bluuebunny/crossref_metadata_2025_split huggingface dataset:
Kinetics of the Caro’s Acid Oxidation of Dimethylanilines
Authors: Ogata Yoshiro , Tabushi Iwao 
Published: July 2006

Abstract
The rates of the Caro’s acid oxidation of dimethylaniline and p-substituted dimethylanilines were measured in aqueous solutions of various pH’s and temperatures. The rates were found to be proportional to the product of the concentrations of both reactants. The effects of pH and p-substituents on the rate constant were estimated. The rate constant in acid media increased with increasing electron-withdrawing power of the p-substituent of dimethylaniline, while the constant in alkaline media increased with decreasing pH or increasing electron-releasing power of the substituent. A probable mechanism involving a rate-determining attack of neutral Caro’s acid molecule on free amine was proposed and discussed.
The Reaction of 1,8-Cineole with Acid Solutions
Authors: Matsuura Tamon , Komae Hisashi , Sait\={o} K\={o}z\={o} 
Published: July 2006

Abstract
The reaction of 1,8-cineole with 60% acetic acid at 70°C for 10 hours under stirring gave dl-α-terpineol (0.12%) and trans terpin (0.03%). By the action of 21% sulfuric acid at 70°C for 3 hours, cineole yielded dl-α-terpineol (4.6%), terpin hydrate (0.20%), trans-terpin (0.12%) and monocyclic hydrocarbons (a small amount). On the other hand, the reaxtion of cineole with 0.6% sulfuric acid solution at 70°C for 10 hours gave dl-α-terpineol and trans-terpin in poor yields. In this case the reaction products are the same as in the case of 60% acetic acid.
Next, terpin hydrate was treated with 64% acetic acid at 70°C for 10 hours. The reaction products were dl-α-terpineol (2.7%) and trans-terpin (trace). By the action of 21% sulfuric acid at 70°C, terpin hydrate was attacked easily, and after 15 minutes it was converted to dl-α-terpineol (17.8%), trans-terpin (0.20%), 1,8-cineole and monocyclic hydrocarbons (11%). The monocyclic hydrocarbons consisted of α-terpinene, dipentene, Δ2,4(8)-p-menthadiene and p-cymene. trans-Terpin was, also, treated with 60% acetic acid at 70°C for 10 hours, the reaction product being dl-α-tepineol (1.8%).
On the basis of the above experiments a reaction mechanism for the action of acid solutions on 1,8-cineole was proposed.
Polymerization of Olefins with Trialkylboron Catalyst. III. Copolymerization of Butadiene, Isobutylene and 1-Phenylbutadiene
Authors: Ashikari Nobuyuki 
Published: July 2006

Abstract
The relative reactivities in the copolymerization of some monomers which do not polymerize alone with alkylboron catalyst, with those which polymerize alone, were obtained. The copolymerization rate of 1-phenylbutadiene with another monomer was so small that the relative reactivity could not be obtained. But, from the studies on the reaction product of 1-phenylbutadiene and methyl methacrylate, it was considered that the former copolymerized with the latter.
Recombination of Hydrogen, Nitrogen and Oxygen Atoms on Copper and Silver Single Crystal Surfaces
Authors: Nakada Kazuo 
Published: July 2006

Abstract
Recombination of hydrogen atoms, nitrogen atoms and oxygen atoms was carried out on single crystal surfaces of copper and silver subjected to various surface pre-treatments.
With both the recombination of hydrogen atoms and that of nitrogen atoms, copper surfaces electrolytically polished have always higher activity than those chemically polished. The Cu(100) surface chemically etched by ammonium persulfate was more active than that etched by nitric acid for both hydrogen atoms and nitrogen atoms, whereas with the Cu(110) the opposite order of activity was obtained. For both silver and copper, no evidence was found to show the different order of activity between the recombination of hydrogen atoms and that of nitrogen atoms. Concerning the recombination of oxygen atoms on single crystal surfaces of silver, the (110) face was found to be more active than the (100) face in accord with the result of our earlier work about the recombination of hydrogen atoms on single crystal surfaces of copper.
Polymerization of Methyl Methacrylate Initiated by the System of p-Toluenesulfinic Acid, Dimethylaniline and Oxygen
Authors: Uehara Ryoichi 
Published: July 2006

