bluuebunny/crossref_metadata_2025 huggingface dataset:
The Determinations of Some Metal Ions by Using Hexamminecobalt(III) Chloride and Sodium Thiosulfate as Precipitants
Authors: Yoshimura Jun , Takashima Yoshimasa , Murakami Yoshio , Kusaba Toyoaki
Published: July 2006

1) When hexamminecobalt(III) chloride and sodium thiosulfate solutions were mixed, a precipitate was formed; the composition of this salt was found to be

[Co(NH3)6](S2O3)Cl·H2O

2) In addition to copper and lead, silver, cadium, mercury and bismuth were precipitated, forming insoluble metal complexes, by adding hexamminecobalt(III) chloride and sodium thiosulfate sloutions as precipitants to the solutions of these salts, except for bismuth salt, were found to be

[Co(NH3)6][Ag(S2O3)2],

[Co(NH3)6]4[Cd(S2O3)3]3·6H2O and

[Co(NH3)6]4[Hg(S2O3)3]3·10H2O

3) Various determination methods based on the formation of metal complexes were studied; that is, silver was studied by volumetrically measuring the excess of sodium thiosulfate with an iodine solution, copper and mercury, by gravimetrically weighing by EDTA titration after their complex salts had been decomposed.
The Mutual Interaction between Solutes in Gas Chromatography
Authors: Amaya Kazuo , Sasaki Kazuko
Published: July 2006

The influence of the mutual interaction between the molecules of different components in the sample on the retention volume of each component has been discussed from the standpoint of a strictly regular solution. The retention volume of each component in the mixture either increases or decreases, compared with that in the single component samples, according to the kinds of sample and of stationary phase liquid.
Electronic States of p-Benzoquinone. VIII. Vibrational Analysis of the Vapor Absorption Spectrum around 2900 Å
Authors: Sadô Akira
Published: July 2006

The absorption spectrum of p-benzoquinone vapor was observed at 2900 Å region and the vibrational analysis was carried out. Two absorption groups were found. The bands in group 1 are sharp and single, but the nature of the transition is uncertain. Group 2 is composed of a doublet whose frequency separation is 45 cm−1. It corresponds to the 1B1g←1Ag transition and is allowed by vibronic interaction with the allowed 1Bi2g←Ag transition. The perturbing vibration is a C=O bending vibration belonging to the b3u species whose frequency is 370 cm−1 in the ground state. The vibration frequencies of the main progression are 444 cm−1and 435, 692 and 1560 cm−1 in the ground and excited electronic states respectively.
Radiation Induced Reaction of Silicon Hydride
Authors: Ando Wataru , Oae Shigeru
Published: July 2006

Silane, at various pressures, has been irradiated with 3.8 kilocuries gamma rays. In all experiments, gaseous products of the reaction were hydrogen, disilane and higher silanes, while G-value for the formation of hydrogen depends on initial silane pressure and total dose. Some polymeric material with the approximate empirical formula of (SiH2)x is also formed.

Mixtures of silane with carbon dioxide, water and acetylene were also irradiated with gamma rays, and the rate of hydrogen formation was found to increase with increasing carbon dioxide and water. This was explained by a charge transfer mechanism.
Spectroscopic Studies of Methylamine Adsorption on Gamma-alumina
Authors: Hirota Kozo , Fueki Kenji , Sakai Tokuji
Published: July 2006

It can be confirmed directly by means of NMR and infrared spectra that methylamine is chemisorbed on dehydrated gamma-alumina at room temperature, making a bond probably with the aluminum atom via the nitrogen atom; this conclusion is supported by the fact that the proton signal of the aminyl group cannot be observed at such a surface coverage when that of the methyl group is observed, and the fact that the deformation band of the NH2 group and the stretching band of CH3 group change as a result of adsorption.
Dye-sensitized Photopolymerization of Vinyl Compounds. Polymerization of Acrylonitrile by Stannous Chloride and Acriflavine. II
Authors: Watanabe Ai
Published: July 2006

The photosensitized polymerization of AN in DMF by acriflavine and stannous chloride in vacuo was investigated. The reaction rate was shown as: ν∝[D]1⁄2[SnCl2] [M]2, where [D] and [SnCl2] were small. The experiments performed examining the photobleaching of dyestuff in various conditions led to the finding that the photopolymerization does not occur by virtue of the transiently-reduced dye. The scheme proposed in Part I, in which the transient tin ion of odd valency (Sn3+ and/or Sn+) initiates the polymerization by interacting with the monomer, was further substantiated.
The Kinetics of Substitution Reactions Involving Metal Complexes. V. Reaction between Copper(II) and Ethylenediaminetetraacetatocadmate(II) Complexes in Aqueous Solutions
Authors: Tanaka Nobuyuki , Kamada Minoru
Published: July 2006

The kinetic study of the substitution reaction of copper(II) and ethylenediaminetetraacetatocadmate(II) complexes in acetate buffer solutions has been carried out by the same method as reported previously. The reaction was found, under the experimental conditions, to proceed simultaneously through four different reaction paths, and the rate constants for the elementary reactions of those reaction paths were determined at ionic strength 0.2 at 5 and 15°C. It was confirmed also that this substitution reaction proceed through both hydrated ion and monoacetato complex.
Photosensitized Oxidation of Leuco-uranine and the Identification of the Photobleached Product of Uranine in Ethanol Solution
Authors: Uchida Kengo , Kato Shunji , Koizumi Masao
Published: July 2006

Leuco-uranine was prepared by reducing uranine with sodium amalgam, and some of its properties were investigated. The aqueous solution of leuco-uranine is stable in the presence of air irrespective of its low oxidationreduction potential.

