bluuebunny/crossref_metadata_2025_split huggingface dataset:
The Radiation-Induced Addition of Acetaldehyde to Isobutylene
Authors: Iizuka Shinji , Hatada Motoyoshi , Hirota Kozo 
Published: July 2006

Abstract
The radiation-induced addition of acetalde-hyde to isobutylene has been found to proceed at room temperature; the G(telomer)’s are smaller by one or two orders of magnitude than those when ethylene or propylene is adopted as the taxogen, and they increase markedly with the temperature, reaching a maximum at 110∼150°C.
It has been shown from the gas chromato-graphic and NMR analyses of the telomer produced that the radical chain mechanism proposed in former papers by the present authors is reasonable, although minor products seem to be formed in accordance to an ionic mechanism.
It has been found that the G values of all the telomers decrease in the presence of several solid materials, suggesting the catalytic decomposition of acetyl and other intermediate radicals.
The Structure of Bis(dithizonato)-zinc(II) and -Cadmium(II)
Authors: Yamamoto Yasuo , Yoshinaga Tetsuo , Yamada Shoichiro 
Published: July 2006

Abstract
Two forms of bis(dithizonato)cadmium(II) have newly been isolated. Upon recrystallization from pyridine, both the forms yielded the same dark red crystalline powder. A comparison of their infrared and ultraviolet spectra shows that the mode of coordination and the configuration of zinc(II) and cadmium(II) are the same as in the mercury(II) complex.
The Dehydrating Cyclization of S-Carboxymethyl-cysteine and N-Acetyl-S-carboxymethyl-cysteine
Authors: Ozawa Hitoshi 
Published: July 2006

Abstract
S-Carboxymethyl-cysteine (SCMC) cyclizes by dehydration to form 3-oxo-5-carboxy-per-hydro-1,4-thiazine (SCMC-lactam) when the aqueous solution was heated at 110∼180°C. SCMC-lactam was also obtained from N-acetyl-SCMC when the latter was treated with N,N′-dicyclohexylcarbodiimide and hydrolyzed subsequently at pH 9.0.
Studies in the Two Phases System Sodium Formate-Pyridine. Extraction of Nickel and Separation from Chromium
Authors: Deshmukh G S , Rao A L J 
Published: July 2006

Abstract
The distribution of nickel in the two phase system, sodium formate-pyridine is studied in detail. The effects of pH, volume of pyridine and molarity of formate are studied and the optimum conditions for the complete extraction are established. The possibility of using this extraction technique for the separation of nickel and chromium has also been worked out and a procedure for the analysis of a syn-thetic mixture of nickel and chromium is given.
The Hydration of Some Organic Compounds in an Aqueous Solution. I. Studies of Aliphatic Aldehydes by Raman-effect Observation
Authors: Matsushima Michiko 
Published: July 2006

Abstract
The Raman spectra of acetaldehyde, its aqueous solution and its heavy water solution have been recorded at various temperatures and in various concentrations in order to find the Raman frequencies characteristic of the hydrated species and in order to investigate the reversible hydration process. Almost all the lines have been assigned tentatively on the assumption that the hydrate molecule has Cs symmetry. The lines at 325, 480, 567, 1353, 1440, 1449, 2874, 2939 and 2996 cm−1 can be referred to as the lines characteristic of the hydrate. Supporting data have also been obtained for the related compounds for the sake of comparison. Moreover, through the intensity measurements, equilibrium constants, as well as the heat of hydration, have been evaluated as the basis for a discussion of the hydration process.
The Determination of the Water Content of the Low Polymers of Formaldehyde by the Karl Fischer Method. I. The Determination of the Adsorbed Water and Bound Water Formed by the Pyrolysis of the Polymer
Authors: Muroi Kaname , Ogawa Kunihiko 
Published: July 2006

Abstract
The adsorbed water of the low polymer of formaldehyde was determined by extraction with dry methanol and Karl Fischer titration. The sum of the adsorbed water and the water formed by the pyrolysis of the sample was determined by titration with the specially prepared Karl Fischer reagent SS, after the sample had been dissolved in propylene glycol by heating. The method of the separation and the determination of the two kinds of water was thus established. When the average numerical degree of polymerization of the polymers was calculated from the content of bound water determined by this method, satisfactory results were obtained. To verify the accuracy of the determination of water content, formaldehyde and methanol were determined independently; their sum was found to be almost 100%.
Ionic Hydration in an Aqueous Electrolyte Solution and Its Parameter
Authors: Tamura Kiyoshi , Sasaki Tsunetaka 
Published: July 2006