Abstract
Initiation of the polymerization of methyl methacrylate with the initiating system, p-toluenesulfinc acid-oxygen-dimethylaniline, has been investigated from the standpoint of chemical kinetics. The initial rate of polymerization of methyl methacrylate was linearly proportional to the square roots of the concentrations of each component of the initiating system, and methyl methacrylate. The polymerization initiating action of the initiating system is lost by changing the sulfinic acid to its anhydride or esters. The formation of a salt from the sulfinic acid and dimethylaniline was suggested as the first step of the initiation of the polymerization.
Synthesis of Polyanhydride. I. Mixed Anhydride of Aromatic and Aliphatic Dibasic Acids
Authors: Yoda Naoya , Miyake Akihisa 
Published: July 2006

Abstract
Copolymerization reactions of mixed anhydrides of aliphatic and aromatic dibasic acids have been investigated. It has been shown that a polyanhydride of regular structure was obtained from diacid chlorides and dibasic acids in organic medium, and that polyanhydrides of random structure were obtained from the mixed aromatic and aliphatic dibasic acids. A polyanhydride having its melting point at 225°C was prepared for terephthalic acid and adipic acid copolymer of regularly linked structure and that having its melting point at 215°C for terephthalic acid and sebacic acid copolymer. It was found that the stability of copolymer towards hydrolytic and thermal degradations was greater for those with regularly linked structure than for a polyanhydride of random structure. The mixed polyanhydrides of random structure were prepared and the diagram of composition versus melting point was obtained. The mole fractions of the two acid components were found to be 35∼40 mol. % of terephthalic acid and 60∼65 mol. % of aliphatic dibasic acid for copolymers melting at 220 to 240°C. It has further been shown that aliphatic and aromatic dibasic acids furnish a series of copolymers in which the solubility decreases and the melting point and the degree of crystallinity increase as the proportion of aromatic dibasic acid is increased.
Self-diffusion of Iodide Ion and Strontium Ion in Strontium Iodide Solutions
Authors: Matuura Ryohei , Koga Yasushi 
Published: July 2006

Abstract
The self-diffusion coefficient of iodide ion and strontium ion in aqueous strontium iodide solutions has been measured by a capillary method. It has been found that the Onsager’s limiting equation can be applied to the self-diffusion of both ions. The Dη⁄η0 vs. \sqrtc relation for iodide ion has been represented by two straight lines, while that for strontium ion has been shown by a much more complicated curve. The latter has been represented successfully by an empirical equation for strongly hydrated ions presented by Matuura and Shimozawa.
The Crystal Structure of Bis(adiponitrilo)copper(I) Nitrate
Authors: Kinoshita Yukio , Matsubara Ikuo , Higuchi Taiichi , Saito Yoshihiko 
Published: July 2006

Abstract
The crystal structure of bis(adiponitrilo)-copper(I) nitrate has been determined by the two-dimensional Fourier method. It is orthorhombic Pnnn with two formula units in a cell of dimensions: a=9.41±0.02 Å, b=13.73±0.02Å and c=5.85±0.01 Å.
The crystal consists of infinite three-dimensional networks of complex ion [Cu(NC–CH2–CH2–CH2–CH2–CN)2]nn+ and nitrate ions. A copper atom is tetrahedrally surrounded by four nitrogen atoms at a distance of 1.98 Å. Each adiponitrile molecule is coordinated to two different copper atoms with nitrogen atoms of both ends, forming a planar zigzag configuration of methylene groups. Thus the copper atoms and the ligand molecules form a complicated threedimensional 4-connected network. The nitrate ions lie perpendicularly to the a-axis. The trigonal nitrate ion seems to have statistical azimuthal orientations in the crystal and its apparent symmetry becomes 222.
All the atoms in the group Cu–N–C–C lie approximately on a straight line. This fact and the observed carbon-nitrogen distance of 1.13 Å suggest that the bond character in the carbon-nitrogen group may essentially be expressed as C≡N.
On the basis of the structures of this and the other related complexes, some remarks have been made on the mechanism of cuprous ion dyeing of polyacrylonitrile fibers.
Studies on the State of Formic Acid Adsorbed on Silica and Alumina by a Combined Method of Nuclear Magnetic Resonance and Infrared Absorption
Authors: Hirota Kozo , Fueki Kenji , Shindo Kotaro , Nakai Yasuo 
Published: July 2006

