bluuebunny/crossref_metadata_2025_split huggingface dataset:
Rapid Colorimetric Determination of Selenium by the Tin (II)-Strong Phosphoric Acid Reduction Method
Authors: Kiba Toshiyasu , Akaza Ikuko , Hachino Hiroaki 
Published: July 2006

Abstract
A new procedure for a rapid determination of selenium has been devised by the present authors. Tin(II)-strong phosphoric acid, previously prepared by the authors, has a remarkable decomposing and reducing power, and selenium in various forms can be reduced to hydrogen selenide which is evolved as a gas from samples. Sulfur in various forms is reduced to hydrogen sulfide at the same time. Solid samples such as pyrite can be allowed to decompose rapidly by simple heating with the reagent in an atmosphere of hydrogen. The gas evolved is introduced into an absorbing solution of 5 n sodium hydroxide. Then, a small volume of 30% hydrogen peroxide solution is added. Thus sodium selenate and sodium sulfate are formed in the solution. After adding an excess of concentrated hydrochloric acid and boiling for about twenty minutes with a reflux condenser, the selenic acid is reduced to selenious acid, while the sulfuric acid remains unchanged. The solution is kept at 45°C for several minutes, and solutions of gum arabic and tin(II) chloride are added successively. The red color of the elementary selenium is measured at 372 mμ by a photoelectric colorimeter. The recovery of selenium is uniform even in the presence of large amounts of sulfur and iron. The analysis of selenium in pyrite was carried out by this procedure, and the results were in good agreement with those obtained by other methods.
Phenothiazine Derivatives. VII. Reactions of Phenothiazines with Sulfuryl Chloride and with Chlorosulfonic Acid
Authors: Fujimoto Manabu 
Published: July 2006

Abstract
Reactions of some phenothiazines with sulfuryl chloride and with chlorosulfonic acid were investigated. With sulfuryl chloride, phenothiazine (I), its 5-oxide (II), and 1,3,7,9-tetrachlorophenothiazine (III) gave the same product, 1,3,7,9-tetrachlorophenazathionium chloride (IV), which yielded the corresponding hydroxide VI by the action of aqueous sulfuric acid and of ethanolic potassium hydroxide. To establish the structural relationship of these substances, mutual transformations were carried out. Treatment of phenothiazine and of its 5-oxide with chlorosulfonic acid gave the inner salt VIII of 3,7-disulfophenazathionium hydroxide, which yielded the inner salt IX of 3-sulfo-7- (chlorosulfonyl)phenazathionium hydroxide by the action of thionyl chloride. Chlorosulfonic acid converted phenothiazine 5,5-dioxide into 3,7-disulf ophenothiazine 5,5-dioxide which was obtained also by the oxidation of the inner salt VIII with 30% hydrogen peroxide in acetic acid.
Action of Reducing Agents on Copper Phthalocyanine and its Chlorinated Derivatives
Authors: Shigemitsu Masahiro 
Published: July 2006

Abstract
Action of reducing agents on copper phthalocyanine and its chlorinated derivatives was studied, and it was found that, while copper phthalocyanine containing no chlorine did not suffer from discoloration, the color of its polychlorinated derivatives darkened. The discoloration, was most conspicuous when 13 to 14 chlorine atoms per phthalocyanine molecule were contained. The chlorinated copper phthalocyanine become stable towared reducing agents when it was exhaustively chlorinated.
It was confirmed that the darkening of the color of pigments was caused by the change of chemical composition, not by the change of size and form of particles.
Protonation Effects on the Electronic Spectra of Pyrazine
Authors: Mataga Shizuyo , Mataga Noboru 
Published: July 2006

