bluuebunny/crossref_metadata_2025 huggingface dataset:
The Oxidation of Fe2+ by Ultrasound
Authors: Prakash Satya , Pandey Jata Dhari , Singh Rajendra
Published: July 2006

With the help of Milliard’s high frequency ultrasonic generator, type E-7562, with a barium titanate transducer with a frequency of 1 Mc, the oxidation of an acidic ferrous ammonium sulphate solution has been studied. The kinetics of the reaction, at six different concentrations of a ferrous ammonium sulphate solution and at four different ultrasonic intensities has been investigated. The reaction has been found to obey the first order kinetics. A probable mechanism based on the Haber-Weiss work has also been proposed.
Analysis of the Volatile Constituents of Hamanasu Absolute Oil
Authors: Nishimura Kiichi , Sakai Tsutomu , Ogawa Mieko , Hirose Yoshio
Published: July 2006

The separation of the carbonyl fraction and the non-alcoholic fraction, by the Girard T reagent and the phthalic anhydride respectively, from the principal constituent, phenylethyl alcohol, of Hamanasu flower absolute oil, and the successive analyses of each fraction have been carried out in order to elucidate the essential olfactory ingredient of the rose oil. The attempt resulted in adding some new components to those listed in the previous report: rose oxide, citronellyl acetate, geranyl acetate and methyleugenol.

The variety of the components has been proven to be essentially the same as in Bulgarian rose oil, although the proportion differs in some compoennts.
The Reduction of Indium(III) in Thiocyanate Solutions at the Dropping Mercury Electrode
Authors: Tanaka Nobuyuki , Takeuchi Takashi , Tamamushi Reita
Published: July 2006

The reduction process of indium(III) at the dropping mercury electrode in thiocyanate solutions has been investigated by direct current polarography, alternating current polaro-graphy and faradaic impedance measurements. The reduction current in the potential region between −0.5 to −0.9 V. vs. saturated calomel electrode is greatly increased by the addition of minute amounts of thiocyanate ions, when a remarkable minimum is observed on the diffusion current plateau at relatively negative potentials. On the alternating current polarogram, indium(III) in a potassium thiocyanate solution gives a negative admittance in the potential region where the minimum appears on the direct current polorogram. The analysis of impedance measurements has shown that the resistance component has a negative value in that potential region. The experimental results have been explained by assuming that the overall electrode process is composed of two simultaneous reactions, one of which proceeds at the naked electrode surface, and the other at the electrode surface covered with adsorbed thiocyanate ions, and by assuming that thiocyanate ions accelerate the reduction of indium (III) at the surface of the electrode.
The Velocity of Ascending Air Bubbles in Aqueous Solutions of a Surface Active Substance and the Life of the Bubble on the Same Solution
Authors: Okazaki Satiko
Published: July 2006

1) The velocity of an air bubble ascending in water is remarkably retarded by the addition of a minute amount of sodium dodecyl sulfate (SDS) or isoamyl alcohol. With an air bubble with a radius ranging from 0.03 to 0.07 cm., the decrease in velocity is perceptible even in a 10−6 molar SDS solution, while it tends to a limiting value in 10−3 and 10−4 molar SDS solutions, where the rising velocity is about half as large as that in pure water.

2) To elucidate this retardation, the static properties of the solution, such as surface tension, density and compressibility, and the dynamic properties, such as viscosity and the change in surface tension with time, have been measured. However, no difference could be found in these properties between pure water and a 10−5 molar SDS solution to account for the retardation phenomena.

3) The rising velocity of a bubble considered to be a rigid sphere calculated by using an empirical formula fails to explain the results, since the formula does not fit our experimental conditions. The rising velocity of a rigid spherical bubble calculated from the observed data of a falling velocity of glass spheres in water in our apparatus is found to be in good agreement with that in 10−3 and 10−4 molar SDS solutions.

4) It has been concluded that, in all concentrations of the solution studied and for the bubble with a radius less than 0.07 cm., the bubble rises as a sphere and that the air circulation inside the bubble is closely related to the rising velocity of the bubble. The air circulation, which is strongest in the rising bubble in pure water, is hindered in 10−5 and 10−6 molar SDS solutions by the formation of an adsorbed film of SDS on this bubble, and the rising velocity is also thereby retarded. The circulation is actually suppressed, and the bubble rises as a rigid sphere in 10−3 and 10−4molar SDS solutions. The retardation of the rising velocity of bubbles with radii larger than 0.07 cm. is due to the deformation of the bubbles from a sphere.

