bluuebunny/crossref_metadata_2025_split huggingface dataset:
Corundum α-Al2O3 Formation from the Dehydration of Boehmite γ-AlOOH under Hydrothermal Conditions. II. The Reaction Rates and the Mechanism
Authors: Yamaguchi Goro , Yanagida Hiroaki , Fujimaru Takeshi 
Published: July 2006

Abstract
The authors have measured the reaction rates of corundum formation from boehmite under some hydrothermal conditions for the purpose of discussing the reaction mechanism. They have proposed that, in such cases as the crystallization of corundum or boehmite, there exists the hydrated poly ion of the structure intimately related to the lattice of the product phase and that the formation process often becomes the rate-determinant if no seed crystals of the product phase have been added beforehand. The seed crystal supplies the poly ions which accelerate the simple ions to transform themselves into the poly ions. The mechanism has been illustrated schematically and discussed in detail.
The Electrokinetic Potential of Lead(II) Sulfate
Authors: Morimoto Tetsuo , Hirata Yutaka , Kittaka Shigeharu 
Published: July 2006

Abstract
The ζ-potential of lead sulfate has been studied by applying the streaming potential method to samples obtained by various preparative methods and subjected to various temperature treatments. All the ζ-potentials measured have a positive sign, irrespective of such conditions as the kind of reagents and excess ions used in the preparation or the pH value of the reacating solution. It has been postulated that the surface of lead sulfate is hydrolysed to produce lead hydroxide, whose ζ-potential is explicit in the measurement of the streaming potential of lead sulfate. This is supported by the pH value of the saturated solution of lead sulfate. The surface behavior of lead sulfate in relation to the dye adsorption can also be explained in this way.
The Spectrophotometric Determination of Gallium(III) with Xylenol Orange
Authors: Otomo Makoto 
Published: July 2006

Abstract
The reaction between gallium (III) and xylenol orange has been studied spectrophotometrically in order to establish the optimum conditions for determining traces of gallium. Depending on the pH value of a solution, gallium (III) reacts with xylenol orange to form two complexes. The 1 to 1 complex which gives a maximum absorbance in the pH range from 1.2 to 1.7 has an absorption maximum at 530 mμ when measured against a reagent blank. The 1 to 2 complex which gives the maximum absorbance in the pH range from 4.5 to 5.5 has an absorption maximum at 502 mμ. Either with 1 to 1 and 1 to 2 complexes, Beer’s law is obeyed up to 60 mμ. of gallium. The apparent molar extinction coefficients of the 1 to 1 and the 1 to 2 complexes have been calculated to be 22900 and 16300 respectively. The present method is comparable in sensitivity with the stilbazo or the luminogallion IREA method. The addition of a small amount of fluoride is effective in eliminating some interfering cations, including aluminum (III), thorium(IV) and zirconium(IV).
The Electrooxidation of Absolute Methanol
Authors: Sasaki Kazuo , Nagaura Shigeo 
Published: July 2006

Abstract
From the several experiments described above, it can be concluded that the electroactive species in the anodic reaction of methanol in the moderate potential range is the methylate anion only.
The evidence for this conclusion will be summarized below.
The static potential of the platinized platinum electrode in absolute methanol is affected by the methylate concentration.
It is confirmed that a definite transition time in an anodic chronopotentiogram is observed only for the case of the methylate ion. The results from the potentiostatic experiments also support this conclusion.
Although this is the case, methanol is still electrolyzed to form formaldehyde at a higher potential range. Product analysis shows that the yield of formaldehyde is affected appreciably by the kind of supporting electrolyte. Except fluorine, an appreciable number of free halogen molecules is detected in the solution after electrolysis. Even in the case of an iodine/iodide couple, the thermodynamic potential is far more positive than that of methanol. It may be understood from this fact that the electrooxidation of neutral methanol is strongly irreversible. Furthermore, it seems quite plausible that some part of the methanol is decomposed by the attack of the free radicals (or atoms) formed by the discharge of salt anion. The reaction scheme can be formulated as follows:
X− → X+e
X+CH3OH → HX+CH3O (or CH2OH)
2CH3O (or CH2OH) → CH3OH+HCHO
Coinciding with this hypothesis, the current efficiencies of formaldehyde formation are increased in the order of the hydrogen-abstracting power of the four halogen atoms examined, i.e.,I&lt;Br&lt;Cl&lt;F (see Fig. 9).
The mechanism of the electrolytic oxidation of methanol in aqueous solution has been studied by many authors, but no mechanism has yet been accepted without any ambiguity. The static electrode potential observed in an aqueous methanol solution rests near the thermodynamic redox couple:
CH3OH=HCHO+2H++2e 0.23 V . NHE
It is evident, however, that the real process does not proceed through such a simple reversible path.
Another mechanism proposed is the catalytic dehydrogenation:
CH3OH=HCHO+2H(Ads)
2H(Ads) → 2H++2e
This mechanism seems somewhat plausible, and some indirect evidence for it has been pointed out by the present authors.12)
Although it is difficult to state a definite conclusion about the reaction mechanism in the aqueous solution, the present conclusion, emphasizing the importance of the methylate ion, seems applicable in the case of the aqueous phase reaction. The fact that the performance of the methanol fuel cell in the alkaline medium is superior to that in the acidic one can thus be understood if the following reaction is taken into account:
CH3OH+OH−=CH3O−+H2O
The Rotatory Dispersion of Cobalt(III) Ammine Complexes Containing Amino Acid as a Unidentate Ligand
Authors: Fujita Junnosuke , Yasui Takaji , Shimura Yoichi 
Published: July 2006