Abstract
Tait’s equation for water and Harned and Owen’s treatment of an electrolyte solution, together with sound velocity data, enabled the calculation of the molar volume of electrolytes in the solution state. The results agreed fairly well with the molar volume of the super-cooled molten electrolyte extrapolated to room temperature.
The concentration coefficient of electrostrictive pressure, L=Pe/C1C2, the volume contraction due to the dissolution of one mole of solute, ΔV, and the volume of hydration water per mole of solute, Vh, as an incompressible part of water have been evaluated. We have found a common variable, [h], for L, ΔV and Vh, and it has been proposed that this variable can be used as a parameter of hydration expressing the mole number of hydration water per mole of electrolyte. A conventional hydration number, [h*], was also proposed.
Influence of Substituent Groups on Nuclear Reactivity in the Formation of Substituted Biphenyls by Reaction of Aromatic Diazo and Related Compounds with Aromatic Liquids. VI. p-Chlorophenylation
Authors: Migita Toshihiko , Morikawa Naotake , Simamura Osamu 
Published: July 2006

Abstract
N-Nitroso-p-chloro(36Cl)acetanilide has been decomposed in mixtures of benzene and mono-substituted benzene C6H5X (X=NO2, Cl, OCH3, and CH3), and the reaction products have been analyzed for 4-chlorobiphenyl and isomeric 4-ClC6H4C6H4X by the isotope dilution method. On the basis of these results, the partial rate factors for the p-chlorophenylation have been calculated to be, for nitrobenzene: o, 4.35; m, 0.61; p, 6.18; for chlorobenzene: o, 2.70; m, 0.87; p, 1.33; for anisole: o, 3.93; m, 0.94; p, 1.54 and for toluene: o, 2.97; m, 1.07; p, 1.32.
The values of the partial rate factor for the meta position give a satisfactory Hammett plot with a slope of −0.27. This fact demonstrates that the p-chlorophenyl radical shows a measure of electrophilic character in the homolytic aromatic substitution.
Influence of Substituent Groups on Nuclear Reactivity in the Formation of Substituted Biphenyls by Reaction of Aromatic Diazo and Related Compounds with Aromatic Liquids. VII. p-Nitrophenylation and p-Methoxyphenylation
Authors: Itô Ryôichi , Migita Toshihiko , Morikawa Naotake , \={O}kuni Morihiko , Simamura Osamu 
Published: July 2006

Abstract
N-Nitroso-p-nitroacet(anilide-14C) and N-nitroso-p-methoxyacet(anilide-14C) have been decomposed at 20.0°C in mixtures of benzene and monosubstituted benzenes C6H5X (X=NO2, Cl, OCH3, and CH3), and the reaction products have been analyzed for 4-nitro-and 4-methoxybiphenyl and isomeric 4-NO2C6H4C6H4X and 4-CH3OC6H4C6H4X by the isotope dilution method.
From the results of these competitive experiments, the partial rate factors for the p-nitrophenylation and p-methoxyphenylation have been calculated (Tables I and II).
The values of the partial rate factor for the meta position give a satisfactory Hammett plot with a slope of −0.81 for the p-nitrophenylation and one with a slope of +0.09 for the p-methoxyphenylation, showing that the p-nitrophenyl radical has a pronounced electrophilic character while the p-methoxyphenyl radical has little, if any, nucleophilic character.
The Stability of Fused Rings in Metal Chelates. II. Copper(II) Complexes of Schiff Bases Derived from Pyruvic Acid and Amino Acids or Diamines
Authors: Nakahara Akitsugu , Yamamoto Haruyo , Matsumoto Hironobu 
Published: July 2006

