bluuebunny/crossref_metadata_2025_split huggingface dataset:
Polarographic and Spectroscopic Studies on the Ion-pair Formation of Trioxalatocobaltate(III) Ions with Cations in Aqueous Solutions
Authors: Tanaka Nobuyuki , Koseki Kazuo 
Published: July 2006

Abstract
The ion association between trioxalatocobaltate(III) anion and uni-, bi- and tervalent cations in aqueous solutions has been studied by polarographic and ultraviolet, visible and infrared spectroscopic methods. The association constants have been obtained by the measurement of the polarographic diffusion current of trioxalatocobaltate(III) ions in the presence of varied concentrations of cations at ionic strength 0.1 (NH4NO3) and 25°C. The influence of ammonium ion was taken into consideration in the treatment of polarographic data. The values obtained are 7.9 for (CH3)4N+[Co(ox)3]3−, 3.7±0.4 for (C2H5)4N+[Co(ox)3]3−, 22±1 for Na+[Co(ox)3]3−, 56±6 for Mg2+[Co-(ox)3]3−, 55±4 for Ca2+[Co(ox)3]3−, 53±3 for Sr2+[Co(ox)3]3−, 55±7 for Ba2+[Co(ox)3]3− and 118±17 for Al3+[Co(ox)3]3−. The association constant of NH4+[Co(ox)3]3− was determined by the conductivity measurement to be 33.6 (logK=1.53) at zero ionic strength. No change was observed in the visible, the ultraviolet and the infrared absorption spectra of trioxalatocobaltate (III) ions upon the addition of various cations even at the concentration at which the ion-pair formation is assumed to occur from the polarographic studies. These facts indicate that, in a sense of equilibrium study, there is no direct interaction between the complex anion and the cation, but one or more water molecules interpose between the two ions.
The Reaction between Hydrocarbon and Hydrogen Cyanide in Silent Electrical Discharge. II. The Formation of Acrylonitrile from Ethylene and Hydrogen Cyanide
Authors: Kawamoto Kazuaki 
Published: July 2006

Abstract
The present investigation was undertaken to examine the possibility of the direct introduction of a cyano radical into ethylene by means of a silent discharge. When a mixture of ethylene and hydrogen cyanide was discharged in an ozonizer under atmospheric pressure, the main liquid product was acrylonitrile, though the formation of telomers, such as ethyl cyanide, n-butyl cyanide and n-hexyl cyanide, was also observed. Besides these compounds, the reaction products were confirmed to consist of s-butyl, n-propyl, isopropyl, n-amyl, and isoamyl cyanides, and a gaseous product. The yield of acrylonitrile was affected by the temperature and voltage of the discharge. It has been found that the yields of the liquid products and the gaseous product increase with the rise in the temperature and voltage of the discharge, while the relative ratio of acrylonitrile to the other liquid product decreases. Judging from the relative concentration of each compound in the reaction products, it may be said that the vinyl radical and the cyano radical are the main intermediates in this reaction system.
UV and Visible Absorption Spectra of Monohalogenated Anthracenes. I. The First Absorption Bands
Authors: Ohno Isao , Iguchi Kaoru 
Published: July 2006

Abstract
UV and visible absorption spectra of monohalogenated anthracenes are measured, and the first absorption band are reported. When anthracene is monohalogenated, the first absorption band slightly shifts toward red or does not shift in accordance with the change in the position and the species of the substituting halogen atom, but the vibrational structure remains unchanged. The sequence of magnitude of red shift due to the position is 9-halo&gt;1-halo&gt;2-halo-anthracene, while that due to the species is different depending on the substituted position: in the 9-position, it is monobromo&gt;monochloro&gt;monofluoro&gt;monoiodo anthracene, and, in the 1 or 2-position, it is monochloro&gt;monofluoro&gt;monobromo\simeqmonoiodo anthracene. For the sequence of red shift due to the species of the substituting halogen atom, there are similarities between the first absorption band of monohalogenated anthracenes and the K or B-band of monohalogenated benzenes. These results are discussed in terms of the simple LCAO MO perturbation treatment.
Studies on the Radical Species in Solid Methylene Blue as Revealed from the ESR Spectra
Authors: Okuda Michio , Kowata Takeo , Usui Yoshiharu , Koizumi Masao 
Published: July 2006