It was found that leuco-uranine is photooxidized to uranine by the use of acridine and some dyes as sensitizers. The reaction may be attributed to the dissolved oxygen and is very reasonable. A quite unexpected result was, however, that a similar reaction takes place more rapidly and more quantitatively in the degassed solution than in the aerated solution. The uranine and acridine employed as sensitizers in this case were ascertained not to sustain any change. The nature of the reaction is not known at the present time.

It was further established that the photobleached product obtained by irradiating the deaerated ethanol solution of xanthene dyes, consists mainly of leuco dye. This was ascertained by comparing their absorption spectra, by the photosensitized coloration, acridine being used as a sensitizer, and, in addition, by means of paper chromatography.
Semiconductivities and Charge Transfer Spectra of Solid Molecular Complexes of 1,3,5-Trinitrobenzene
Authors: Kuroda Haruo , Yoshihara Keitaro , Akamatu Hideo
Published: July 2006

A series of solid complexes of aromatic hydrocarbons and amines, with 1,3,5-trinitrobenzene as the common electron acceptor, were prepared. These complexes were of the loose molecular complex type, and the charge transfer bands were observed with the solid complexes, which showed only small red-shifts from the corresponding bands of the solutions. These solid complexes are poor semiconductors, and the energy gap for the excitation to the conduction state is relatively large, and is nearly coincident with the energy for the charge transfer excitation. From these results, it has been suggested that the charge transfer state in the crystal may not be very different from the corresponding state in the isolated (1 : 1)-complex in the solution. The relation between the charge transfer state and the conduction state has been discussed, and a probable model for the formation of a charge carrier has been suggested.
Dielectric Properties of Monohalogenobenzenes in the Microwave Region
Authors: Okabayashi Hideo
Published: July 2006

The dielectric constants and the loss factors of liquid monohalogenobenzenes were measured in the microwave region by the free wave method and the waveguide method. The experimental results were discussed on the basis of the formula of the local field previously proposed. In the cases of liquid monohalogenobenzenes, the experimental facts can be explained by a single relaxation time.
A Simple Molecular Orbital Method for Discussing the Electronic Structures of Stereoisomers—The Theoretical Method and ESR Hyper fine Splittings of the Terephthalaldehyde Anion
Authors: Morokuma Keiji , Yonezawa Teijiro , Fukui Kenichi
Published: July 2006

A new simple molecular orbital method with parameters modified by electronic interactions was developed so as to discuss simply the difference in electron distributions between stereoisomers. An application was made to the proton hyperfine coupling constants of the cis- and trans-isomers of the terephthalaldehyde anion radical, and the assignment of the constants was proposed on the basis of molecular orbital calculations.
Studies on the Silk-Rhodium Catalyst
Authors: Akamatsu Akira , Izumi Yoshiharu , Akabori Shiro
Published: July 2006

1) The most active catalyst was obtained when 400 mg. of silk-fibroin was boiled with 30 ml. of 0.5% aqueous solution of rhodium chloride for ca. 30 min., and the resulting chelate was then reduced.

2) The activity of this catalyst was not influenced significantly by the conditions for its preparation and was maintained or even increased greatly on storage for a long period. Benzyl mercaptan, ferric and cupric ions poisoned the catalyst, but the inhibition by the metal ions could be restored by ethylene-diaminetetraacetic acid.

3) This catalyst was extremely active for the hydrogenation of the types C=C double bonds C=CHCH2OH and C=HCOOH but inactive for carbonyl groups. For the hydrogenation of other types of C=C double bonds and of nitro groups, the catalyst seems to be less active.
Electrolytically Regenerated Ceric Sulfate for the Oxidation of Organic Compounds. I. Oxidation of p-Xylene to p-Tolualdehyde
Authors: Ramaswamy R , Venkatachalapathy M S , Udupa H V K
Published: July 2006

1. The current efficiency for the oxidation of cerous sulfate in sulfuric acid at a lead dioxide in an undivided cell was generally found to be 70%.

2. By using a paste of cerous sulfate in sulfuric acid, ceric sulfate reagent is obtained in a concentrated form.

3. A kinetic study of the oxidation of p-xylene by ceric sulfate is described and apparent energy of activation is calculated.

4. The process of oxidation of p-xylene to p-tolualdehyde is made cyclic and continuous by regeneration of ceric sulfate at a lead dioxide anode.
Effect of the pH Value on the Rate of the Photoreduction of Methylene Blue by N-Phenylglycines
Authors: Matsumoto Shiro
Published: July 2006

The effect of the pH value on the rate of the photoreduction of methylene blue by N-phenylglycines was studied in detail in the range between 5.9 and 10.5, attention being paid to the effects of buffer solutions and to a possible change in the ionic species of N-phenylglycines with the change in pH value. N-Phenylglycine behaved as a monobasic acid of pKa 4.3 to base titration, so that it existed solely as a univalent anion C6H5NH·CH2COO-in this pH value range. The pKa of several other N-phenylglycines was given also. The concentration and ionic strength of the buffer solutions had some effect; they must be kept constant and as small as possible.