5) The life time of bubbles on an aqueous, solution is affected by the surface active substance as sensitively as in the case of the effect of the same substance on the velocity of the rising bubble. Both phenomena are explained by the common factor of the retardatoin of the flow around the bubble surface.
The Thermal Membrane Potential as a Function of the Apparent Ionic Transport Number of Membranes
Authors: Ikeda Toshio , Tsuchiya Masao , Nakano Masaru
Published: July 2006

The thermal membrane potential (TMP) has been studied as a function of the apparent ionic transport number of ionselective membranes. The temperature coefficient of TMP, the thermoelectric power, has been found to be a continuously increasing function of the apparent ionic transport number of the membranes used, starting from zero at the neutral point, where the membrane exhibits no selectivity for ions, and approaching with acceleration when the ionic transport number of the membrane is increased until it reaches its highest limit at the perfect ion permselectivity. The sign of the thermoelectric power has been found to be positive for negative membranes, and negative for positive membranes. The absolute value of the thermoelectric power is higher for positive membranes than for negative membranes at equivalent degrees of ion permselectivity.
Ammonia-Synthesis Iron Catalysts Containing Magnesia as Their Principal Promoter. II. The Texture and Structure of the Catalysts
Authors: Uchida Hiroshi , Terao Iwao , Ogawa Kiyoshi , Oba Masaaki
Published: July 2006

This paper has presented data on such textures as the specific surface area, the pore volume, the average diameter of particles and pores, the fraction of the surface occupied by free iron and so forth, and on such structures as the lattice constant in the oxidic state and the crystallite width after the synthesis run of individual catalysts of the magnesia-promoted type, together with data on both a pure magnetite and a catalyst of the alumina-promoted type. It has also included the results of the examination of the catalysts by means of optical and electron microscopy.

Although the magnesia used as a promoter may be surface-inactive at the earlier stage of reduction, it tends at the later stage to cover the major portion of the particle surface and acts to retard the particle growth as well as the crystallite growth. The retarding effect on the growth is cancelled out when potash is added as the second promoter, but it is considerably pronounced in the presence of silica. Apart from the catalyst doubly promoted by magenesia and potash, the particle size of the promoted catalysts ranges from 700 to 2600 Å, but the crystallite widths lie in a far narrower range, between 250 to 390 Å. The specific activity per unit of the surface area is not always higher for the catalysts of the smaller particle sizes.

The lattice constant of a pure magnetite is not changed by the addition of magnesia, indicating that the Mg2+ ions occupy the empty interstices is the magnetite lattice.

The microscopic and electron-microscopic structeres of the polished and etched surfaces of oxide catalysts of the magnesia-promoted type are very different from those of the alumina-promoted type. In view of the change in the mocroscopic structure of the surface with the reduction progress, an explanation in terms of the different reduction rates between the two types of catalysts is probable.

On the basis of the fact that the subparticles of the catalyst after the synthesis run still retain the original shape of the corresponding oxide catalyst, either plate-shaped or massive, the electron-microscopic as well as the microscopic observation of the polished and etched surface of the oxide catalyst can afford a means for predicting the promoter-composition which will produce a highly active catalyst.
The Structure of Glassy Carbon
Authors: Noda Tokiti , Inagaki Michio
Published: July 2006

The structure of glassy carbon has been investigated by determining the interlayer spacing, crystallite size and disorganized carbon content, and by an analysis of the radial distribution function.

Glassy carbon has been found to be a typical non-graphitizing carbon. From the analysis of the first peak of the radial distribution curve, it has been assumed that not only trigonal but also tetrahedral carbon atoms exist in glassy carbon. A structural model of glassy carbon has been proposed; in this model tetrahedral carbon atoms form the main part of the criss-cross linkages which link graphite-like layers in a random way.
Semiconductivity of Phenanthrene Single Crystals
Authors: Matsumoto Shoichi , Tsukada Tomomichi
Published: July 2006

Phenanthrene single crystals have been grown by means of a modified Bridgeman method. The electrical conductivity has been measured for two crystallographic directions, ⊥ ab and // ab.

