the presence of less than 1% SO42− did not disturb the coating formation when an appropriate amount of accelerator was added to the phosphatizing solution.
Transition Energy Diagram for Solvated Electrons and Its Application to the Interpretation of Their Absorption Spectra
Authors: Noda Syozi , Fueki Kenji , Kuri Zen-ichiro 
Published: July 2006

Abstract
The energy levels of solvated electrons have been calculated as a function of the static dielectric constant and of the cavity radius on the basis of a continuous dielectric model with an adiabatic approximation, and a contour diagram has been drawn up for the transition energy of solvated electrons. Using this diagram and the observed absorption spectra, the quantities on solvated electrons in alcohols have been estimated. The cavity radius, R, ranges from 0.9 to 1.6 Å, the charge distribution for the ground state, from 2.4 to 3.2 Å, and the variation in cavity radius, from 0.50 to 0.60 Å, at room temperature. From the calculations of the temperature dependence, d(hv)/dt, of the transition energy, it can be said that, for solvated electrons in alcohols, the contribution to d(hv)/dt of the change in R with the temperature is rather more dominant than the change in the static dielectric constant with the temperature. It has also been found that there exists a correlation between the dR/dt value and the ratio of the number of the OH bond to the total number of bonds involved in each alcohol.
Determination of Kinetic Parameters of the Electrode Reaction of Ethylenediaminetetraacetatoaquochromate(III) Ions by the Potentiostatic Method
Authors: Yamada Akifumi , Tanaka Nobuyuki 
Published: July 2006

Abstract
Kinetic parameters of the electrode reaction of ethylenediaminetetraacetatoaquochromate-(III)/ethylenediaminetetraacetatoaquochromate(II) at the dropping mercury electrode have been determined by the potentiostatic method in sodium chloride solutions of ionic strength 0.5 containing 0.1 m acetate buffer. The measured standard rate constant (ks)ms is 2.1×10−1cm sec−1 and the measured transfer coefficients (αc)ms and (αa)ms are 0.58 for the cathodic and 0.39 for the anodic process. The correction for the effect of the electrical double layer has been made on these parameters. The values obtained are: (ks)corrc=1.7×10 cm sec−1, (αc)corr=0.54 and (αa)corr=0.43. The standard potential −1.220 V vs. SCE determined by the potentiostatic method is compared with −1.218 V vs. SCE obtained by the measurement of the equilibrium potential. These values are in good agreement within the experimental error.