With these precautions, the pH value dependences of Φ∞ , 1/b and B=1/(Φ∞·b), which characterize the quantum yield of the photoreduction, were determined for several electron donors. They were similar in all cases. Semicarbazide was found to be effective as an electron donor for this photoreduction. Log B varied linearly with the pH value in the pH range between 7.0 and 9.0. The slopes were nearly 0.5 for all the N-phenylglycines studied. This means that, if the excited metastable state of the dye formed a complex before the oxidation-reduction reaction, the rate constant of its formation must vary as the root of the hydroxide ion concentration.
Photosensitized Oxidation of Leuco-uranine. I. Qualitative Studies of the Nature of the Reaction in the Deaerated Solution
Authors: Uchida Kengo , Koizumi Masao
Published: July 2006

The nature of the photosensitized oxidation of leuco-uranine (in the deaerated condition), using uranine or acridine as a sensitizer, was investigated from various viewpoints. The possibility of either an oxidizing or a reducing impurity taking part in the reaction was definitely ruled out. The uranine (Remark: Graphics omitted.) leucouranine reaction could be repeatedly carried out in the presence of palladium asbestos. When uranine was used as a sensitizer (alkaline solution), an appreciable quantity of semiquinone could be detected as an intermediate. Reexamination of the spectra of acridine (when acridine was used as a sensitizer) showed that in some cases acridine takes part in the eventual reaction.

It is concluded from various pieces of indirect evidence that the overall reaction is the evolution of hydrogen gas from the leuco dyealthough the direct detection of hydrogen formation has yet been successful.
Electrochemical Fluorination of Aldehydes
Authors: Nagase Shunji , Baba Hajime , Kojima Rimpei
Published: July 2006

Aldehydes were fluorinated electrochemically to prepare prefluorocarboxylic acids. The results were compared with those obtained from the fluorination of alcohols, esters, ketones and unsaturated compounds.

Generally, the yield of perfluorocarboxylic acids was considerably lower in aldehydes because of a great fragmentation or polymerization in the fluorination reaction. No evidence could be obtained for the formation of a detectable amount of partially fluorinated aldehydes or perfluoroaldehydes in the reaction. The mechanism for the formation of perfluorocarboxylic acid fluorides from aldehydes was discussed.
Studies of 2-Oxazolidinones. III. Kinetics of the Pyrolytic Decarboxylation of 2-Oxazolidinones
Authors: Oda Ryohei , Miyanoki Masahiko , Okano Masaya
Published: July 2006

The kinetics of the pyrolytic decarboxylation of 3-substituted 2-oxazolidinones have been studied and the following results obtained. (1) This decomposition is an autocatalytic reaction, in which the amine formed acts as a catalyst. (2) In the decarboxylation of 3-aryl-2-oxazolidinones, the electronic effect of the substituent on the benzene ring indicates that the fission of the N–C bond of the urethane group in the 2-oxazolidinone ring is rate-determining. (3) The initial rate of the aliphatic amine-catalyzed decarboxylation of 3-aryl-2-oxazolidinones is of the pseudo-first-order; it also depends on the concentration and structure of the amine. A mechanism has been proposed which involves a nucleophilic attack of amine on the carbonyl-carbon atom. An amine having an hydroxyl or amino group on the β-carbon shows a large rate-acceleration; this suggests the simultaneous electrophilic participation by the active hydrogen of these groups. (4) The initial rate of the decarboxylation of 2-oxazolidinone itself, catalyzed by aliphatic amine, is of the second-order in oxazolidinone and of the first-order in amine. From this a concerted mechanism has been inferred, in which the amine acts as a nucleophile and the other oxazolidinone acts as an electrophile.
The Behavior of Heat-treated Graphitizing Carbons in Wet Oxidation
Authors: Tagawa Hiroaki , Nakajima Hitoshi
Published: July 2006

The wet oxidation of three kinds of heattreated graphitizing carbons, petroleum coke, anthracite and coal coke, in a solution of potassium dichromate in phosphoric acid has been studied in order to clarify the relationship between the chemical reactivity and the carbon structure.

Changes in the interlayer spacing and crystallite size, which are used as a measure of graphitization, have been examined by X-ray diffraction method for each specimen over the range of heat treatment temperatures from 1100 to 2800°C.

The oxidation velocity increases with the degree of graphitization. The quantity of carbon dioxide evolved, V, is generally expressed by the following equation, V=atb. The b-value depends on only the degree of graphitization and varies from 0.8 to 1.5 according to the increase of graphitization, but it does not depend on the oxidation temperatures.
The Mechanism of the Gelation of a Lead Aldose-cysteinate Solution
Authors: Takahashi Fujio , Mizuguchi Jun
Published: July 2006

The mechanism of the gelation of a solution containing aldose-cysteine and lead salt was studied by measuring various developments such as the pH value, the conductivity, the optical density, and the gelation time. From these results, it was suggested that the gelation occurred when the complex ion of hydrated lead glucose-cysteinate was transformed into an “ol” structure with dehydration. The process of this olation was found to follow the laws of ordinary chemical reaction. The reaction was of the second order.
Synthesis of Histidyl Peptides. II. Synthesis and Properties of Dicarbobenzyloxyhistidylamino Acid Esters
Authors: Sakiyama Fumio
Published: July 2006

Three different methods for the synthesis of dicarbobenzyloxy-l-histidylamino acid esters were studied. The general procedure of the hydrolysis of dicarbobenzyloxyhistidylamino acid esters were reported and the mechanism of this hydrolysis reaction was also discussed.
The Behavior of Various Inorganic Ions in the Separation of Calcium Carbonate from a Bicarbonate Solution
Authors: Kitano Yasushi
Published: July 2006

The author has shown the effect of various inorganic ions on the polymorphic crystallization of calcium carbonate from a bicarbonate solution. No definite conclusion regarding the mechanism to give calcite, aragonite or vaterite can yet be made, but these data help to give a pattern of the influence of inorganic ionic species and the concentration of the mother solution on the polymorphic crystallization of calcium carbonate.