Abstract
Fifteen new cobalt(III) ammine complexes containing amino acids as unidentate ligands have been prepared. The infrared, visible and ultraviolet absorption spectra of these complexes indicate that the oxygen of the carboxyl group acts as a donor atom. The circular dichroism and the rotatory dispersion of the unidentate complexes of the optically active α-amino acids and such chelate amino acid complexes as [Co(l-α-ala) (NH3)4]2+ have been measured. The results suggest that the magnitude of the anomalous dispersion of the α-amino acid complex in the region of its first absorption band seems to depend mainly on the conformational mobility of the optically active ligand in the coordination sphere.
The Separation of Rare Earths by Paper Electromigration and Focusing Chromatography
Authors: Kiso Yoshiyuki , Yamada Itsuko , Yamamoto Yuroku , Shinagawa Mutsuaki 
Published: July 2006

Abstract
The optimum pH value and concentration of EDTA for separating rare earths (lanthanum, cerium, praseodymium, neodymium, samarium and yttrium) by the technique of paper electromigration have been evaluated on the basis of the migration theory. The validity of the theory has then been justified experimentally. The best condition for separating was at the range of pH 1.7–2.1 of 5×10−3 m EDTA. Also, the applicability for focusing chromatographic separation has been examined with several pH arrangements between hydrochloric acid on the anodic side and a EDTA complexing agent solution on the cathodic side. Summarizing the above results, it has been concluded that the initial optimum pH of an anodic solution for separation may be obtained by selecting the pH range close to the expected one for the ordinary electromigration, while the effect of pH in a cathodic solution was not as severe as the former.
Effect of Density in the Radiolysis of n-Butane
Authors: Miyazaki Tetsuo , Shida Shoji 
Published: July 2006

Abstract
A study has been made of the effect of density on the radiolysis of n-butane at 170°C over the density region 0.006–0.575 g. cc−1. While G(H2) and G(C2H6) are not affected by the density change, G(CH4) and G(C3H8) decrease sharply in the density region from 0 to 0.1 g. cc−1. The latter facts may be interpreted in terms of the collisional deactivation of the excited ion. The rate constant of the fragmentation of the butane ion has been estimated from the deactivation-fragmentation competition scheme and compared with the rate constant calculated from the quasi-equilibrium theory. Agreement is satisfactory. The formation of methane by ionic fragmentation near the critical state has also been considered.
The Nitration and Sulfonation of 2,4,6-Triphenyl-1,3,5-triazine
Authors: Ogata Yoshiro , Izawa Yasuji , Kawashima Yuji 
Published: July 2006

Abstract
The nitration of cyaphenine (2,4,6-triphenyl-1,3,5-triazine) with a mixture of nitric and sulfuric acids has been found to give products with mostly meta- and partly para-substituted benzene rings. The composition of products varies with the varying reaction conditions. m,m′-Dinitrocyaphenine is the product of the highest number of nitro groups. The sulfonation of cyaphenine with oleum gives trisulfonated cyaphenine at meta-positions of benzene rings; it suffers desulfonation when left standing in the reaction mixture for a long time.
The Radiolysis of Mono-, Di- and Trimethylamine in the Gas Phase
Authors: Takamuku Setsuo , Sakurai Hiroshi 
Published: July 2006