Abstract
The state of formic acid adsorbed on silica and alumina has been studied by a combined method of nuclear magnetic resonance and infrared absorption. The adsorbed formic acid in a monomolecular layer has been found not to be dissociated in the case of silica, but to be dissociated in the case of alumina.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. I. Biphenyl
Authors: Suzuki Hiroshi 
Published: July 2006

Abstract
1) The ultraviolet absorption spectra of biphenyl in the crystalline state, in the solution state, and in the vapor state have been discussed in detail.
2) The relation between the position of conjugation band in the spectra of biphenyl and the spatial configuration of the molecule has been clarified by calculations based on the simple LCAO molecular orbital method.
3) By using the results of the calculations, it has been inferred from the analysis of the absorption spectra that the angles between the planes of the two benzene rings in the most probable conformations of biphenyl in the solution state and in the vapor state are about 20°C and about 40∼43°C, respectively. These values coincide fairly well with the values estimated by other workers on different grounds.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. II. o-Alkyl-and o,o′-Dialkylbiphenyls
Authors: Suzuki Hiroshi 
Published: July 2006

Abstract
The method described in the preceding part of this series has been applied with allowance for the electronic bathochromic effect of the substituents to o-alkyl- and o,o′-dialkylbiphenyls, and the relation between the ultraviolet absorption spectra and the most probable spatial configurations of these compounds has been clarified, resulting in the conclusion that the interplanar angle in o-methylbiphenyl as well as its analogues is about 60°C and that o,o′-dimethylbiphenyl as well as its analogues has the cis-configuration in which the interplanar angle is about 70°C.
On the basis of the result, the interpretation by Braude and Forbes of the spectra of o-methyl- and o,o′-dimethylbiphenyl has been criticized.
In addition, the inferred spatial configurations of these biphenyl derivatives have been correlated with some physical and chemical properties of these and some related compounds.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. III. o,o′-Bridged Biphenyls
Authors: Suzuki Hiroshi 
Published: July 2006

Abstract
The ultraviolet absorption spectra of some o,o′-bridged biphenyls and their relations to the spatial configurations have been discussed. The method developed in the earlier parts of this series has been applied to these compounds, especially o,o′-three-atom-bridged (o,o′-7-memberedring-bridged) and o,o′-four-atom-bridged (o,o′-8-membered-ring-bridged) biphenyls, and the interplanar angles have been calculated to be about 44.5∼47.3° (average, 46°) for the former compounds and about 58.0∼61.5° (average, 59.8°) for the latter.
Effect of Dry Grinding on Gibbsite
Authors: Yamaguchi Goro , Sakamoto Kenichi 
Published: July 2006

Abstract
The effect of dry grinding on gibbsite was examined by X-ray diffraction, X-ray small angle diffraction and differential thermal analysis. It has been found that there are two sorts of structural change in the process of dry grinding. One, which occurs early in this process, is the slip of layers. In this stage (002) reflection retains its intensity. The other, which takes place after grinding of about 10 hr., is the three-dimensional disintegration of the crystal structure and the intensities of all diffractions become weak. Since only two reflections (002) and (110) are observed after 40 hr., it can be known that the direction of the slipping of layers is [110].
DTA-curve of gibbsite exhibits three endothermic peaks in the beginning of grinding but comes to exhibit only one peak which indicates the decomposition of gibbsite to alumina. This means that ground gibbsite decomposes directly to χ-alumina as fine gibbsite and boehmite is not produced in this process.
The Kinetics of Substitution Reactions Involving Metal Complexes. II. Effect of Acetate Ions on the Reaction between Copper(II) and Lead-Ethylenediaminetetraacetate Complexes
Authors: Tanaka Nobuyuki , Kato Kiyoko 
Published: July 2006

Abstract
The effect of acetate ions on the rate of the substitution reaction of copper(II) and lead-EDTA complexes is explained quantitatively on the basis of the formation of acetato complexes of copper (II) and lead(II) in acetate media and on the assumption that the substitution reaction proceeds only through the hydrated metal ions. The rate constants, the heats of activation and the entropies of activation for three elementary reactions are recalculated with the experimental results obtained previously.
Studies on the Graphitization II. Sub-structure and Crystallite Growth of Carbon Black
Authors: Kuroda Haruo , Akamatu Hideo 
Published: July 2006