Abstract
The preparation and some properties of four new copper(II) chelates of Schiff bases produced from pyruvic acid and amino acids or diamines have been reported.
The relative stability of these compounds as well as of other rather popular copper(II) chelates has been discussed on the basis of spectroscopic and polarographic investigations.
It has been demonstrated that any stress on any individual ring in metal polydentatechelates does not generally tend to be deposited in the same ring, but rather spreads to some extent over the whole fused-ring system,, sometimes strengthened and at other times weakened or even completely cancelled by another stress on another ring in the system. Therefore, the stability of fused rings should not be discussed on the basis of a simple summation of the stability of individual rings contained in the fused-ring system. It has been concluded that the stability of metal polydentate chelates increases with a decrease in stress over the whole fused-ring system.
Studies of the Transient Intermediates in the Photoreduction of Methylene Blue
Authors: Kato Shunji , Morita Masaharu , Koizumi Masao 
Published: July 2006

Abstract
The intermediate species which are produced in the course of the photoreduction of methylene blue have been investigated by flash photolysis in plain aqueous, borate and phosphate buffer solutions with and without reducing agents. In an acidic solution, an absorption band with the lifetime of 30μsec. appears at 375 mμ, while in neutral and basic solutions, two bands appear, at 415 and 520 mμ, with lifetimes of 70∼90 μsec. The bands at 375 and 415 mμ are considered to be due, respectively, to the acidic and basic forms of the triplet state, since the transient spectra change with pH, making an isosbestic point.
The band at 415 mμ is overlapped by another one with a lifetime longer by several hundred microseconds; this is presumed to be semiquinone. The intensity of the band at 520 mμ decreases upon the addition of reducing agents and increases upon the introduction of oxygen.
Hence, this band may be due to the halfoxidized form of the dye. These results support the reaction scheme that the excited state of the dye reacts with the ground state, which has been proposed in the investigation of steady light photobleaching.
The Preparation of 2, 5-Thiophenedicarboxaldehyde
Authors: Sone Tyo 
Published: July 2006

Abstract
The application of Kröhnke’s method to 2,5-bis(chloromethyl)thiophene has afforded 2,5-thiophenedicarboxaldehyde, from which some condensation products with amines and active methylene compounds have then been derived. 2-Methyl-5-acetyl-3-thiophenecarboxaldehyde and 2-methyl-3,5-thiophenecarboxaldehyde have also been prepared, from 2-methyl-3-chloromethyl-5-acetylthiophene and 2-methyl-3-chloromethyl-5-thiophenecarboxaldehyde respectively, by the Sommelet procedure.
Entropy and Molecular Motion in the Condensed Phases of Tetrahedral Molecules
Authors: Chihara Hideaki , Shinoda Takako 
Published: July 2006

Abstract
By a comparison of the entropies of sublimation at the triple points of carbon tetrafluoride, carbon tetrachloride and neopentane with those of inert gas solids, it has been shown that these molecules are in the state of hindered rotation rather than of reorientation in the solid at the respective triple points, with heights of the potential barrier of 1.0, 2.4 and 1.3 kcal./mol. respectively. The hindering potential has been shown to be proportional to the transition temperatures of these solids.
A simple model for the structure of liquid carbon tetrachloride has been presented to account for its entropy of vaporization; the model consists in assuming nearest neighbor crystallite embryos in the liquid.
The Synthesis of Methylacetylene by the Pyrolysis of Propylene. II. The Mechanism of the Pyrolysis
Authors: Sakakibara Yasumasa 
Published: July 2006

Abstract
A study has been made of the mechanism of the pyrolysis of propylene at high temperatures (800∼1400°C). Of the gaseous products, hydrogen, methane, ethylene, allene, and 1-butene, obtained in the yields of 25, 43, 40, 27, and 9 mol. per 100 mol. of propylene pyrolyzed (3% conversion) respectively, have been found to be the primary products, while methylacetylene, acetylene, and butadiene, obtained in the yields of 9, 4, and 2 mol. respectively, have been found to be the secondary products. In view of the results of the pyrolysis of allene itself, even at a low conversion of 3%, allene appears to undergo considerable secondary reactions, such as isomerization to methylacetylene, addition to propylene and allyl radicals, and decomposition, for example, to acetylene and methane via methylacetylene. On the basis of the observed results, free-radical mechanisms have been proposed for the primary reactions and main secondary reactions. The mechanism for the primary decomposition reaction is a chain process in which the chain is initiated by the reaction C3H6→C3H5· (allyl radical) + H, and is, via the chain-propagating step, terminated by two types of reactions, C3H5·+H→ C3H6 and C3H5· + CH3·→1-C4H8. The formation of allene-methylacetylene has been satisfactorily explained by considering secondary reactions.
Nature of the π-Electronic Spectra of Aromatic Compounds I. Aromatic Hydrocarbons and Their Hydroxyl Derivatives
Authors: Nishimoto Kichisuke , Fujishiro Ryoichi 
Published: July 2006