(1) Alkali chlorides in the mother solution inhibited aragonite formation and favored calcite formation. The extent of the inhibition of the aragonite formation decreases in the sequence: ammonium chloride>lithium chloride, sodium chloride>potassium chloride >rubidium chloride, >cesium chloride (sodium nitrate).

(2) (a) Sodium chloride and sodium nitrate in the mother solution inhibited aragonite formation, sodium chloride more strongly than sodium nitrate, (b) With a moderate increase in the amount of sodium bicarbonate (sodium carbonate) added to the mother solution, the percentage of aragonite formation increased to a maximum. With a further increase in the amount, however, the percentage began to decrease and reached zero, (c) When sodium hydroxide was added to the mother solution, only calcite was formed. Aragonite was never formed from the solution which had made alkaline with sodium hydroxide, (d) The presence of sulfate ions favored aragonite formation.

(3) (a) Magnesium ions in the mother solution favored aragonite formation very strongly. The presence of magnesium chloride in the mother solution was more favorable to aragonite formation than that of magnesium bicarbonate or magnesium sulfate. Magnesium was not co-precipitated with calcium carbonate, (b) The presence of calcium chloride in the mother solution had no effect on the crystallization. (c) With an increase in the strontium concentration in the original solution, the percentage of aragonite formation increased to a maximum (optimum strontium content: approximately 2 mg./l). The percentage began to decrease with a further increase in strontium concentration. The strontium was always entrained in calcium carbonate precipitates, even when the strontium concentration was very low. (d) The presence of a small number of barium ions in the mother solution favored calcite formation. The presence of a large number of barium ions favored vaterite formation. Even at a low concentration in the mother solution, barium was always entrapped in the precipitates.
The Chemical Reaction in Silent Electric Discharge. II. The Frequency Effect on Ozone Formation
Authors: Morinaga Kihei , Suzuki Momotaro
Published: July 2006

1. The ozone formation in the silent electric discharge was investigated with a current of higher frequency. The rate is independent of the electric source frequency but dependent solely upon the value of the pulse current, and the rate per pulse current is linear in relation to the electrode area divided by the gap length. The above findings are similar to those in the case of 50 c/sec.

2. At a higher value of pulse current, the ozone formation rate is no longer linear to the pulse current and shows a type of saturation curve.

3. Some relations at a high frequency discharge among pulse current, electrode area and gap length have been discussed.
Studies on Solvent Extraction using Radioactive Isotopes. IX. Solvent Extraction of Carrier-free Cerium-144 with Acetylacetone
Authors: Suzuki Nobuo , Oki Shohachiro
Published: July 2006

144Ce was extracted with acetylacetone in a benzene or in a carbon tetrachloride solution by shaking for 3 min. at a pH range of 4∼9. Though an oxidizing agent such as bromate was not always necessary, the presence of bromate makes the time for extraction shorter. Decontamination from other fission products, 90Sr (90Y), 106Ru, 137Cs, and rere earths (e.g.,152,154Eu), expect 95Zr (95Nb), was found to be negligible. The contamination of 95Zr (95Nb)) was reduced to a negligible amount by repeating the cycle of extraction and stripping or by masking 144Ce with thiocyanate. The separation of 144Ce from fission products with acetylacetone was attempted. 144Pr with a radio-chemical purity of more than 99% was easily obtained by washing the organic phase with an acetate buffer solution of pH 5∼8.
On the Mode of Interaction of Surface Active Agents with Gelatin
Authors: Isemura Toshizo , Tokiwa Fumikatsu , Ikeda Shoichi
Published: July 2006

The mode of the binding of detergents, SDBS, CPC and DPB, by gelatin in the region of low detergent-gelatin ratios, where solutions are stable without precipitation, was investigated by determining the bound detergents by means of equilibrium dialysis.

Detergents bind with gelatin in accordance with the isotherm r=Kcn, where K and n (>1) are constants which measure an affinity for the binding and an extent of cooperative interaction respectively. The value of K, which is dependent on pH and temperature, decreases with increasing pH for the binding of SDBS and vice versa for CPC. The value of n is characteristic of a given detergent. The value of n for SDBS is significantly greater than that for CPC. Thus the extent of the cooperative stabilization of a bound detergent is higher for SDBS than for CPC.

Both anionic SDBS and cationic CPC combine with gelatin, but cationic DPB scarcely combines with it. Further, it was inferred that a detergent, especially SDBS, binds with gelatin, forming aggregates on it in such a manner as the micelle formation.

The sign of charge of the detergent is of essential importance for the binding of the detergent by gelatin, and the length of the alkyl chain of detergent also has additional effects on the binding. The effect of chain length was examined with cationic detergents.
Electron Spin Resonance Hyperfine Spectra of Diphenyl Nitric Oxide
Authors: Deguchi Yasuo
Published: July 2006

Liquid solutions of diphenyl nitric oxide reveal well-resolved proton hyperfine spectra either in mixed solvents of glycerine and ethyl alcohol in a suitable mixed ratio or in vacuum-sealed, degassed solvents.

Assuming odd electron spin densities at the ring carbon atoms and applying Kivelson’s theory, one can explain the experimental results. Moreover, the effect on the ESR spectra of the addition of a methyl group to a benzene ring has been reported on.