Abstract
The γ-radiolysis of methylamines in the gas phase has been investigated, applying the absolute dosimetry involving the measurement of saturation ion currents in the gases during irradiation. The major volatile products are hydrogen, methane and ammonia. Ion-pair yields of hydrogen for mono-, di- and trimethylamine are 3.10, 2.78 and 1.78 respectively. Those of methane are 0.10, 0.45 and 0.41 respectively. The yields of hydrogen and methane are independent of the pressure up to 300 mmHg, but at pressures less than 100 mmHg there are slight decreases in hydrogen yields. The rate of hydrogen formation from methylamine is proportional to the radiation intensity, and the yield decreases in the presence of a small amount of ethylene. By kinetic analyses of the results with an added scavenger, it has been observed that 81% of the hydrogen formed from methylamine is caused by a radical process, while the value is 41% for trimethylamine.
The Ionization Constants of Organic Compounds. I. The Microscopic Ionization Constants of Tyrosine and Related Compounds
Authors: Yamazaki Futaba , Fujiki Kiyoko , Murata Yasue 
Published: July 2006

Abstract
A method has been formulated for the estimation of the microscopic ionization constants from spectroscopic data which measure the fractional ionization of one of the groups as a function of the pH value. This method has been applied at the ionic strength of 0.05 to the ionization of tyrosine (I), tyramine (II), 3-iodotyrosine (III), tyrosine methyl ester (IV), tyrosine ethyl ester (V), 3,5-diiodotyrosine (VI), and 3,5-dibromotyrosine (VII). The microscopic constants obtained are 9.55, 9.57, 10.08, 10.06 for I; 9.70, 10.09, 10.72, and 10.33 for II; 8.00, 8.70, 9.52 and 8.82 for III; 8.41, 7.27, 8.99 and 10.13 for IV, and 8.43, 7.31, 8.97 and 10.09 for V, in the order of pka, pkb, pkc, and pkd. For VI and VII, the pka values are 6.44 and 6.29, and the pkb values are 9.36 and 9.22, respectively. It has been illustrated that the method may be applied even in cases where ka&lt;&lt;kb. This approach can probably be extended to other Systems containing two dissociable protons, one of which affects the ultraviolet absorption and the other does not.
Stability Order in Metal Chelate Compounds. IV. 2-Pyridylmethanol Complexes
Authors: Murakami Yukito , Takagi Makoto 
Published: July 2006

Abstract
The complexing behavior of 2 - pyridylmethanol with magnesium(II), manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) has been studied in aqueous media at 25.0±0.1°C and an ionic strength of 0.10 m (KNO3). The stability constants for the 1 : 1 (ligand to metal) complexes of manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) with the neutral 2-pyridylmethanol and also for the 2 : 1 complexes of nickel(II) and copper(II) have been evaluated. The resulting stability order with respect to the bivalent metals has been found to follow the sequence:
Cd(II)&lt;Mn(II)&lt;Zn(II)&lt;Co(II)&lt;Ni(II)&lt;Cu(II)
The higher stability of the present complexes relative to the corresponding pyridine complexes may be ascribed to the formation of a chelate ring which involves the hydroxyl group of the ligand.
After the complex formation between metal ions and the neutral ligand has proceeded to a certain extent, the liberation of a hydroxyl proton from the complex was observed to occur in several metal complex systems. This tendency was greatest for the copper complex, followed by the zinc, nickel and cobalt complexes in this order. Acid dissociation constants for the 1:1 and 2:1 copper complexes have also been evaluated.
Several pieces of evidence have been obtained in support of the coördination ability of the hydroxyl group of the present ligand in its anionic form.
The neutral copper chelate, bis(2-pyridylmethanolato)copper(II), as well as other various copper 2-hyridylmethanolate chelates which involve acetate, chloride, iodide, nitrite and thiocyanate ions as the third component, has been isolated. Acetato(2-pyridylmethanolato)-copper(II) has been found to exist as the tetrameric form in chloroform.
Small Ring Compounds. VII. The Syntheses of 3-Oxabicyclo-[3.1.0]hexane and Its Derivatives
Authors: Shono Tatsuya , Oku Akira , Morikawa Takeshi , Kimura Masatoshi , Oda Ryohei 
Published: July 2006