The electrical resistivity is not affected appreciably by ambient oxygen. The temperature dependence of electrical resistivity can be described as ρ=ρoexp(Δε⁄2kT), where the activation energy (Δε) is 1.14 eV. for ⊥ ab and 1.15 eV. for // ab; the two values agree well. A large anisotropy has been found in the resistivity at 15°C. The resistivity is 4.8×1015Ω cm. and 1.9×1014Ω cm. for ⊥ ab and // ab respectively.

It has been concluded that, although phenanthrene is an isomer of anthracene, the electrical properties of phenanthrene differ considerably from those of anthracene.
A Study of the Hydration of Calcium Orthoplumbate. III. The Behavior of Dehydration
Authors: Koishi Masumi
Published: July 2006

The behavior of the dehydration of a hydrate mixture of calcium orthoplumbate and calcium hydroxide and of the hydrate of calcium orthoplumbate has been studied with a thermobalance and by differential thermal analysis.

It has been shown that the dehydration of crystalline water in the hydrate mixture was retarded by the presence of the calcium hydroxide liberated; this conclusion has been based on both the activation energy of the hydrate and its loss of weight.

It seems that calcium orthoplumbate fills the space in a network consisting of calcium hydroxide particles.
A Semi-empirical MO Theory of σ Electron Systems. I. General Theory
Authors: Hamano Hidekazu
Published: July 2006

A semi-empirical MO theory is proposed for complex saturated molecules. In a first-order treatment, each MO is represented as a localized function that contains only the AO connected with one bond or atom. This enables us to define a set of bonding, anti-bonding and lone-pair orbitals. The molecular wave function is obtained as an anti-symmetrized product of the bonding and lone-pair orbitals. In this approximate theory we discuss the definitions of the electronegativity scale and of the inductive effect; the electronegativity scales proposed by Moffitt and Mulliken are obtained as special cases. In a subsequent, more accurate second-order theory each MO is represented as a linear combination of all bonding, anti-bonding and lone-pair orbitals; this treatment is made by means of the perturbation theory. A semi-empirical approach is developed by taking the interactions between different bonds as empirical parameters. No applications of the general theory are presented here; they will be discussed in subsequent papers.
Proton Magnetic Resonance Spectra of Polypropylene in Solution
Authors: Kato Yoshinori , Nishioka Atsuo
Published: July 2006

The application of the NMR method to the study of commercial polypropylene seems to be restricted by some difficulties. A weak thermal degradation technique has therefore been employed to reduce the molecular weight of the polypropylene sample. However, the correspondence between the resultant molecular weight and the resolution of the spectrum is not always unique.

A remarkable difference between the NMR spectrum of isotactic polypropylene and that of atactic polypropylene can be found in the methylene resonance region. As an approximation, one may assume that the methylene groups of isotactic polypropylene give rise to the partial spectrum of an ABC2 spin system, whereas those of syndiotactic polypropylene give rise to the partial spectrum of an A2B2 spin system. By means of an electronic computer, the best set of the δ and J parameters for the methylene resonance of isotactic polypropylene has been obtained. The results fit the observed spectrum fairly well. Using this information, the degree of stereoregularity (isotaxy) of a given polypropylene can be calculated. This method is applicable if an well-resolved NMR spectrum is available.
Theoretical Studies of Light Scattering by Polydispersed Colloidal Systems of Spherical Particles
Authors: Nakagaki Masayuki , Shimoyama Tsugiyo
Published: July 2006

In order to study the light scattering of polydispersed colloidal systems of spherical particles, a weight distribution function, W(α), of the relative particle radius α has been assumed to be a modified Gaussian function with three parameters: the most probable α-value, αm; the width of the distribution, 〈Δα〉, and the dissymmetry of the distribution, Δ. The values of Yθ, which is proportional to the specific scattering intensity, for θ=45°, 90° and 135°, and the dissymmetry factor, z=Y45⁄Y135 have then been computed.