Abstract
The protonation effect on the electronic structure and spectra of pyrazine has been studied theoretically employing quantum mechanical calculation. Semi-empirical Hartree-Fock SCF MO’s for pyrazine interacting with two protons have been computed with two different methods, respectively.
i) Electrostatic potential due to proton has been added to the core potential in the total electronic Hamiltonian and nuclear attraction integrals which arise owing to the proton potential have been computed theoretically employing the usual Slater 2pπ AO’s.
ii) The doubly protonated pyrazine has been replaced by doubly charged pyrazinium ion and molecular integrals have been evaluated semi-empirically using valence state ionization potential and electron affinity of the N+ atom.
The calculated spectra with method i are in a very good agreement with the experiment. The calculation with method ii has led to a result which is in rather poor agreement with the experimental observation. On the basis of these results, some discussions about the protonation effect on the electronic structure of this molecule have been given.
The Formic Acid Rearrangement of 3,4-Dimethyl-1-pentyn-3-ol and 3-Isopropyl-4-methyl-1-pentyn-3-ol
Authors: Takeshima Tatsuo , Nagaoka Ken , Yokoyama Masataka , Morita Shigeki 
Published: July 2006

Abstract
The behavior of 3,4-dimethyl-1-pentyn-3-ol (II) and 3-isopropyl-4-methyl-1-pentyn-3-ol (III) toward formic acid was investigated. The carbinols, as in the previous report, were chosen as model ones in which the tertiary carbon atom is adjacent to the carbon atom carrying the hydroxyl group. Both carbinols gave a significant quantity of the respective aldehydes. These aldehydes were easily isolated on simple distillation.
II gave 3,4-dimethyl-3-penten-2-one (IIa) in 45% yield and 3,4-dimethyl-2-pentenal (lib), a new aldehyde, in 5% yield. Ill gave 3-isopropyl-4-methyl-3-penten-2-one (IlIa) in 55% yield and 3-isopropyl-4-methyl-2-pentenal (IIIb) in 6% yield. These carbonyl compounds were characterized. IIIb was hydrogenated to give 3-isopropyl-4-methylpentanal (IV) as the 2,4-dinitrophenylhydrazone.
Analysis of the Multi-azeotropes in Terms of the Zeroth Approximation
Authors: Yamada Ikuho , Yoshida Takatoshi , Kawase Osamu 
Published: July 2006

Abstract
Assuming the zeroth approximation for the vapor-liquid equilibrium in multicomponent systems the authors have analyzed multi-azeotropes, and the following results have been obtained.
1) For the condition of azeotropic formation in multi-component systems, Eq. 8 should hold for all combinations of n components.
2) The constancy of ωij is shown as Figs. 1 to 3.
3) Azeotropic composition effect upon temperature is given by solving Eq. 13, and the breaking temperatures are obtained by substituting Xi=1 or 0 into Eq. 13.
4) Azeotropic temperature can be deduced from Eqs. 2, 4 and 13.
Study on Zinc Oxide-Chromium Oxide Catalyst. IV. Dependency of Catalytic Activity on Catalyst Structure
Authors: Ogino Yoshisada , Oba Masaaki , Uchida Hiroshi 
Published: July 2006

Abstract
So far as catalysts made from pastes of zinc oxide powders kneaded with chromic acid solutions are considered, granules in the reduced ones are built up of extremely fine particles which usually are as small as individual crystallites of zinc chromite spinel as well as zinc oxide. The fine particles appear by way of the large particles of zinc-hydroxychromates in the raw catalysts. However, once the raw catalyst comes to contain a greater amount of chromic acid than that corresponding to zinc-hydroxychromate Iβ, the granules in the reduced one are composed of the larger particles, an individual one of which is an assembly of a number of the crystallites.
On the basis of the results available on the catalyst structures, the intracrystalline promoting action of chromium oxide can be explained from Cremer’s viewpoint of the compensation effect. The catalytic activity can be increased by adding an appropriate amount of acetic acid into the paste, the increase being nearly parallel to an increasing extent of the specific surface area. The increase by the addition, however, is expected only with the catalyst produced from the paste of a low chromic acid content.
The Role of the Cationic Group in Anionic Detergents
Authors: Kashiwagi Maresuke , Ezaki Heihachi 
Published: July 2006