Abstract
Some bicyclic ethers containing a cyclopropane ring, i.e., 3-oxabicyclo [3.1.0] hexane derivatives, have been synthesized. Two methods have been used in the syntheses of these compounds. One of them has been the dehydration of cis-1,2-dimethylolcyclopropane derivatives, and the other, the addition of some carbenes to 2,5-dihydrofuran. The Simmons-Smith method has also been adopted. The NMR spectra of these bicyclic ethers have been examined. The types of their spectra are fairly simple. The chemical shifts and the coupling constant of some protons have also been measured. Attempts to polymerize these bicyclic ethers, unfortunately, have been unsuccessful.
The Electronic Spectra of Aniline and N-Methylaniline Adsorbed on Aluminum Chloride. I
Authors: Sato Hiroyasu , Hirota Kozo , Nagakura Saburo 
Published: July 2006

Abstract
The electronic spectra of aniline and N-methylaniline adsorbed on evaporated film of aluminum chloride have been measured (150–300 mμ for the former adsorbate and 185–300 mμ for the latter). In the case of N-methyl-aniline, a spectrum which is nearly the same as that of ethylbenzene has been obtained. In the case of adsorbed aniline, the spectrum shows features intermediate between those of the aniline vapor spectrum and those of the toluene vapor spectrum. These results can be interpreted in terms of the electron donation from the lone-pair electrons on the nitrogen atom of these molecules to some electron-accepting center on aluminum chloride, presumably to the vacant sp3-orbital of the aluminum atom on the surface, resulting in the weakening of the conjugation between the amino- (or N-methylamino-) group and the benzene ring. The positions of the absorption bands are interpreted qualitatively in terms of the relative location of charge-transfer and locally-excited configurations in these molecules.
Formation Constants of Sulfato, Acetato and Sulfatoacetato Complexes of Copper(II) at Ionic Strength 1.0
Authors: Tanaka Nobuyuki , Saito Yu , Ogino Hiroshi 
Published: July 2006

Abstract
The polarographic method for the determination of the formation constants which is based on the measurement of the effects of acetate and/or other co-existing ions on the equilibrium of the substitution reaction, M+M′L\ightleftarrowsML+M′, has been developed, and applied to the study of the copper(II) complexes with acetate and/or sulfate ions. The formation constants obtained at 25°C and ionic strength 1.0 are: 2·0×10 for KCu(OAc), 1·1×102 for KCu(OAc)2, &lt; 3 for KCuSO4, ∼3×10 for KCu(SO4)2, 4×10 for KCu(OAc)(so4) and ∼7×10 for KCu(OAc)(SO4)2.
The Spectrophotometric Determination of Anions by Solvent Extraction with Metal Chelate Cations. VIII. A New Method for the Determination of Cadmium
Authors: Kotsuji Keiya 
Published: July 2006

Abstract
A new method for the determination of cadmium has been proposed. The method is based upon solvent extraction of the associated complex formed between 2,2′-dipyridyl iron(II) chelate cation and tetraiodo-cadmium complex anion and upon estimation of the absorbance due to the chelate cation in the organic phase.
The NMR Signal Shape of Identical Nuclei Exchanging between Two Different Environments
Authors: Nakagawa Toshio 
Published: July 2006

Abstract
The Gutowsky-Holm equation has been transformed into a formula which expresses the signal as a function of dimensionless parameters (a=2πτ|νA–νB|, r=1⁄2πT2|νA–νB| and pB) and a dimensionless variable (f=(ν–νA)/(νA–νB)). The shape function in this form is convenient for graphic representation and can be easily calculated for a desired combination of the parameters by using a suitable computer. The exchange rate can be determined by searching for a theoretical curve that agrees with the shape of the experimental signal.
The Surface Adsorption of Sodium Alkyl Sulfates from Dioxane-Water Mixtures
Authors: Shirahama Keishiro , Nakao Kiyoshi , Endo Hiroko , Matuura Ryohei 
Published: July 2006

Abstract
The surface adsorptions of three sodium alkyl sulfates (C12, C14, C16) from dioxane-water mixtures have been measured by using 35S-labeled surfactants; it has been found to decrease with an increase in the dioxane concentration. This decrease has been explained in terms of the following factors; (1) the variation in the standard chemical potential of the surfactant in the bulk phase, or the free energy of transfer, (2) the surface tension of the solution, and (3) the dielectric constant of the solvent. In a solvent containing more dioxane than 40wt.%, it has been shown, both by experiment and by theory, that these alkyl sulfates lose their surface activities.
The Coprecipitation Behavior of Rare Earth Elements with Calcium Oxalate upon Precipitation from a Homogeneous System
Authors: Matsui Masakazu 
Published: July 2006