Abstract
The π-electronic spectra of a number of aromatic hydrocarbons and their hydroxyl derivatives have been theoretically studied by the ASMO-CI method within the framework of a limited LCMO approximation. The calculated singlet frequencies are in satisfactory agreement with the experimental findings. The experimental Clar relation is obtained theoretically. The present theory suggests that the substitution of a hydroxyl group at the α-position of the parent hydrocarbon has effects of a substantial red shift in the 1La band and a rather small shift in the 1Lb band, but the band characteristics are practically the same as those of the parent hydrocarbon. On the other hand, the substitution at the β-position has the effect of mixing the 1La species with the 1Lb species to a considerable extent, so that the band characteristics of the parent hydrocarbon should be considerably modified by this type of substitution. In the light of the present theory, it is better to regard the spectra of phenanthrene and pyrene as modified biphenyl spectra. A plot of the calculated frequency against the corresponding Hückel energy gives a rather good correlation.
Studies of the Hydration and the Structure of Water and Their Roles in Protein Structure. I. The Effective Volumes of 1-1 Electrolytes in Aqueous Solutions and the Electrostriction of Water
Authors: Goto Sachio 
Published: July 2006

Abstract
The effective volumes, the apparent volumes and the magnitudes of electrostriction for various 1-1 electrolytes in aqueous solutions have been determined from an analysis of the densities of solutions at various concentrations. The molar values thus obtained are stoichiometrically additive. The state of water molecules around ions and particularly the existence of clathrates around various univalent ions, such as lithium, rubidium, cesium, bromide and iodide, and the numbers of hydration water have also been discussed.
Studies of Ammonium Dioxovanadium(V) Bisoxalate Dihydrate
Authors: Sathyanarayana D N , Patel C C 
Published: July 2006

Abstract
A simple method for the preparation of the yellow diamagnetic complex, (NH4)3[VO2·(C2O4)2]·2H2O, is described. Around 200°C, the complex suffers decomposition, giving a bluish-grey paramagnetic compound (NH4)2·[(VO)2(C2O4)3]. The infrared spectrum of the yellow complex shows a covalent bonding between vanadium and the oxalate groups.
The absorption in the ultraviolet region is due to the electron transfer within the VO2 group. An octahedral structure, with the two linearly-arranged oxide oxygens at unequal lengths from vanadium(V), is suggested for the complex anion.
Characterization of the Alumina-Boria Catalyst
Authors: Izumi Y\={u}suke , Shiba Tadao 
Published: July 2006

Abstract
This study has aimed to secure an optimum means for the preparation of an alumina-boria catalyst by a systematic examination of the relationship between the physical characteristics of the catalyst and its activity, and to clarify the mechanism of the development of activity on the basis of the experimental evidence about the chemical interaction of alumina with boric acid and about the chemical structure of the catalyst. The applicability of the catalyst has been studied kinetically for some specific reactions relating to the transalkylation of aromatic compounds. It has been found that alumina-boria shows a higher activity for these reactions than does silica-alumina.
The results and conclusion may be summarized as follows:
I) Boric acid is dehydrated to produce metaboric acid as a probable intermediate and reacts with an active alumina at about 130°C with little disturbance of the crystal structure of alumina, and effective acidic centers are produced. Most of the acid centers are of the Brönsted type. Alumina-boria does not show any definite chemical structure characteristic of aluminum borates, such as 9Al2O3·B2O3, 2Al2O3·B2O3 or Al2O3·B2O3. It is suggested that such a bond as Al-O-B-O-Al may be formed between surfaces of the crystal structure of alumina and may result in acidic centers.
II) The catalytic activity of toluene disproportionation shows a good correlation with the Bronsted acidity. This is well compatible with the likely theory that the reaction proceeds via a carbonium ion mechanism.
III) The activity of the disproportionation is considerably affected by the structure of the alumina used as the catalyst base as well as by the boria content of the catalyst. The catalyst prepared from η-alumina shows a higher activity than that from χ-alumina, while α-alumina does not give an active catalyst because of its poor reactivity with boric acid. A rise in the crystallinity of alumina lowers the reactivity. Excessive boria reduces the catalytic activity. An effective catalyst for the transalkylation of aromatic compounds can be obtained when alumina-boria is calcined above 400°C.
IV) The results of such reactions as the disproportionation of toluene, the isomerization of xylene and the transethylation between benzene and diethylbenzene can be well interpreted kinetically by assuming that the rates of these reactions are controlled by surface reactions between adsorbed molecules of the reactants.
V) In the disproportionation of toluene, a decrease in the activity of the catalyst with the length of the run was observed. This phenomenon can be explained analytically by taking into account the fact that some contaminant such as the carbonaceous material, which is produced by side reactions (cracking of toluene and xylene), covers effective sites of the catalyst.
VI) It seems to be due essentially to the higher concentration of active sites in alumina-boria that its activity of the transalkylation of aromatic compounds is higher than that of silica-alumina.
Physical Properties and Structure of Polyacetonitrile
Authors: Oikawa Eizo , Kambara Shu 
Published: July 2006