In principle, it should be possible to determine three parameters of the particle size distribution, αm, 〈Δα〉 and Δ, from the observed values of three independent quantities, Y45, Y90 and Y135. It has, however, been concluded that practically the method requires very precise experiments. If one is satisfied with a distribution function of two parameters, αm and 〈Δα〉, the values of these parameters can be determined from the experimentally-obtained Y90 and z values on the basis of a chart constructed theoretically.

The value of αw, which is the cubic root of weight-averaged 〈α3〉, is equal to the α value obtained from the measured specific scattering intensity by assuming that the system is monodispersed when α is small. If α is not small, the value of αw can be obtained according to the empirical equation:

αw⁄α90=1+k(z⁄z90−1)

The error will be within about 5% if αw<1.5.
The Mechanism of the Formation of Terephthalic Acid from Benzonitrile
Authors: Ogata Yoshiro , Furuya Yoshiaki , Noshiro Tadashi , Go Tadahiro
Published: July 2006

A mixture of benzonitrile, cadmium iodide and potassium carbonate has given, when heated in a sealed tube at 360∼500°C, terephthalic acid (21∼33%), together with a considerable amount of isophthalic acid. The reaction was possible without a cadmium catalyst, but the yield of terephthalic acid was poorer (8.0%). The tracer study with K214CO3, as well as the identification of cyanate in the products, showed that the reaction proceeds by way of the conversion of benzonitrile to potassium benzoate and potassium cyanate, followed by the disproportionation of potassium benzoate to potassium terephthalate and isophthalate. Potassium cyanate seems to be a weak catalyst for the disproportionation.
The Gamma Ray-Induced Addition of Acetaldehyde to Cyclohexene and Normal Hexene
Authors: Hatada Motoyoshi , Takezaki Jun’ichi , Hirota Kozo
Published: July 2006

By the radiation-induced telomerization of acetaldehyde-hexene mixtures, McHK has been produced when cyclohexene is used, while MnHK and MiHK have been produced when normal hexene is used. The G(MnHK) at room temperature has been found to be 400 (dose rate=9.7×104r/hr.), which is larger by a factor of ten than the G(MiHK) and the G(McHK). Irrespective of the dose rate, a G(MnHK)>G(McHK)>G(MiHK) relation always exists.

It has been found that: (i) the G(MnHK) value, as well as the G(MiHK) and the G(McHK) values, increases with the rise in temperature, they all show however, maxima at 70∼80°C, because of the thermal decomposition of the acetyl radical, (ii) sharp maxima are shown in the curves of G(telomer) vs. initial composition at 5 mol.% of hexenes, (iii) the analytical data of the gaseous products establish that the radiation-induced decomposition of aldehyde and hexene occurs in parallel with the telomerization, and (iv), upon the addition of benzene or cyclohexane to the system, the G(telomer)’s decrease slightly in both systems, suggesting that they act as diluents rather than as agents of the energy transfer.
Studies of the Hydration and the Structure of Water and Their Roles in Protein Structure. II. The Hydration of Electrolytes by Ultrasonic Interferometry and Its Temperature Dependence
Authors: Isemura Toshizo , Goto Sachio
Published: July 2006

The numbers of hydration of various 1-1 and 1-2 electrolytes in aqueous solutions and their dependence on the temperature have been determined by the method of ultrasonic interferometry. The relation between the hydration and the compressibility of aqueous electrolyte solutions has been discussed and further evidence obtained for the existence of the clathrates as hydration shells, as was suggested in the previous paper.
The Preparation of Phosphorus-32 in a High Specific Activity Using the Szilard-Chalmers Effect
Authors: Tanaka Kichizo
Published: July 2006

A process has been developed for obtaining phosphorus-32 free from phosphorus-33 and with a high specific activity. Phosphorus-32 has been prepared by an anion exchange method, in which a chloride solution containing 0.025m of potassium chloride and 0.025m of hydrochloric acid of neutron irradiated phosphate was passed through the column of a strongly basic anion exchanger, and the adsorbed phosphorus-32 has been eluted with 8m hydrochloric acid. The anhydrous orthophosphate shows a good recovery compared with several orthophosphates, sodium orthophosphite and sodium hypophosphite. The recovery is not much affected by the irradiation time. Enrichment factors higher than 103 have been obtained.
Thermoanalytical Studies of the Thermal Stability of High Polymers. II. The Differential Thermal Analysis and Thermogravimetric Analysis of Some Polyethylenes
Authors: Igarashi Shoichi , Kambe Hirotaro
Published: July 2006

The thermal stability of polyethylenes has been studied by differential thermal analysis and by thermogravimetric analysis in air and in a nitrogen atmosphere.