Finally, the solvent effect on the ESR spectra has been discussed.
The Systematic Analysis of Silicate Rocks using Ion Exchange Resin
Authors: Ôki Yasue , Ôki Shôhachirô , Shibata Hidekata
Published: July 2006

An accurate and rapid systematic analysis of ordinary silicate rocks was studied with a column of an ion exchange resin (Amberlite IR-120). A powdered rock sample was decomposed by the usual method of Berzelius. Iron was extracted from 6 n hydrochloric acid solution into ether before chromatographic separation Metal ions absorbed on the column are eluted as follows : With 0.4 n HC1 Na and K, with 0.8 n H2SO4 Ti(IV), with 0.8 n HCl Mg, Mn(II), and Ca, and with 4 n HCl Al are eluted successively. A complete analysis of an ordinary rock sample can be carried out in only 3 days by this method.
De-localization of Bond Eigenfunctions in π-Electronic Systems. I. Proposal of an Approximate Method for the Calculation of the π-Electronic States of Molecules
Authors: Takekiyo Shozaburo
Published: July 2006

The influence of the multiple exchange integrals in the HLSP method for the π-elec-tronic systems has been investigated by means of the illustrations of trans-butadiene and cyclobutadiene molecules. Their importance for the theory, including ionic structures, has been emphasized. For avoiding difficulties in calculations due to the presence of many resonance structures in complex compounds, an approximate method has been proposed. In that method, the degree of energy determinants is diminished.
Studies on the Micro-paraffins. V. X-Ray Investigation of Various Paraffin Waxes
Authors: Negoro Kazuo
Published: July 2006

From the X-ray diffraction of n-dotriacontane, various paraffin waxes, micro-paraffin, and each fraction of micro-paraffin separated by the urea method and chromatography, the chain length and the spacings (110) and (200) of each crystal have been computed. Furthermore, the carbon number of the chain, the lengths of the a- and b-axes, the cross-sectional area occupied by one molecule, and the molecular volume have been calculated. They have been calculated on the assumption that thay were in normal crystal form, but in order to make it exact, it is necessary to work with a single crystal. The author would like to try further experiments.
σ-Electronic Structure in Conjugated Systems
Authors: Fukui Kenichi , Kato Hiroshi , Yonezawa Teijiro , Morokuma Keiji , Imamura Akira , Nagata Chikayoshi
Published: July 2006

The σ-electronic structures and σ-electron densities of σ skeletons in some conjugated compounds are calculated by a simple LCAOMO method developed by the present authors.

The inductive and hyperconjugative effects, dipole moment, proton shift, and so on, are briefly discussed. Agreements of the results with experiments seem to be almost entirely satisfactory.

A part of the calculation has been carried out with the KDC–I digital computer of Kyoto University.
The Infrared Absorption Spectra of 1,3,5-Trichlorobenzene, 1,2,4,5-Tetrachlorobenzene and their Deuterated Derivatives
Authors: Saëki Shinnosuke
Published: July 2006

The infrared absorption spectra of 1,3,5-trichlorobenzene, 1,3,5-trichlorobenzene-d3, 1,2,4,5-tetrachlorobenzene and 1,2,4,5-tetrachlorobenzene-d2 were observed in a gaseous state from 700 to 300 cm−1 with a cesium bromide prism and in a solid state from 300 to 100 cm−1 using a grating spectrometer. Furthermore, the spectra in the sodium chloride region were carefully observed in the ranges where the main absorption bands appear, using a long path (720 cm.) high temperature cell. The obtained accurate frequencies and envelopes of the absorption bands have been reported on.

On the basis of these results, the assignments of the infrared active normal vibrations of these substances have been determined and checked by the product rule.

The assignments of the overtone and combination bands have also been determined using the assigned frequencies and species of infrared active and Raman active fundamental vibrations.
Studies on Solid Carbons. II. The Gas-phase Oxidation of Solid Carbons
Authors: Sakaguchi Masakazu
Published: July 2006

The gas-phase oxidation of five sorts of carbons with nitrogen dioxide has been measured under a pressure range from 2.4 to 9.0 cmHg at 150°C by a static method, in order to determine, primarily, the relation between the reaction rate and the physical properties of carbons (B. E. T. area, degree of graphitization, particle shape, micro-pore volume and mean micro-pore radius).

The rate of consumption of nitrogen dioxide has been determined photometrically.

The well-graphitized carbons did not react with nitrogen dioxide, while the rate curves obtained on the amorphous carbons showed as bent straight lines, the inclination of which is steep at the initial stage, followed by a slow second stage. The activation energy in the reaction is very small (<3 kcal.).

The explanation of the results is as follows: the consumption of nitrogen dioxide in the initial stage relates mainly to chemical reaction on the free surface of the carbon, and the rate is controlled by the free surface area and the concentration of the edge atoms of the surface. The rate of the second stage relates to the diffusion process the micro-pore of carbon particles, and it is controlled by the physical fine structure of the surface.
Condensed Vanadate-Phosphates
Authors: Ohashi Shigeru , Matsumura Tadashi
Published: July 2006

Glasses of sodium vanadate-phosphates with P/V ratios of 1∼200 were prepared from mixtures of sodium metaphosphate, vanadium (V) oxide and sodium carbonate. Crystals of sodium vanadate-phosphates with P/V ratios of 7, 10 and 50 were also prepared.

During the preparation of the glasses and the crystals, a part of the vanadium(V) is reduced to vanadium(IV). The percentages of vanadium(IV) in relation to the total vanadium increase with an increasing P/V ratio.