Abstract
Various salts of dodecyl sulfate (DS) and alkylbenzene sulfonate have been investigated surface-chemically and from the viewpoint of their bulk properties. It was shown that these organic salts of DS occupy the same surface area as that of SDS, on the substrate of concentrated anmonium sulfate, independent of the nature of the cationic group attached to the sulfate anion. CMC values determined by two different methods (i. e., surface tension and foaming power) show practically the same value. These results are approximately in accord with the known principle that the number of carbon atoms in the molecule of the normal straight chain colloidal electrolyte of one particular class is the determining factor for the value of CMC, although a slight but definite shift in CMC value is observed with variation in substituting group. On the other hand, bulk properties such as viscosity and solubility are influenced remarkably by the substitution of cationic group in anionic detergents.
Polymerization of Aminoacetonitrile
Authors: Hanafusa Hidesaburo , Akabori Shiro 
Published: July 2006

Abstract
Aminoacetonitrile sulfate was heated with kaolin and/or Japanese acid clay at 120∼140°C for 5 hr. The presence of glycyl-glycine and glycyl-diglycine in the extract and the partial hydrolysate of this reaction product was confirmed by paper and column chromatography.
Hydrothermal Reaction of Aluminumtrihydroxides
Authors: Yamaguchi Goro , Sakamoto Kenichi 
Published: July 2006

Abstract
In saturated vapor, the aluminumtrihydroxides dissolve in the water and the velocity of dissolution of the trihydroxides becomes larger as the temperature rises. When this solution is supersaturated over the solubility of boehmite, transformation proceeds. The alkalinity and the boehmite added to the hydroxides accelerate the transition. The former makes easy the dissolution of trihydroxides, and the latter acts as the seed and accelerates the velocity of the crystallization of boehmite.
Distribution of Neptunium between TBP and Some Mineral Acids
Authors: Ishimori Tomitaro , Nakamura Eiko 
Published: July 2006

Abstract
Neptunium-239 is used as the tracer for studies on solvent extraction behaviors of neptunium in the following system:
1. Nitric acid solution and TBP.
2. Hydrochloric acid solution and TBP.
3. Sulfuric acid solution and TBP.
4. Perchloric acid solution and TBP.
Kd values are measured by combinations of scrubbing techniques and chemical treatments. In nitric, hydrochloric and sulfuric systems, neptunium gives three kinds of Kd, distribution ratio which could be assigned to oxidation states of (IV), (V) and (VI). On the other hand, in the perchloric system neptunium does not show Kd value which should be assigned to the oxidation state (IV).
Some of these results are compared with those of uranium, plutonium and other elements. In the nitric system, neptunium (VI) shows an acid dependence of Kd value similar to those of uranium (VI) and plutonium (VI). Kd values of neptunium (IV) and plutonium (IV) vary in almost the same way against the acid concentration of nitric acid. There is also a strong similarity between acid dependences of uranium (VI) and neptunium (VI) in the hydrochloric system.
Behavior of neptunium (V) are compared with those of protactinium.
Finally a simple method for isolation of neptunium from irradiated uranyl salt is stated.
The Crystal Structure of Bis(succinonitrilo)copper(I) Nitrate
Authors: Kinoshita Yukio , Matsubara Ikuo , Saito Yoshihiko 
Published: July 2006