Abstract
The ESR signals of polycrystalline methylene blue (MB) salts have been investigated in respect to a) temperature effect, b) anion effect, c) influence of the addition of donor and acceptor and d) response to visible light irradiation, a) The signal intensity in general increases with the rising temperature, but a sharp difference in the ESR behavior has been found above and below room temperature. Response to the temperature change at low temperature is reversible and the apparent activation energy is ca. 0.03 eV (L-type behavior) whereas the high temperature behavior has a marked tendency of irreversibility and the activation energy is at least one order larger (H-type behavior), b) No essential anion effect has been observed on g-value, line shape and spin concentration for chloride, iodide and phosphate, c) The addition of trinitrobenzene and paraphenylenediamine in 10 : 1 to MB chloride also had no essential effect, d) Corresponding to the L-type and H-type behavior observed in a), visible light irradiation has been found to cause a decrease or an increase in signal intensity respectively at low and high temperature. From these findings it has been concluded that there are at least two kinds of defect (L-type and H-type) and that the formation of radical species occurs only on such defect sites. Some suggestions have been made on the nature of these two types of defects and on the molecular processes occurring at or near these defect sites. The radical formation reaction is most likely to be connected with dyedye interaction, D++D+\ightleftharpoonsD+++D.
Gel Filtration of Surfactants on Sephadex
Authors: Tokiwa Fumikatsu , Ohki Kenji , Kokubo Isao 
Published: July 2006

Abstract
An attempt has been made to apply gel filtration on Sephadex to micellar solutions of surfactants. The data on the gel filtration of surfactants were interpreted by taking into account the fact that there exist both micellized and unmicellized species in the solutions. A simple method for obtaining the retention volume of the micelle (VM) of a surfactant directly from the elution curve was developed. Further, the relation between the values of VM and the micellar molecular weights (MMW) was examined for various types of surfactants. A linear relation was found between VM and log MMW, with the exception of a surfactant with a heterocyclic structure. It appears that gel filtration offers a convenient way for roughly estimating the MMW’s of surfactants.
The Crystal Structure of l-Cysteic Acid
Authors: Konishi Hideaki , Ashida Tamaichi , Kakudo Masao 
Published: July 2006

Abstract
The crystal structure of cysteic acid, C3H7NO5S, has been determined. The crystal is orthorhombic with a space group of P212121, and four molecules are in a unit cell with these dimensions: a=8.35, b=10.16, and c=7.44 Å. The molecule is a zwitter ion, −O3SCH2CH-(NH3+)COOH; its dimensions are generally similar to those found in other amino acids and sulfonic acids. The acidic groups occupy the trans positions with respect to the Cα–Cβ bond, while the amino group is in a gauche position to the sulfonic group and forms an intramolecular hydrogen bond between them.
Certain Interactions between Transition Metal Ions and the NCS Group in Chromium(III) Isothiocyanato Complexes. II. Reinecke’s Salt Type Complexes Involving Nickel(II), Manganese(II) and Iron(III) Ions
Authors: Oki Hisaya , Kyuno Eishin , Tsuchiya Ryokichi 
Published: July 2006