Abstract
The fact that a polymer containing C=N double bonds is formed from saturated nitrile complexes with metal chlorides is supported by the infrared absorption at about 1600 cm−1 and the characteristic addition of silver nitrate. The polyacetonitrile has an electric conductivity from 10−10 to 10−5Ω−1 cm−1 and an energy gap from 0.4 to 1.2 eV., indicating that the polymer is an organic semiconductor.
The electric conductivity increases and the energy gap decreases with increases in the heating time and temperature, suggesting a more extensive formation of a conjugated system, including also C=C double bonds among polymer chains at a higher temperature. This theory is supported by the evolution of ammonia, resulting in simultaneous decreases of the H and N contents of the polymer, the appearance of the absorption at 840 cm−1, by oxidation by potassium permanganate, by analyses of ESR line shapes, and by viscometric measurements. This structual change may bring about a noncrystalline pattern in X-ray diffraction. Therefore, it is indicated that polyacetonitrile does not have a complete C=N conjugated sequence because of some pyrolysis, accompanied by the extension of a conjugated sustem such as cross-linking at a higher temperature and a longer heating.
The Electrical Conductivity of Heterocyclic Compounds. Fluoridine and Triphenodioxazine
Authors: Inoue Hiroo , Noda Kazuo , Imoto Eiji 
Published: July 2006

Abstract
The electrical conductivities of fluoridine and triphenodioxazine have been measured, and it has been confirmed that (1) the ρ0 of three compounds decreased in the following order: triphenodioxazine &gt; fluoridine in the surface-type cell and fluoridine &gt; triphenodioxazine &gt; pentacene in the sandwich-type cell; (2) Δε depended on the 1E1 of the absorption spectrum; (3) in the presence of oxygen, the dark- and photo-current of fluoridine increased, while those of triphenodioxazine decreased; (4) the photo-current of fluoridine was less than that of triphenodioxazine, and (5) the generation of the charge carrier in both fluoridine and triphenodioxazine was bimolecular in the absence of oxygen.
The Kinetics of the Reaction of Formaldehyde with Ammonia
Authors: Ogata Yoshiro , Kawasaki Atsushi 
Published: July 2006

Abstract
The kinetics of the reaction of formaldehyde with ammonia to form hexamethylenetetramine has been investigated in dilute aqueous solutions at 20°C in the pH range between 6.3 and 11.9. The reaction was first-order with respect to ammonia and second-order with respect to formaldehyde. The rate increased sharply with the increasing pH to a maximum between 9 and 10, and then it decreased gradually. These results may be explained by a mechanism involving a rate-determining attack of methylolamine on free formaldehyde to form dimethylolamine, followed by the formation of hexamine through cyclotrimethylenetriamine and 1,5-endomethylene-1,3,5,7-tetrazacycloöctane.
On the Electrolytic Rectification Effect in Ion-exchange Membranes
Authors: Sen\={o} Manabu , Yamabe Takeo 
Published: July 2006

Abstract
The electrolytic rectification effect has been observed in a double-membrane system. The static and dynamic current-voltage characteristics have been measured, and it has been demonstrated that the mechanism of the rectification similar to that of the p-n semiconductor junction holds true for this system. Reasonable values have been estimated for the characteristic parameters, although there are many discrepancies requiring further examination.