The crystallinities of some polyethylenes have been evaluated from the data of differential thermal analysis. These values are smaller than the reported value. This discrepancy may be due to differences in the methods.

In the differential thermal analysis curve for low-pressure polyethylene Hizex 5000 in air, two small exothermic peaks due to oxidation were observed at about 200 and at about 390°C. The endothermic peaks at 135 and at 457°C correspond to the melting and to the thermal decomposition points of polyethylene.

In thermogravimetric analysis in a nitrogen atmosphere, the thermal decomposition of lowpressure polyethylene takes place over the range from 380 to about 450°C, and that of high-pressure polyethylene, from 360 to about 450°C. In the presence of air, the oxidative degradation of low-pressure and high-pressure polyethylenes occurs in three stages: the first from about 200 to 350°C, the second from about 350 to 390°C, and the third from about 390 to 455°C.

It has been concluded that the thermal stability of high-pressure polyethylene is smaller than that of low-pressure polyethylene. This may be attributed to the difference in branching of commercial polyethylenes.
A Possibility for Determining the Entropies of Electrolytes from the Initial Thermoelectric Powers of Thermocells
Authors: Ikeda Toshio
Published: July 2006

An alternative method for determining the third-law partial molar entropies of electrolytes in aqueous solutions from the data on nonisothermal systems has been presented. They can be obtained from the difference between the initial thermoelectric powers of two different thermocells, the one being formed by cation-reversible electrodes and the other being formed by anion-reversible electrodes, both with common electrolytes of the same concentration. The partial molar entropies have been calculated to be 31.59, 37.53 and 42.87 e.u. for hydrochloric acid, hydrobromic acid, and hydroiodic acid respectively at 25°C and 0.01 m.
Some Properties of Polyoxyethylene Dodecyl Ether over a Wide Range of Polyoxyethylene Chain-lengths
Authors: Tokiwa Fumikatsu
Published: July 2006

The fundamental properties of polyoxyethylene dodecyl ether (PODE) with different polyoxyethylene chain-lengths (p) have been studied over a wide range of p values. The molecular weights of the PODE, purified by the extraction method using water-saturated n-butanol and n-butanol-saturated water, have been determined by both the freezing point depressions of benzene solutions and the hydroxyl values of PODE; the molecular weights as determined by the different methods are in nearly complete agreement with each other. The Rf-values of the original samples containing small amounts of PEG are slightly lower than those of the purified samples, and the PEG contained in original samples show an almost constant Rf-value, irrespective of the p value.

The infrared spectra of purified PODE have been compared with those of the original ones. The spectra of the purified PODE with p-values smaller than about 16 exhibited a carbonyl absorption at 1725 cm−1. However, the reason for this could be established only partially. The effect of the carbonyl group found in the above PODE on the surface tension of aqueous solutions was not observed distinctly.

The solubilization behavior of PODE differs somewhat from the behavior of ordinary ionic surfactants, and some solubilization can take place in the region of the surfactant concentration which is lower than the CMC. There appears to be a simple relationship between the CMC values, obtained from solubilization vs. concentration curves, and the p values of PODE over a wide range of p values.
The Direct lodination of Polyalkylbenzenes by the Crossed Jacobsen Reaction
Authors: Suzuki Hitomi , Sugiyama Takashi , Goto Ryozo
Published: July 2006

A method has been developed for the direct iodination of certain polyalkylbenzenes by the transfer of an iodine atom of iodoanisole. It consists of the simultaneous addition of iodoanisole and sulfuric acid to the polyalkylbenzene to which the transfer is to be made. In this way, iodo compounds have been prepared from eight polyalkylbenzenes.
The Steric Requirements and the Nature of the Intramolecular Hydrogen Bonding of o-Methoxybenzoic Acid
Authors: \={O}ki Michinori , Hirota Minoru
Published: July 2006

The infrared and ultraviolet absorption spectra of derivatives of salicylic acid with alkyl sub-stituents at the 2-O-, 3- and/or 6-positions have been measured, and much information on the nature of the intramolecular hydrogen bonding has been obtained from these data. The infrared O-H stretching absorption measurement shows that a substituent at the 6-position inhibits the formation of hydrogen bonding and that a substituent at the 3-position has some unfavorable steric effects.