Abstract
Nickel (II), manganese (II) and black iron(III)-tetraisothiocyanatochromate(III) were prepared by the reaction of nickel(II) nitrate, manganese (II) sulfate and iron(III) chloride with Reinecke’s salt, respectively. Each salt exhibits a gradual color change from reddish-purple to brownish-orange, red and black, respectively, when exposed to dry air after preparation, except for the orange iron(III) salt prepared in hydrochloric acid solution, which shows no color change from the original orange. Their absorption spectra give evidence that each salt will dissociate into a metal cation and Reinecke’s anion in aqueous solution. Splittings due to the C–N stretching vibration were not observed in the IR spectra. The effective magnetic moments were evaluated as 3.96, 5.13, 5.0 and 4.81 B. M. for the nickel(II)-, the manganese (II)-, the black iron(III)- and the orange iron(III)-salts, respectively. They show that the salts are nearly low spin types, or a type somewhere between low and high spin. From X-ray diffraction analyses, the unit cell of all the salts were found to be tetragonal.
The Dechloro-addition of β-Chloropropionitrile to Acrylonitrile with a Sodium Amalgam
Authors: Misono Akira , Osa Tetsuo , Asano Takamasa , Suzuki Takeo 
Published: July 2006

Abstract
The reaction of a mixture of β-chloropropionitrile, acrylonitrile, and water with a sodium amalgam was investigated. The main product was adiponitrile, which was formed mainly via a route consisting of three steps: I. The replacement of the chloride of β-chloropropionitrile with sodium. II. The addition of the organometallic intermediate formed to acrylonitrile. III. The replacement of the sodium in the final intermediate with hydrogen. The amount formed through the Wurtz reaction was small. The by-products were propionitrile, acrylonitrile, polymers of acrylonitrile, and organometallic compounds. The details of this reaction are given in this paper.
Catalytic Activity of Polymeric Vitamin B12 Model Compounds
Authors: Sasaki Tadashi , Matsunaga Fujinao 
Published: July 2006

Abstract
[CoX(DH)2·P-4VP] (X: CN, Cl)-type polymeric complexes were prepared from dimethylglyoxime (DH2) and poly-4-vinylpyridine (P-4VP) by a procedure similar to that reported for the preparation of [CoX(DH)2·Pyr] (Pyr: pyridine) (T. Sasaki and F. Matsunaga, submitted to Bull. Chem. Soc. Japan). Moreover, their catalytic activities in the decomposition reaction of hydrogen peroxide were compared with those of the corresponding monomeric complexes [CoX(DH)2·Pyr]; it was found that their activities decreases in the following order:
[CoCl(DH)_2·P-4VP]&gt;[CoCl(DH)_2·Pyr]&gt;&gt;[CoCN(DH)_2·P-4VP]&gt;[CoCN(DH)_2·Pyr]
About the relationship between structure and activity, it was concluded that the activity is much influenced by the nature of the X ligand of cobaloximes. It increases with a decrease in the interaction between the cobalt and nitrogen of a pyridine ring and with a weakening in the basicity of the coordinated bases. The structures of the polymeric complexes are discussed on the basis of their spectral data.
Azetidines. V. Preparation and Deamination of Azetidinylpropylamines
Authors: Chen Teng-Yueh 
Published: July 2006

Abstract
The addition of 3,3-diethylazetidine to acrylonitrile and crotononitrile, followed by reduction, gave the corresponding azetidinylpropylamines. The deamination products of the amines were identical with the alcohols prepared by the addition of diethylazetidine to methyl acrylate and crotonate, followed by reduction with lithium aluminum hydride.
Unperturbed Dimension of Poly(butylene oxide)
Authors: Matsushima Masahiro , Fukatsu Masaaki , Kurata Michio 
Published: July 2006

Abstract
Viscosity and light scattering measurements of poly(butylene oxide) were carried out in various solvents, including a theta solvent, isopropanol. The intrinsic viscosity vs. molecular weight relationships obtained in the range of molecular weight from 2.1×105 to 2.3×106 were:
& [η]=3.39×10^-5M_w^0.84 in benzene at 30°C,
& [η]=4.08×10^-5M_w^0.79 in methyl ethyl ketone at 30°C,
& [η]=8.65×10^-4M_w^0.50 in isopropanol at 29.8°C.
The ratio σ between the end-to-end distance of the polymer chain in the unperturbed state and that in the freely rotating state was estimated to be 1.66.
Synthesis of Sulfosodalite, an Ultramarine-Relating Phase
Authors: Yamaguchi Goro , Kubo Yasushi 
Published: July 2006