Abstract
The sub-structures of carbon black and its change with heat-treatment have been investigated by means of X-ray small-angle scattering and electron microscopy.
With heat-treatment, the X-ray small-angle scattering intensity increases in the higher angle region, indicating the development of heterogeneous sub-structures to minute crystallites. Above 2000°C, the crystallite growth is rapidly accelerated, and at an extreme, a carbon black particle disintegrated to smaller crystalline units. Electron microscopic observations, especially for Thermax which has a large particle size, revealed that the crystallites, are in alignment with their c-axes being in the direction of normal to the particle surface. This alignment leads to the polyhedral shape of the heat-treated particles. From these observations, the substructures and the mechanism of crystallite growth in carbon black particles have been discussed.
Electron Diffraction Investigation on the Molecular Structure of 1,1,2-Trifluoro-1,2,2-trichloroethane
Authors: Iwasaki Machio 
Published: July 2006

Abstract
The molecular structure of 1,1,2-trifluoro-1,2,2-trichloroethane was investigated by means of the sector-microphoto-meter method of electron diffraction. The existence of the two isomeric forms, Cs and gauche was ascertained and the amount of the gauche form was found to be 76±7 per cent at 20°C. This corresponds to the energy difference of 270±250cal./mol., the gauche form being more stable than the Cs form. The interatomic distances were determined as follows: C–F1=l.379±0.021Å, C–F2=1.329±0.014Å, C–Cl1=1.747±0.027Å, C–Cl2=1.758±0.020Å and the equilibrium angle of the gauche form is 59.5±3.5°, where the C–C bond distance and the bond angles were assumed to be equal to the value of CF2Cl–CF2Cl and CFCl2–CFCl2 molecules, which have already been investigated by the present author.
Studies on Antibiotics and Related Substances. VIII. Syntheses of the Two Enantiomorphs of 5-Methylenecyclopentanone-3-carboxylic Acid
Authors: Kinoshita Mitsuhiro , Umezawa Sumio 
Published: July 2006

Abstract
1) The two diastereoisomeric mixtures (IIa and lIb) of 5-(dimethylaminomethyl)-cyclopentanone-3-carboxylic acid hydrochloride were synthesized from the two enantiomorphs of cyclopentanone-3-carboxylic acid by means of the Mannich reaction.
2) The two diastereoisomeric mixtures (IIIa and IIIb) of methyl 5-(dimethylaminomethyl)cyclopentanone-3-carboxylate hydrochloride were degraded to give methyl (+)- and methyl (−)-5-methylenecyclo-pentanone-3-carboxylates (IVa and IVb), which were hydrolyzed into (+)- and (−)-5-methylenecyclopentanone-3-carboxylic acid (Va and Vb), respectively.
3) It was found that IVa and IVb possess high potency against Staph. aureus and both Va and Vb show significant antitumor activities of the same extent.
Studies on Organic Reagents for Inorganic Analysis. V. m-Nitrophenylfluorone for the Spectrophotometric Determination of Zirconium
Authors: Sano Hirotoshi 
Published: July 2006

Abstract
The spectrophotometric determination of a micro amount zirconium, using m-nitrophenylfluorone, has been described. The method recommended here, which is carried out in 0.1 n hydrochloric acid solution, shows nearly fifty times the sensitivity of the alizarin red S method, about five times that of the quercetin method, and about 1.2 times that of the phenylfluorone method reported previously as the most sensitive reagent by the author and K. Kimura. The solution becomes stable enough to carry on the spectrophotometric determination by adding some cyclohexanol and ethanol, and no precipitation is found for the small amount of zirconium. Furthermore, the stability for increasing acidity in the solution is greater than that of the phenylfluorone method. The method is found to be suitable for the determination of 0 to 0.5 p.p.m. of zirconium. Transfer the sample solution (less than 10 ml.) to a 25 ml. volumetric flask. Then add additional acid to bring the acidity up to 1.0 n hydrochloric acid and 7.5 ml. cyclohexanol-ethanol (1:2) mixed solution, and 5 ml. ethanolic solution containing 3 mg. m-nitrophenylfluorone in that order. Adjust the volume to 25 ml., shake the solution, allow to stand for one hour, and read the absorbance of the solution with a spectrophotometer at 550 mμ with 1-cm. glass cells and distilled water as a control solution. Oxalate, fluoride, phosphate, titanium, germanium, iron(III) and antimony cause serious interference.
Changes of Dynamic Properties of Some Kaolin Minerals by Heat-treatment
Authors: Mochida Shigeru , Kawasaki Isao , Nishimura Yoichi 
Published: July 2006