These data imply the importance of the coplanarity of the carboxyl group with the benzene nucleus; moreover, a consideration of these data, together with the infrared C=O streching and ultraviolet spectral data, leads to the conclusion that the structure of the hydrogen-bonded trans isomer Ia may be expresed as a resonance hybrid among XXIV, XXV, XXVI and XXVII, the contribution of XXIV being the most important and that of XXV the next most important.
Infrared Spectroscopic Studies of Hexammine- and Pentammine-chromium(III) Complexes
Authors: Tanaka Nobuyuki , Kamada Minoru , Fujita Junnosuke , Kyuno Eishin
Published: July 2006

Twenty-nine samples of hexammine and pentammine complexes of chromium (III) and cobalt (III) have been prepared, and their infrared spectra have been measured in the region of 2∼25μ. The absorption peaks of these complexes have been found to shift to higher frequencies in the N-H stretching vibrations, and to lower frequencies in the N-H deformation and the Cr-N stretching vibrations in the order of the chlorides, the bromides and the iodides. In a potassium bromide prism region, three absorption bands due to the Cr-N stretching vibrations have been observed in hexammine- and halopentamminechromium(III) halides, but only one in the aquopentamminechromium(III) complexes. The shifts of the absorption bands observed have been discussed from the standpoint of the hydrogen bond formation.
The Cationic Copolymerization of Styrene and Isobutene in Liquid Sulfur Dioxide
Authors: Iino Masashi , Tokura Niichiro
Published: July 2006

The copolymerizations of styrene and iso-butene in liquid sulfur dioxide and in mixtures of liquid sulfur dioxide with nitromethane, ethylene dichloride, nitrobenzene and benzene have been carried out at −78°C. The r1 and r2 values have been estimated by the intersection method. When M1 stands for styrene and M2 for isobutene, r1 and r2 are 1.1 and 3.1 in liquid sulfur dioxide. The r2 values vary, as the added solvent is changed. Two sets of r1 values, approximately unity and 0.5, have been found. The meager solubility of polyisobutene and isobutene sequence in the copolymer may be responsible for the findings.
Analytical Studies Using the Convection Electrode. VII. The Use of the Pushed-out Mercury-drop Electrode
Authors: Suzuki Junsuke , Ozaki Tokuro
Published: July 2006

The limiting currents with the PMDCE depend on the factors of both convection and diffusion. The PMDCE is easy to prepare and to manipulate, and it has an excellent sensitivity. It can be used even in a strongly alkaline or acidic medium and can be reused many times with good reproducibility. Therefore, various applications to analytical chemistry can be expected.
The Thermal and Radiation Oxidation of Benzene to Phenol in Aqueous Solutions Containing Metal Ions at Elevated Temperatures. IV. The Effect of Impurities in Benzene
Authors: Suzuki Nobutake , Hotta Hiroshi
Published: July 2006

The yield of phenol from the oxidation of unpurified benzene catalyzed by metal ions in an aqueous solution is much larger than from that of purified benzene. Phenol is produced in a good yield at temperatures lower than 160°C only in an oxygenated solution, in which OH radicals are produced, either with or without irradiation. Therefore, the autoxidation of impurities in benzene, initiated by OH radicals, is the initiation reaction of the chain oxidation process. On the other hand, phenol is also produce above 180°C even when OH radicals are not produced. Therefore, it is considered that the hydroperoxides of impurities are formed at higher temperatures without the OH radical by means of their autoxidation. Moreover, the yield of phenol in a cupric sulfate solution decreases remarkably with an increase in the sulfate concentration.
The Formation of Methyl Methanethiolsulfonate, an Antibacterial Substance, from Dimethylsulfoxide
Authors: Tsuchiya Tsutomu , Iriyama Setsuko , Umezawa Sumio
Published: July 2006

1) Methyl methanethiolsulfonate has been obtained from the reaction product of dimethyl sulfoxide with hydrogen chloride. Methyl methanethiolsulfonate has been found to have antifungal and antibacterial activities.