Abstract
A sulfur-containing sodalite-type aluminosilicate, 6NaAlSiO4·Na2S (designated sulfosodalite in this paper), was synthesized in the system NaAlSiO4-Na2S at temperatures 850 to 950°C in an H2 or N2 atmosphere. All of the sulfur in this substance was contained as sulfide ion S2−, and its equilibrium content in a unit cell increases with temperature from 1.5 S at 850°C to 1.8 S at 950°C. This substance was only pale colored, yellowish or pinkish, but the partial substitution of Si for Al produced a deep vermilion red color.
The Isokinetic Temperature of the Acylation of l-Menthol
Authors: Akiyama Fuminori , Tokura Niichiro 
Published: July 2006

Abstract
The acylations of l-menthol with p-substituted benzoyl- and substituted acetyl chlorides were carried out, and it was found that the electron-releasing substituents accelerate the reaction rate in chloroform even though the reaction is completely of the SN2 type. This result is interpreted in relation to the low isokinetic temperature, the reaction itself being carried out above that temperature. Such a phenomenon is discussed in terms of the configurational and the solvent effects on the entropy of activation.
Relative Determination of Soret Coefficients of Alkaline Earth Chlorides
Authors: Ikeda Toshio , Ohe Hidefusa , Kawamura Saburo 
Published: July 2006

Abstract
The Soret coefficients of aqueous solution of alkaline earth chlorides were determined indirectly using combined thermocells. “Combined thermocell” refers to a cell system of a back to back combination of two thermocells made of common electrodes and different electrolytes without liquid junction. The values are −2.79 for MgCl2, −3.43 for CaCl2, −4.09 for SrCl2, and −4.73 for BaCl2, respectively (in the unit of 10−3 deg−1) at 0.005 m and 25°C. These agree with reported values found by the direct method.
Radiolysis of Hydrogen Cyanide in an Aqueous System. II. Effects of Additives and Reaction Mechanism
Authors: Ogura Hajime 
Published: July 2006

Abstract
The 60Co γ-irradiation of dilute aqueous solutions of hydrogen cyanide (6 mm) in the absence of oxygen yielded mainly ammonia with G=1.9, formaldehyde with G=1.1, and carbon dioxide with G=0.8, while G(–HCN)=5.8 molecules per 100 eV. Polymeric hydrogen cyanide was also observed with the G(–HCN(polymer))\simeq4, which showed an intense broad absorption band in the UV region upon γ-irradiation. The following material balances were observed with the main products:
G(-HCN)\simeqG(NH_3)+G(-HCN(polymer))\simeqG(CO_2)+G(HCHO)+G(-HCN(polymer))
The results can be interpreted in terms of a mechanism involving HCN−, H2CN, and H(OH)CN radicals. The ratio of the rate constants for the reactions of e−aq and H atoms with hydrogen cyanide to those with several scavengers have been determined as k(e−aq + HCN)/k(e−aq + NO3−)=0.019 and k(H + HCN)/k(H + 2-propanol)=1.4, all at 17°C.
Phase Transitions in Crystalline Divalent Metal Dicalcium Propionates. II. Proton Magnetic Resonance Investigation
Authors: Nakamura Nobuo , Suga Hiroshi , Chihara Hideaki , Seki Syûzô 
Published: July 2006