Abstract
The crystal structure of bis(succinonitrilo) copper(I) nitrate has been determined by two dimensional Fourier method. It is monoclinic P2⁄a with two formula units in a cell of dimensions: a=11.62±0.03 Å, b=5.31±0.01 Å, c=9.53±0.03 Å and β=98.8°±0.2°. The crystal consists of nitrate ions and polymeric chains of the following composition:
(Remark: Graphics omitted.)
These chains run parallel to the a-axis-A succinonitrile molecule takes a gauche form with respect to the central C2–C3 bond. A copper atom is surrounded tetrahedrally by four nitrogen atoms with Cu–N distances of 1.96 and 2.02 Å. These facts are in close agreement with infrared spectral observations.
All the atoms in the group Cu–N–C–C lie almost on a straight line. This fact and the observed C–N distance of 1.14 Å suggest that the bond character in the C–N group may essentially be expressed as C≡N.
Studies on the Sapogenins of Dioscorea tokoro Makino. III Synthesis of Isorhodeasapogenin and Some Reactions of Tokorogenin
Authors: Morita Katsura 
Published: July 2006

Abstract
(1) Reduction of anhydrotokorogenin with lithium aluminum hydride led to a new dihydroxysapogenin, desoxytokorogenin; the structure 25D-5β-spirostan-1β,3β-diol was assigned on the basis of various reactions and theoretical considerations.
(2) Desoxytokorogenin, 25D-5β-spirostan-1β,3β-diol, was incidentally found to be identical with isorhodeasapogenin, the structure of which had so far been left unclarified.
(3) Identity of tokorogenic acid with isorhodeasapogenic acid was also confirmed.
(4) Tokorogenin was correlated with samogenic acid and yonogenin via a diosphenol, 25D-5β-spirost-1-en-2-ol-3-one, whose structure was unambiguously established.
On the Crystal Growth of Zinc Sulfide Phosphor
Authors: Otomo Yoshiro 
Published: July 2006

Abstract
(1) The zinc sulfide, before firing, is a large aggregate of crystallites with the crystal diameter of about 150 Å and contains about 8% of α-form.
(2) The crystal growth of zinc sulfide phosphor takes place at about 500°C regardless of whether there is flux or not, but the rate of the growth is much affected by the flux. Without flux, the crystal grows as step-wise piled layers, but, with flux, it grows isotropically showing no influence from the crystal symmetry. Concerning the above difference, there has been discussion, taking into account the density of kinks at the step-wise surfaces of crystals and the change of diffusion constant of zinc sulfide molecules adsorbed at the surfaces.
(3) The transition, α-form ↔ β-form, of zinc sulfide phosphor is rather easy, but becomes difficult without flux. Also, the transition is completed in thirty minutes of firing at 800°C with the flux of 2 wt.% of sodium chloride, but it is completed within ten minutes of firing at 1000°C.
(4) It is probable that there is a metastable state of α-form at about 600°C, but it requires further consideration.
Studies on Antibiotics and Related Substances. VII. The Structure of Kanamycin
Authors: Umezawa Sumio , It\={o} Yukio , Fukatsu Shunz\={o} 
Published: July 2006

Abstract
Evidence is presented to show that both the two aminohexose moieties in kanamycin are directly joined to deoxystreptamine through hydroxyl groups by glucosidic linkages. Proof for the sites of attachment of the two aminohexose moieties rests on the periodate oxidation of the optically inactive 1,3-diamino-4,6-dihydroxy-5-methoxycyclohexane and its N-acetyl derivative which were obtained by the degradation of exhaustively methylated N-acetylkanamycin by acid hydrolysis followed by acetylation. Kanamycin is therefore represented by formula VII.
On the Reactivity of Amide Group of ε-Caprolactam Derivatives
Authors: Ogata Naoya 
Published: July 2006

Abstract
The dipole moments, infrared spectra and rate constants of hydrolysis of ε-caprolactam derivatives have been determined in order to elucidate the difference in reactivity. The great stability of N-methyl-ε-caprolactam is expected, due to the increase of reasonance of amide linkage. Ring dimer of ε-caprolactam is stable for hydrolysis due to the strong intramolecular hydrogen bonds and the reactivity of ring oligomers of ε-caprolactam increases as the ring becomes larger.
On the Dissolution of Na2O–CaO–SiO2 Glass in Acid and in Water
Authors: Tsuchihashi Shoji , Sekido Eiichi 
Published: July 2006