2) It has been suggested that methanesulfenyl chloride is formed from the diacid salt of DMSO and that it reacts with methanesulfinic acid to yield methyl methanethiolsulfonate.
Tensammetric Waves in Oscillographic Square-wave Polarography
Authors: Okamoto Koichi
Published: July 2006

The possibility of observing the tensammetric waves of surface-active agents by an oscillographic square wave polarograph has been investigated. Well-defined tensammetric waves of some aliphatic alcohols, as well as those of some synthetic surface-active agents, can be obtained both in the cathodic and anodic sweep processes. The summit potential values, measured by the oscillographic method and pen-recording method, are almost identical. The relations of the concentrations and temperature to the summit potentials obtained by the two methods are almost equivalent, also. However, the summit current observed by the oscillographic method is higher than that obtained by the pen-recording method, and also the relation of logC to is is not equivalent.

In order to measure the CMC of surfaceactive agents, the author had made use of the fact that, at the CMC of the agents, the form of the reduction or the oxidation wave of a metallic ion added to the solution of the agent changes remarkably. This method is thought to be superior to the conventional d. c. polarographic method, for the reduction and also the oxidation waves of a metallic ion can be observed, and the response to the change in the reversibility of the electrode reaction is much faster than with the d. c. method.
Stereochemical Studies of Monoterpene Compounds. I. The Conformation of (+)-p-Menthane-3,4-diol Obtained by the Performic Acid Oxidation of (+)-p-Menth-3-ene
Authors: Suga Takayuki , Shishibori Tsuyoshi , Matsuura Tamon
Published: July 2006

The conformational analysis of (+)-p-menthane-3,4-diol, which had been obtained by the hydroxylation of (+)-p-menth-3-ene with performic acid in the presence of water, has been performed mainly by means of infrared spectra. It has been shown that the two hydroxyl groups at the C3- and C4-positions take a diaxial conformation, that they are, accordingly, trans to each other, and that the methyl group presumably holds an equatorial orientation. It has also been found that p-menthane-trans (diaxial)-2,3-diol results from the p-menth-2-ene coexisting in the sample of p-menth-3-ene. A stereochemical course of the hydroxylation reaction has been discussed.
The Reaction of Carbon Monoxide with Organometallic Compounds.
Authors: Ryang Membo , Rhee Ilsong , Tsutsumi Shigeru
Published: July 2006

The reaction of iron pentacarbonyl with aryllithiums at −50∼60°C has yielded the corresponding aromatic aldehydes in good yields. 2,6-Dimethylbenzaldehyde (36.4%), 2,4-dimethylbenzaldehyde (65.4%), p-t-butylbenzaldehyde (47.0%), o-t-butylbenzaldehyde (54.3%), p-methoxybenzaldehyde (24.2%) and 2,4,6-trimethylbenzaldehyde (60.5%) have been prepared by this method.
The Normal Vibrations of Diketopiperazine and Its N-Deuterated Compound
Authors: Fukushima Kunio , Ideguchi Yoshiko , Miyazawa Tatsuo
Published: July 2006

The normal vibrations of diketopiperazine and its N-deuterated compound have been calculated, with the metylene groups treated as mass points. An assignment of the infrared absorption bands has been made on the basis of the calculated frequencies and potential energy distributions, and the nature of the characteristic vibrations of the cis-amide group has been discussed.
The Formation of Sulfur Compounds in the Radiolysis of a Toluene Solution of Sulfur
Authors: Ando Wataru , Sugimoto Ken’ichi , Oae Shigeru
Published: July 2006

The radiolysis of a toluene solution of sulfur has been investigated. The formations of benzyl mercaptan, hydrogen, and hydrogen sulfide have been observed, and their amounts determined under various considerations. The amounts of mercaptan formed increase linearly with the concentration of sulfur, and the reactions seem to proceed through the initial decomposition of toluene to form the benzyl radical, which then opens the S8 ring molecule to form the mercaptan. The G-value of hydrogen formation is considerably larger than that of hydrogen sulfide. Similar studies were made of the systems of toluene - cyclohexane - sulfur and of toluene - carbon disulflde - surfur in order to clarify the nature of the radiolysis of toluene and sulfur.
Decomposition and Energy Transfer in the Radiolysis of Sulfur Compounds in Toluene
Authors: Ando Wataru , Sugimoto Ken’ichi , Oae Shigeru
Published: July 2006