Abstract
The motions of the propionate anions in strontium-, lead-, and barium-dicalcium propionates were examined with the proton magnetic resonance method at low temperatures. It was found that the methyl groups rotate about the C3-axes even at 20°K in the Sr-, and the Ba-salts. In the Sr-salt the gradual decrease of the second moment below the ferroelectric transition point was observed and this phenomenon was related to the large angle torsional oscillations of the ethyl groups about the C3′-axes as introduced in Part I: Near the ferroelectric transition point the observed second moment shows the possibility of excitation of the C3′-rotation which would make the crystal to be paraelectric above the transition point. It was expected that the C3′-torsion is to some extent excited in the Pb-salt at liquid nitrogen temperature, a slight discrete change being observed at the lower transition point. A sharp line width transition was also observed in the Ba-salt and this fact resulted in the finding of a new λ-type phase transition with the peak at about 204°K by the differential thermal analysis. A slight decrease of the second moment was observed at the upper transition point and the C3′-rotation was assumed to be fully excited above that point.
Studies on the Sol-Gel Transformation of Aluminium Hydroxide in the Presence of Dyes
Authors: Malik Wahid U , Khan Iqbal A 
Published: July 2006

Abstract
The influence of dyes on the gelation of aluminium hydroxide sol has been studied with the help of viscometric and pH metric methods. From these studies it is inferred that the behaviour of acid dyes towards alumina is different from that of basic dyes. The results have been interpreted in terms of various structural changes taking place in the dye molecule. Adsorption studies reveal that the data do not fit well into the Langmuir or Freundlich adsorption isotherm equation in the case of alizarin sulphoric acid, while in the cases of methyl orange, methylene blue, and malachite green, the data are found to fit well into the Langmuir adsorption equation.
Kinetics of Isotopic Exchange between Acetylacetone-14C and Tris-acetylacetonatoaluminum in Tetrahydrofuran
Authors: Saito Kazuo , Masuda Kazuyo 
Published: July 2006

Abstract
Tris-acetylacetonatoaluminum [Al(acac)3] is precipitated crystalline from tetrahydrofuran (THF) solution containing an excess of acetylacetone (acacH) by adding chilled petroleum ether. This fact enables a kinetic study of isotopic exchange of acac− between [Al(acac)3] and acacH with the aid of acetylacetone-14C. The exchange rate is independent of the concentration of acacH and dependent on that of water. The rate formula at 25°C is as follows:
R=[Al(acac)_3](6×10^-5+2.0×10^-2[H_2O]) mol l^-1min^-1
This exchange reaction is catalysed by acids; the stronger the acid, the greater the catalytic effect. One of the acetylacetonate ligands would be present with one end free, and break of the remaining bond of unidentate acetylacetonate seems to be the rate determining step. Water can occupy the vacant coordination site of aluminum ion to retard recombination of the unidentate ligand. The donation of proton to the free end of acetylacetonate appears to impede the recombination, too, and facilitate the exchange. Hydronium ion seems to be the unique proton carrier.
Studies of Organic Catalytic Reactions. VI. The Function of Pyridine and Copper in the Rosenmund-von Braun Reaction
Authors: Ito Takehiko , Watanabe Ken-ichi 
Published: July 2006

Abstract
The Rosenmund-von Braun reaction with aryl halide, with its Ar-X+CuCN-Base→Ar-CN+CuX-Base, has been studied in nitrobenzene in place of an organic base at 160–180°C. The free nitriles formed during the reaction were determined exactly by gas chromatography. In the use of bases with suitable coordination forces to CuCN, the reactivity of the base for the substitution was found to be in the order: prim.&gt;sec.&gt;tert. A steric hindrance of the base was observed, and the reactivity of the pyridine homologue followed the order: pyridine&gt;quinoline&gt;α-picoline&gt;2, 6-lutidine. Ortho-substituted groups in the halobenzene seem to manifest no steric hindrance on the reaction. From the results of the kinetic study, it can be said that CuCN participates in the reaction essentially in the form of a Base(1 mol)-CuCN complex. The overall reaction is second-order, dc⁄dt=k[Complex][Ar-X]. The rate-determining step may be in the halogen exchange stage in the intervening complex, Base-CuCN-Ar-X, where the plane including CN-Cu-X and that of the benzene ring may be nearly perpendicular to each other. When an excess of CuCN over the base is used, the base is liberated from the Base-CuX complex, after the displacement, and then coordinates to the unreacted CuCN again.
The Dimerization of Propylene over a Nickel Oxide-Silica-Alumina Catalyst
Authors: Imai Hisao , Hasegawa Touji , Uchida Hiroshi 
Published: July 2006