From the paper chromatographic analyses of the aqueous solutions of the glasses and the crystals, it may be presumed that the glasses are mainly composed of chain structures such as

……O–P–O–P–O–V–O–P–O–……

and that the crystals contain considerable amounts of a vanadate-phosphate ring as follows:

(Remark: Graphics omitted.)
A Study of the Adsorption of Detergents at a Solution-Air Interface by the Radiotracer Method. V. The Effect of Inorganic Salts on the Surface Behavior of the Dodecyl Sulfate Ion
Authors: Matuura Ryohei , Kimizuka Hideo , Matsubara Akira , Matsunobu Kenji , Matsuda Tadashi
Published: July 2006

The adsorption of 35S-labeled dodecyl sulfate ion in the presence of excess sodium salts with anions of various valencies was measured directly by the radiotracer method. The anions of the excess salts were chloride, nitrate, carbonate, ferricyanide and ferrocyanide ions, and the concentrations of the excess salts were all 0.1 n. It was found that the adsorption of dodecyl sulfate ion increased remarkably due to the presence of the excess salt and that the surface tension curves and the adsorption isotherms were almost independent of the type of anions.

The behavior of dodecyl sulfate ion was discussed by using the result of the present study together with the previous one, in which the effect of cationic valency and the salt concentration was studied. The logarithmic value of CMC was found to be linear against the logarithmic concentration of excess sodiumchloride and against the valency of cation when the concentrations were all 0.1 n.

The reduced surface pressure and the reduced concentration referred to CMC were proposed, and it was found that the surface tension data of the solutions of sodium dodecyl sulfate containing various kinds of salts and varying concentration of sodium salts were correlated approximately to one curve regardless both of the types and the concentrations of the excess salts. The curve was well expressed by the reduced equation for the surface pressure as a function of the reduced concentration. By combining the reduced equation with the Gibbs equation of n=1, the reduced adsorption isotherm was derived.

It was shown that these reduced equations enable us to reproduce the surface tension and adsorption data of the solutions of sodium dodecyl sulfate in the presence of sodium salts with varying valencies of anions.
Colloid Chemical Studies on Starching Materials. IV. Viscoelasticity and Structure Change of Starch Solutions
Authors: Nakagaki Masayuki
Published: July 2006

Modified Rouse’s equations were applied to solutions consisting of a mixture of highly aggregated and less aggregated polymer molecules. The fraction of higher aggregates, x1, was calculated for 3 and 5% potato starch solutions, a 5% sweet potato starch solution, and a 5% rice starch solution. The value of x1 decreased linearly with the increase of log ω, except for the rice starch. The x1 value of the latter increased rapidly when the log ω became very large.
Effects of Nonelectrolytes on the Temperature of the Maximum Density of Water. I. Alcohols
Authors: Wada Goro , Umeda Saburo
Published: July 2006

The effects of various kinds of alcohol on the temperature of the maximum density of water were observed. The results revealed are as follows :

1) The change in the temperature of the maximum density due to alcohols, ΔT, is not proportional to the solute concentration, disobeying Despretz’s rule and in contrast with ordinary electrolytes.

2) The ΔT for univalent aliphatic alcohols at low concentrations is generally positive; that for tert-butyl alcohol is the largest. The ΔT is likely to become high as the number of carbon atoms and the degree of branching in alkyl radicals increase.

3) The elevation of the temperature of the maximum density due to the interaction of alcohol and water, ΔT′, depends upon the weakness of the cohesion of alcohol and the strength of the hydration of the hydrophilic molecules.

4) As the concentration of alcohol increases, there occurs a lowering of ΔT as a result of interaction between the solute molecules themselves. Similar interactions are seen between different alcohol molecules in ternary systems, but can not be seen between alcohol and electrolytic ions, where the solutes behave independently of each other. In the last case, the additivity of ΔT is realized fairly well.
On the Mechanism of Pulp Bleaching. V. Further Investigations on the Residual Lignosulfonic Acid in Unbleached Sulfite Pulp
Authors: Sato Koichiro , Kobayashi Akio , Mikawa Hiroshi
Published: July 2006

1) By beating unbleached sulfite pulp step by step and changing the beating water, four fractions of residual lignosulfonic acids were obtained. Analytically not very distinct differences were observed between these fractions.

2) The residual lignosulfonic acids isolated by beating and by dimethyl sulfoxide were oxidized with nitrobenzene, and the yields of vanillin obtained from these lignin preparations were comparad with that from ordinary lignosulfonic acid separated from waste liquor. Almost no difference was observed.

3) The amounts of residual lignosulfonic acid dissolved by beating and by dimethyl sulfoxide extraction were in good agreement with those calculated from the amount of the residual lignosulfonic acid remaining in the pulp, thus proving the accuracy of the estimation. Approximately 40 and 20% of the total lignin in unbleached sulfite pulp were dissolved by beating and by dimethyl sulfoxide extraction respectively.
Dehydration Reaction of Hydroxamic Acids with Unsaturated Ethers
Authors: Mukaiyama Teruaki , Nohira Hiroyuki , Asano Siro
Published: July 2006

Dehydration reactions of hydroxamic acids with unsaturated ethers have been studied. The reaction of hydroxamic acids with ethoxyacetylene or methylketene diethylacetal led to the formation of corresponding isocyanates, along with ethyl acetate or ethyl propionate and ethanol, through the intermediate of addition compounds of hydroxamic acids and the dehydrating reagents.