Abstract
The effects of the pH value, the concentration of organic acid and several other variables upon the distribution coefficient were studied for the coprecipitation process of the calcium-lanthanide oxalate system. The logarithmic distribution law was followed in all cases of the coprecipitation of rare earth elements. Of the several variables studied which affected the logarithmic distribution coefficient, the most important were the pH value and the concentration of an organic acid. The coefficient decreased as the acid anion content increased. This can be attributed to the fact that the acid anion formed complex compounds with lanthanide and calcium. The distribution coefficients of several rare earth elements in producing the precipitate from a similar solution were closely related to their basicity or to the solubility of their oxalate salts. The order of the magnitude of the distribution coefficient was as follows: Lu&gt;Y&gt;Eu&gt;Ce; this was in the reverse order of the basicity of rare earth elements or of the solubility of their oxalate salts.
Studies of Aminosugars. XI. Configurational Studies of Aminosugar Glycosides and Aminocyclitols by a Copper Complex Method
Authors: Umezawa Sumio , Tsuchiya Tsutomu , Tatsuta Kuniaki 
Published: July 2006

Abstract
An extensive study has been made of the determination of the rotational shift of aminosugars in three kinds of cuprammonium solutions, i. e., in solutions of tetramminecopper(II) sulfate, ammoniacal cuprous chloride and Cupra B, with special consideration of the spacial relationships between adjacent amino and hydroxyl groups in six-membered chair molecules. This paper is an extension of the work of Reeves which provided a tool for the determination of the spacial relationships between adjacent two-hydroxyl groups. Some significant generalizations have been obtained. About ten derivatives of glucosamine have been prepared, and their structures, as indicated by their rotational shifts, have been discussed. The absolute configurations of d- and l-trance-2-aminocyclohexanol have been successfully determined.
Organic Sulfur Compounds. VI. The Reactions of Arylsulfinic Acids with Alkyl Chlorocarbonates
Authors: Kobayashi Michio , Terao Miki 
Published: July 2006

Abstract
The reactions of the arylsulfinic acid salts with alkyl chlorocarbonates in various alcohols as solvents gave the alkyl sulfinates, in which the alkoxyl groups originated from the solvent alcohols, not from the chlorocarbonates. Sodium p-toluenesulfinate-18O and ethyl chlorocarbonate in a large excess of methanol gave methyl p-toluenesulfmate-18O, which was shown to contain about half of the 18O atoms of the starting salt. The mixed anhydride of sulfinic acid and monoalkyl carbonate is postulated as an intermediate, the alcoholysis of which would give the sulfinate ester. Reactions have been studied also in the nonhydroxylic solvents.
The Non-Newtonian Flow of Poly(Dimethyl Siloxane)
Authors: Ito Yoshio 
Published: July 2006

Abstract
The non-Newtonian flow of poly (dimethyl siloxanes) with a wide variety of degrees of polymerization (Z), 31.6 to 6.02×103, was studied by using short capillary viscosimeters. Measurements were performed in the range of rate of shear from 10−1 to 3×106 sec−1. It was found that the flow behavior was markedly affected by the value Z of the test materials. That is, the flow was practically Newtonian over the entire range of shear rates when Z was less than 1.55×102. For higher values of Z, however, typical non-Newtonian behavior was observed in the range of moderate shear rates. At extremely high shear rates, the materials with Z=3.23×102 to 2.63×103 exhibit the upper (or second) Newtonian flow, but the materials with still higher values of Z exhibit the spiral flow. It was also found that the Shishido equation (J. Chem. Soc. Japan, Pure Chem. Sect. (Nippon Kagaku Zasshi), 84, 889 (1963)) was applicable to this polymer in describing the observed viscosity vs. shear rate dependence. Finally, an empirical method was proposed for estimating the upper Newtonian viscosity value from the viscosities at zero shear stress and at the inflection point of the flow curve.
A Spectroscopic Study of Alkylnitrobenzene Anion Radicals
Authors: Nakai Yasuto 
Published: July 2006

Abstract
A series of alkylnitrobenzene anion radicals has been studied by both electron spin resonance and infrared spectroscopy. It has been shown that there is a relationship between the magnitude of the nitrogen hyperfine splitting constant and the steric effect of the bulky alkyl group adjacent to the nitro group. In addition to the physical deformation factors, the effects of solvents, counter-ions, and temperature variation have been discussed. In the infrared spectra, the differences between anion radicals and neutral molecules have been found to be small, except for the change in the absorption intensity of the nitro-group stretching vibration.