Abstract
The composition of hexene isomers produced by the dimerization of propylene over a nickel oxide-silica-alumina catalyst has been examined under the following experimental conditions: 10–300 kg/cm2, 100 and 200°C. Under a typical set of experimental condition (50 kg/cm2, 200°C), eight hexene isomers, i.e. 4-methyl-trans-2-pentene, 4-methyl-cis-2-pentene, 2-methyl-1-pentene, trans-2-hexene, cis-2-hexene, 3-methyl-trans-2-pentene, 3-methyl-cis-2-pentene, and 3-methyl-1-pentene, have been found to be the primary products of the dimerization. Among these, more trans isomers are produced initially than the corresponding cis isomers for 4-methyl-2-pentenes and 2-hexenes, but the reverse is true for 3-methyl-2-pentenes. Under higher pressures, 2,3-dimethylbutenes are also produced at 200°C. A reaction scheme assuming the intermediates of cyclobutane derivatives has been proposed to explain the above findings. The scheme may also explain the unique order of the activity of the present catalyst for a series of n-olefins.
Effect of Pressure on Graphitization of Carbon. I. Heat Treatment of Soft Carbon under 1,3 and 5 kbar
Authors: Noda Tokiti , Kamiya Kanichi , Inagaki Michio 
Published: July 2006

Abstract
Polyvinylchloride coke was heat-treated under the quasi-hydrostatic pressure of 1,3, and 5 kbar by using a simple piston cylinder type high pressure apparatus. The process of graphitization under pressure was studied kinetically by analyzing the profile of the (002) diffraction line. It was found that the accelerating effect of pressure on the graphitization of carbon became more pronounced at higher pressure. The process of graphitization under 3, and 5 kbar seemed to take place in at least two stages. In the first stage, the profile of the (002) line shifted simply from the position of the original line to 26.0° in 2θ, which corresponded to a c0-spacing of 6.85 Å. In the next stage, a new component, having a c0-spacing of about 6.72 Å, appeared in addition to the first component, having a c0-spacing of 6.85 Å. Therefore, the profiles of the (002) line became composite. Under 1 kbar, however, no composite profiles were observed and the c0 Spacing decreased gradually with heat treatment. Approximate values for the activation energy and activation volume for graphitization under 3–5 kbar were estimated to be 80–120 kcal/mol, and −7–−9 cc/mol, respectively.
High Pressure Copolymerization of Styrene and Vinyl Acetate with Vinyl Chloride
Authors: Imoto Tatsuya , Ogo Yoshiaki , Nakamoto Hideo 
Published: July 2006

Abstract
The radical copolymerization of vinyl chloride and styrene, and that of vinyl chloride and vinyl acetate, were investigated in an acetone solution at 50°C under high pressures of up to 3000 kg/cm2. The monomer reactivity ratios of these copolymers were not affected by the pressure, while their molecular weights and overall rates of copolymerization increased with the pressure. The increments of the four rate constants of the growing chain of copolymerization (k11,k12,k21, and k22) with the pressure are all of the same order. In such a case, ΔV*11 is ΔV*12, and ΔV*22 is ΔV*21 (ΔV*ij is the activation volume in which the i radical reacted with the j monomer). The conclusion drawn from our previous works, that the monomer reactivity ratios of the copolymerization between nonconjugated monomers are independent of the pressure was supported by the experimental results of this report.