The reaction of hydroxamic acids with n-butyl vinyl ether, on the other hand, led to the formation of dihydroxamic acids, along with acetaldoxime and acetaldehyde dibutyl-acetal. This type of reaction was further extended to the reactions of hydroxamic acids with propenyl ether, acetals and aldehydes, and the formation of dihydroxamic acids was confirmed.
The Rate of Formation of Cobalt Hydrocarbonyl under Various Conditions of Oxo Reaction
Authors: Iwanaga Ryoji
Published: July 2006

By treating a solution of dicobalt octacarbonyl in toluene at 100°C under various partial pressures of carbon monoxide and hydrogen, and by determining the initial rate of formation of cobalt hydrocarbonyl, we have found that the initial rate increases with the increasing pressure of hydrogen and decreases with the increasing pressure of carbon monoxide. These effects of partial pressures on the initial rate of formation of cobalt hydrocarbonyl are parallel with the effects of partial pressures on the rate of the oxo reaction reported by Natta.

In addition, the amount of cobalt hydrocarbonyl in the system during the oxo reaction of methylacrylate and cyclohexene in toluene at 120°C was determined; it was found that only a trace of cobalt hydrocarbonyl appears when acrylate is present, while a large amount of it is present even when cyclohexene is present in the system.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. V. Appearances, Densities, and X-Ray Analysis of Crystal Structures of Cobalt Soaps
Authors: Kambe Hirotaro
Published: July 2006

Crystallinities of cobalt stearates with different colors have been compared. Blue soap shows a prismatic crystal form, but red soap a plate-like form. The apparent density of blue soap in air is much denser than other soaps. Red soap shows a larger density in acetone than in air. True densities measured in acetone show that the density of red soap is higher than that of blue soap.

X-Ray diffraction patterns show the difference between red or pink soap and blue soap. Red soap has a lamellar structure like that of fatty acid, while blue soap shows a quite different structure. Exact X-ray analysis was not ex-ecuted, however, because single crystals of cobalt soaps have not yet been obtained.
Studies on Antibiotics and Related Substances. XIII. Syntheses of 10-Methylene-11-oxododecanoic Acid and 9-Methylene-10-oxoundecanoic Acid, Antitumor Substances
Authors: Kinoshita Mitsuhiro , Nakada Sabur\={o} , Umezawa Sumio
Published: July 2006

1) 10-(Dimethylaminomethyl) -11-oxododecanoic acid hydrochloride (Ia) and 9-(dimethylaminomethyl) -10-oxoundecanoic acid (Ib) have been obtained from the mother liquors remaining after filtration of 13-(dimethylamino)-11-oxotridecanoic acid hydrochloride and 12-(dimethylamino)-10-oxododecanoic acid hydrochloride, respectively.

2) 10-Methylene-11-oxododecanoic acid (IVa) and 9-methylene-10-oxoundecanoic acid (IVb) have been synthesized from the Mannich bases Ia and Ib, respectively.

3) Antitumor activities of IVa and IVb have been described.
Dipole Moments of Polyethylene Glycol Diethyl Ethers
Authors: Kotera Akira , Suzuki Keizo , Matsumura Kimiyoshi , Nakano Takao , Oyama Toshiko , Kambayashi Utako
Published: July 2006

The dipole moments of six lower members of the polyethylene glycol diethyl ethers have been measured, and their configurations have been studied. As the configurations of these compounds the two models have been considered; one is a mixture of the various rotational isomers, and the other a model in which the positions of the internal rotations of two C–O bonds around the C–C bond approximately take the gauche positions with regard to each other, and the positions of the C–O bond and the C–C bond around the C–O bond take positions similar to those mentioned above with regard to each other.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. VI. Some Observations on Thermal Transitions of Cobalt Soaps, by Differential Thermal Analysis, Thermogravimetry, and Magnetic Measurement
Authors: Kambe Hirotaro , Ozawa Takeo , Onoue Masao , Igarashi Shoichi
Published: July 2006

The thermal transitions of red dihydrate and blue anhydrate of cobalt stearate have been measured by differential thermal analysis, thermogravimetry, and magnetic measurement.

Differential thermograms of anhydrous blue soap showed two peaks at high temperatures (about 100°C). When it was heated repeatedly, a new peak appeared at a lower temperature (about 50°C). A low temperature transition is considered to be a transition between mesomorphic phases. The first high-temperature transition corresponds to a transition from a crystalline to an upper mesomorphic state, which disappeared on repeated heating. Red dihydrate soap showed a large peak at 90°C owing to the removal of hydration water. Thereafter it appeared in an anhydrous state.

Thermogravimetric analysis showed the dehydration process in red soap, but not in blue anhydrate. The decomposition of cobalt stearates to stearone and cobalt oxide was found in thermogravimetric curves.

The magnetic susceptibility of cobalt soap obeys Curie-Weiss’ law below the melting temperature, but above it the susceptibility decreases abruptly and anomalous behavior is observed.