Abstract
(1) The first step in the attack of water on glass is the exchange reaction between the proton and Na+ on the glass surface. Sodium hydroxide thus produced in the boundary layer opens the Si–O–Si bond, and consequently silica passes into solution.
(2) When the exchange reaction between Na+ in glass and H+ in acid solution takes place, more metallic ions will be drawn out of the network owing to the influence of anions existing in the solution. Consequently more cations pass into the solution, while the silica network will be stabilized by acid so that the silica in the solution will be reduced remarkably.
Complexometric Titration of Rare Earth Elements. Dissolution of the Rare Earth Oxalate with Ethylenediaminetetraacetic Acid and Back Titration with Magnesium Sulfate
Authors: Misumi Seizo , Taketatsu Tomitsugu 
Published: July 2006

Abstract
The processes for dissolution of the oxalate and complexometry to determine the small amounts of rare earth rapidly and accurately, were studied. Crystalline rare earth oxalate was precipitated and filtered. The precipitate was dissolved completely with EDTA in alkaline solution and the excess of EDTA in solution was back titrated with standard magnesium sulfate solution. By this procedure, rare earth in the range of a content about 1 to 5mg., was determined rapidly with a good accuracy.
Bond Localization and the Hyperconjugative Effect in the Aromatic Carbonium Ions. II. Electronic Structures of the Carbonium Ions of Isomeric Xylenes
Authors: Morita Toshifumi 
Published: July 2006

Abstract
By means of the LCAO MO method, the π-electron energies of xylene carbonium ions are calculated, for all possible models, with respect to the positions of proton attack, on the basis of the bond localization hypothesis. It is indicated that the explanation of the basic behaviors of isomeric xylenes is impossible merely by the bond localization theory of their carbonium ions, and hyperconjugation should be taken into account.
It is indicated that, when the difference of hyperconjugation energies between protonated m- and p-xylene is about eight kcal./mol., the experimentally observed basic behavior of m- and p-xylenes is understandable.
Studies on Crystal Hydrates. VI. Thermodynamics of Dehydration of Crystal Hydrates. A New Criterion for the Continuous Zeolitic Dehydration. Capillary Condensation of Water Vapor into Exactly Uniform Pores and an Experimental Test of the Kelvin Equation. Case of Dl-Tris-ethylenediaminecobalt(III) Chloride Hydrate
Authors: Chihara Hideaki 
Published: July 2006

Abstract
A simple theory of the thermodynamics of hydrates is developed, which is able to show that the differential molar entropy of dehydration changes with the water content continuously if the hydrate undergoes zeolitic (continuous) dehydration. In this case the integral molar entropy of dehydration does not agree with the differential entropy. The same is true for the heat contents. For stepwise dehydration, on the other hand, both differential and integral entropies coincide in values. A new criterion, termed “entropy criterion”, is presented that if the differential entropy of the water of crystallization, obtained by subtracting the entropy of dehydration (determined by the pressure measurements) from the standard entropy of water vapor 45.1 e. u., differs greatly from 10 e. u., the hydrate should undergo zeolitic dehydration and should have water molecules weakly bonded to the crystal lattice, from which water can be removed without causing collapse of the lattice. This new criterion is equivalent to using the current “isotherm criterion”.
Dl-[Co en3]Cl3·nH2O (n≤4) presents a notable exception to both criterions in that the crystal undergoes zeolitic dehydration in spite of its entropy of dehydration and its isotherm indicating the stepwise dehydration. The failure of the criterions in this crystal is due to the extreme uniformity of pore structure of the hydrate. The Kelvin equation for calculating the pore radius (giving 5.8Å) from the dehydration isotherm is tested against the pore radius obtained by the X-ray crystal structure analysis (giving 2.9 to 3.4Å). It may be concluded that the Kelvin equation is considered to give only the order of magnitude for micropore size. This cobalt complex hydrate is one of the rarest examples having exactly uniform pores and the criterion for the type of dehydration here presented is still effective in most cases.
Intramolecular Interaction between Hydroxyl Group and π-Electrons. IV. Rotational homers of Alcohols and Shift of νO–H Absorptions in Phenyl Substituted Alcohols
Authors: Oki Michinori , Iwamura Hiizu 
Published: July 2006