Abstract
When kaolin mineral is heat-treated at a relatively low temperature region, its density has the minimum value between 500 and 800°C and the maximum at about 1000°C.
The value of dynamic properties of kaolin mineral increases slightly until about 800°C but increases rapidly beyond 1000°C to reach the maximum value. Then, the value is inclined to decrease rapidly beyond the temperatures, at which the maximum value is yielded. Similarly, the filling ratio also has the minimum value at about 800°C and increases rapidly beyond 1000°C to reach the maximum value. This indicates that when kaolin mineral is heat-treated at a relatively low temperature region, its dynamic properties have a close relation with its filling ratio. It is considered that these phenomena are due not only to the sintering of clay mineral by heat-treatment but also to the structural changes as shown in X-ray diffraction data.
The changes of dynamic and physical properties and of the structures of kaolin mineral heated in a closed vessel take place later than those heated in the open air. It may be due to the fact that the oxidation of the organic matters contained in kaolin mineral is oppressed in a closed vessel.
Studies on Explosion Reaction of Ethylene Mixed with Oxygen or Air. II. On the Explosion Peninsula
Authors: Suga Masao 
Published: July 2006

Abstract
In the previous paper, the explosion limit of ethylene mixed with oxygen and with air by the “admission method” was presented. It was pointed out that the explosion peninsula lies in the region between the first and the second pressure limit of explosion. The results of observation in this region differ from those in thermal explosion.
In the present experiment, the following results have been obtained.
(1) The explosion peninsulas of ethylene-oxygen and ethylene-air mixtures lie approximately in the range of the same temperature and pressure limits as that of carbon monoxide-oxygen mixture.
(2) If ethylene concentration exceeds ca. 25% ethylene with oxygen, the explosion peninsula disappears.
(3) The induction period of explosion in the explosion peninsula is relatively longer than those of other thermal explosions.
(4) In the explosion within the explosion peninsula, the apparent activation energy estimated in accordance with Seme-noff’s theory is of abnormally high value. Merely from these facts, it is difficult to determine the explosion mechanism of ethylene-oxygen mixture, but it is possible for one to assume that the explosion within the explosion peninsula has a different mechanism from other thermal explosions.
If one refers to the studies of Neumann and Serbinoff, Norrish and Food, and Lewis on the explosion of methane-oxygen mixture, he will find that the explosion peninsula which is observed in the explosion limit of ethylene-oxygen or -air mixtures is not always related to the nature of ethylene itself. In other words, ethylene-oxygen mixture is decomposed into carbon monoxide first in the definite range of temperature and pressure. Furthermore, it is considered that carbon monoxide which is produced and accumulated in slow oxidation of ethylene, i. e., slow reaction, is ignited in the definite condition. Thus, if ethylene concentration is greater than the stoichiometric value crresponding to C2H4+3O2=2CO+2H2O, the oxygen which is required to oxidate this carbon monoxide is insufficient, and therefore the explosion peninsula disappears. The conclusion is a little too speculative, but it is considered that the explosion peninsula of ethylene-oxygen or -air mixtures originates in the oxidation of carbon monoxide which is accumulated in slow reaction.
Formation and Aging of Precipitates. XII. Studies on Types of Crystal Growth of Barium Sulfate by Dissolution in Water
Authors: Takiyama Kazuyoshi 
Published: July 2006

Abstract
The oval and rectangular crystals of barium sulfate precipitates seem to grow through the dendritic and perfect crystal growth processes, respectively. These particles dissolve in the process of diffusion washing. The oval particles dissolved slightly show the dendrite structure in them, and the rectangular particles dissolved slightly show the large steps around the particles. Thus these particles proved to have grown through dendritic and perfect crystal growth processes, respectively. The surface of the aged particles of both oval and rectangular crystals become stable by digestion in mother liquid; hereby the dissolution rate of inner parts of particles is faster than that of surface parts of them.