Melted soap is in an amorphous state, which was certified by X-ray measurement. Its color and magnetic moment show that melted soap is different in nature from red and blue soaps.
Studies of the Urushibara Catalysts. I. Some Structural Features Revealed by X-Ray Diffraction
Authors: Taira Shin-ichi
Published: July 2006

Some structural features in the Urushibara catalysts were revealed by means of X-ray diffraction, and a hypothesis regarding the activity of the Urushibara catalysts was proposed.
Molecular Association and the Dielectric Constant of a Solution
Authors: Kimura Ko , Fujishiro Ryoichi
Published: July 2006

The formation constant of the nitrobenzene dimer in carbon tetrachloride was estimated as of the order of 0.01 from the dielectric constant of the solution by the use of Scholte’s model. The configuration of the dimer is probably such that one of the constituent molecules lies upon the other. The small formation constant and the configuration of the dimer suggest that there is no need to consider some special forces between molecules such as the Charge tranfer force. The result deduced expermentally are interpreted satisfactorily in terms of the electrostatic force.
Effects of Solvents on the Rate of Oxo Reaction of Methylacrylate
Authors: Iwanaga Ryoji
Published: July 2006

The rates of methylacrylate oxo reactions in a variety of organic solvents were measured by a batch system at 120°C. In general, the rate varies widely in the following order: alcohols > acetone > toluene; this order did not correspond with the order of their dielectric constants nor with the rates of their “base reactions” with dicobalt octacarbonyl, but it does agree with the order of their rates of formation of cobalt hydrocarbonyl under oxo conditions. tert-Butanol shows a positive but small effect on the rate as compared with toluene. When ethylene glycol and formamide having higher dielectric constants were used as solvents, the oxo reaction did not take place. On the bases of these results the mechanisms of the effects of the solvents have been discussed.
Determination of Small Amounts of Copper and Iron with X-Ray Fluorescent Spectroscopy. Combination with Organometallic Precipitation
Authors: Hirokawa Kichinosuke , Gotô Hidehiro
Published: July 2006

The simultaneous determination of small amounts of copper and iron with X-ray fluorescent spectroscopy combined with organic precipitation was investigated. Using an alizarin blue solution, which reacts with copper and iron at a low pH value, as the precipitant, satisfactory results were obtained. The amounts of copper and iron in aluminum, zinc, manganese and nickel were rapidly determined with X-ray fluorescent spectroscopy after this separation.
Electrical Conduction in the Violanthrene-Iodine System
Authors: Uchida Tokiko , Akamatu Hideo
Published: July 2006

Electrical conduction and ESR absorption in the violanthrene-iodine system have been investigated, varying the iodine content. Observation of the Hall effect has been attempted, but the Hall voltage was so small that the effect could not be determined. It was pointed out that, concerning conductive behaviors, the violanthrene-iodine system is analogous with the nickel(II) oxide-lithium oxide solid solution, and that the hopping model of electrical conduction can be applied. From such a view point, the correlation between the observed unpaired spins and charge carriers has been estimated.
Study on Nickel Oxide-Silica-Alumina Catalyst for Ethylene Polymerization. II. Catalyst Structures Related to Catalyst Activity
Authors: Uchida Hiroshi , Imai Hisao
Published: July 2006

After nickel oxide is removed from the catalysts consisting of nickel oxide, silica, and alumina, the catalysts usually show a much lower activity than the original catalysts, with a slight increase in the specific surface area.

The acidity of the original catalysts indicates a maximum at the Al/(Al+Al) ratio of 0.05 and diminishes to some extent after the removal of the nickel oxide. The difference between the acidities before and after the removal of nickel oxide, which is a measure of the acidity originating from nickel oxide, is larger in the range of the higher acidity of the original catalysts. The valence state of nickel is found to be 2 in the Al/(Al+Si) range from 0.03 to 0.1, while it is a little higher than 2 with both decreasing and increasing aluminum contents.

Very few definite relationship have been found between the catalyst activity and acidity. However, when both the activity and the acidity originating from nickel oxide are considered on the basis of the unit surface area, an approximately linear relationship is found between them. The structure of the acid site produced by an addition of nickel oxide is discussed from the view point of an extension of Thomas’ proposal for silica and other binary oxide mixtures.
The Phase Transition of Crystalline Potassium Thiocyanate, KSCN. II. X-Ray Study
Authors: Yamada Yasusada , Watanabé Tokunosuké
Published: July 2006

The phase transition of potassium thiocyanate has been investigated by the X-ray diffraction. It was confirmed that it is an order-disorder type transition with regard to the orientation of the thiocyanate ions. The temperature dependence of the ordering and the anomalous volume expansion near the transition temperature seem capable of being interpreted by the molecular field approximation if the volume dependence of the interaction energy is taken into account.
The Reduction of Aquopentamminechromium(III) Ions at the Dropping Mercury Electrode
Authors: Tanaka Nobuyuki , Sato Yuichi , Tamamushi Reita , Satô Gen
Published: July 2006

The reduction of aquopentamminechromium-(III) ions at the dropping mercury electrode has been studied in acid solutions by means of the measurement of the direct current, the alternating current and the Kalousek polarograms and the current-time curves. The d. c. polarogram gives a well-defined wave corresponding to the one-electron reduction of chromium (III) to chromium (II). All polarograms, including the Kalousek ones, indicate the irreversibility of the reduction of aquopentamminechromium(III) ions. The heterogeneous rate constants at 0 V. vs. SCE at various temperatures have been presented, and the possible mechanisms for the electrode process have been discussed.
An NMR Study of Acetaldehyde Methanol Solutions
Authors: Fujiwara Yuzuru , Fujiwara Shizuo
Published: July 2006

By the NMR method, the methanol solution of acetaldehyde was studied; in this solution all the species of hydrogen of each molecule are measurable, and a kinetic study of the system was readily performed. This could be compared with any other conventional methods, by which some of the species usually present in the system are directly measured. The formation rates of hemiacetal and acetal were measured as (8.5±1)×10−5 and (2.1±0.5)×10−5 l./mol./hr., respectively, in the absence of a catalyzer. The hydrogen exchange rates for three kinds of OH’s were also obtained. When compared with the related values in the literature, agreement is satisfactory. The relaxation times show a difference in the molecular motion corresponding to molecular structure and in the interaction with surrounding molecules.