Abstract
The authors observed symmetric νO–H absorptions for methanol and tertiary alcohols and unsymmetric bands for primary and secondary alcohols. The unsymmetric band was divided into two bands, assuming that the band is an overlap of the two symmetric bands. The idea of the rotational isomerism was successfully introduced for assigning the band and the following points were concluded.
1) Types I and IV show absorption bands at 3644∼3636 cm−1, type II at 3626∼3629 cm−1, type III at 3615∼3618 cm−1, type V at 3616∼3619 cm−1, type VI at 3608∼3611 cm−1, and type VII at 3613∼3617 cm−1.
2) The exception is dialkylphenylcarbinols which show the νO–H absorptions at about 3620 cm−1 and 3608 cm−1, the former being assigned to type III and the latter to type VII. This ruling-out may be attributed to the steric effect and the rotation around the CPh–Cα axis.
The steric effect on the integrated intensities and on the wave number where νO–H absorption falls is also discussed. The differences between types II and IV and between types III and VI were attributed to the existence of the intramolecular interaction between the hydroxyl group and π-electrons of the benzene nucleus. The same reason may cause allyl alcohol to show its main νO–H absorption at about 3620 cm−1.
Stability of Complexes of Several Carboxylic Acids Formed with Bivalent Metals
Authors: Yasuda Motoo , Yamasaki Kazuo , Ohtaki Hitoshi 
Published: July 2006

Abstract
Stability constants of the bivalent metal complexes formed with several mono- and dicarboxylic acids were determined at 25°C and ionic strength of 0.1. For monocarboxylic acids and several dicarboxylic acids having no double bond or forming larger chelate rings than six membered rings the following stability order held: Pb&gt;Cu&gt;Cd&gt;Zn&gt;Ni. It is very remarkable that lead showed the highest stability among bivalent metals.
The Effect of Chain Branching and Molecular Weight of Polyethylene on its Glass Transition Temperature
Authors: Tanaka K\={o}ji 
Published: July 2006

Abstract
A series of measurements by volume dilatometry were performed in order to know whether short chain and long chain branchings, and molecular weight of polyethylene affected the glass transition temperature or not. The glass transition temperature, Tg, was obtained from the intersection of two straight lines of volume-temperature curve and from the discontinuity of the curve obtained by plotting the volume temperature derivatives as a function of temperature. Tg lowered with the increasing amount of short chain branching and there seems to be a linear relationship between Tg and the degree of short chain branching. No appreciable effect of long chain branching on Tg was observed. Tg rose apparently with the increase of molecular weight, but the true rise of Tg was only less than 2°C as molecular weight increased from 10,000 to 50,000. The degree of cubic expansion above and below Tg increased generally as the amount of short chain branching increased.
Halogen Substitution in Liquid Sulfur Dioxide. I. Formation of Alkyl Halides from Alcohols and Halogens
Authors: Tokura Niichiro , Tada Ritsuro , Igarashi Ryoichi 
Published: July 2006

Abstract
The reaction between aliphatic alcohols and bromine in liquid sulfur dioxide at room temperature was investigated in order to obtain further information concerning the behavior of bromine in liquid sulfur dioxide. The reactivity of the alcohols increased in the order of primary &lt;secondary&lt;tertiary.
In addition to alkyl bromides, higher boiling bromides were also produced. The latter resulted from further elimination, dimerization and bromine addition. The rather complicated feature of the bromination is attributable to the presence of sulfur trioxide secondarily formed in the reaction mixture.