The decomposition yields of organosulfur compounds in toluene have been studied using DPPH as a radical scavenger. The effect of the concentration of sulfur compound is quite marked, and the irradiation energy absorbed in the solution of toluene seemed to be transferred to the sulfur compound. The largest energy transfer from toluene has been observed in the decompostion of benzyl mercaptan, while the disulfide has been shown to absorb the energy from the excited toluene less than half as effectively as does the mercaptan. As compared to the mercaptan or the disulfide, benzyl sulfide is far less effective in energy absorption.
The Radiation-induced Reaction of Benzyl Mercaptan and p-Tolyl Mercaptan in Various Organic Solvents
Authors: Ando Wataru , Sugimoto Ken’ichi , Oae Shigeru
Published: July 2006

The decomposition of benzyl mercaptan and p-tolyl mercaptan in various organic solvents has been studied, and the following conclusions have been obtained. 1) A radiation-sensitive solvent such as hexane is readily attacked by the benzyl mercapto radical. 2) When the resulting mercapto radicals are stabilized substantially by resonance, solvent radicals from the radiolysis of solvents will abstract hydrogen from the mercaptan. 3) The G-values of mercaptan decomposition in such solvents as hexane, cyclohexane, acetone, methanol and dioxane are relatively higher than those in carbon disulfide, benzene, toluene and nitrobenzene. The reaction presumably proceeds through the energy transfer process from solvent to mercaptan. When an aromatic π-electron system is present in any solvent, the radiation energy absorbed will be dissipated quite readily through electronic excitation to lower-energy levels of the solvent molecule.
The Preparation of Dimer Aldehydes and Dimer Alcohols in an Oxo Reactor. II. The Initial Rate of the Hydroformylation of Propylene in the Presence of Magnesium Methylate as a Modifier
Authors: Uchida Hiroshi , Matsuda Akio
Published: July 2006

The effect of magnesium methylate addition upon the initial rate of propylene hydroformylation has been explained in terms of Arrhenius plots of the initial rate constants, and in terms of the activation energy as a function of Mg/Co. Moreover, the plot of the logarithm of the frequency factor vs. the activation energy appears to be linear, which indicates that a compensation takes place with respect to the initial rate in the presence of magnesium methylate. The extension of Cremer’s view about the compensation effect in heterogeneous catalysis into this kind of liquid-phase reaction leads one to expect another catalyst besides that of cobalt carbonyl.

The determination of the cobalt carbonyl anion in the reaction product obtained from raw material either with no or with a large excess of magnesium methylate (Mg/Co=3) indicates that in the former product scarcely no cobalt is detectable as the carbonyl anion, whereas in the latter product a part of the cobalt exists as such. The anion is to be ascribed to that of a mixed metal carbonyl of [Co(CO)4]2 Mg, which facilitates the production of dimer aldehydes. Further, the infrared spectrum of the latter product differs markedly from that of the former product. This may afford evidence for the other catalyst expected.
Adsorption of Congo Red and Fuchsine Base by Hydrous Beryllium Oxide Aged for Different Periods
Authors: Dutta Rup
Published: July 2006

Three samples of hydrous beryllium oxide, of different character, were prepared by adding different quantities of an alkali to a fixed volume of beryllium sulfate solution for precipitation. These samples were allowed to age progressively and there adsorptive capacities for dye-stuffs were studied. It has been found that the adsorptive capacity of the samples decreases with aging of the hydroxide and the adsorption data dye-stuffs reveal that the three samples possess different adsorptive capacities.
Kinetic and Spectrophotometric Studies of the Homogeneous Catalytic Activity of Iron(III) Complexes upon the Decomposition of Hydrogen Peroxide in Aqueous Solution
Authors: Wada Goro , Nakamura Tadayoshi , Terauchi Kunio , Nakai Toru
Published: July 2006

Hydrogen peroxide is catalytically decomposed by the Fe3+ ion, the activity of which is remarkably affected by the kind and the number of ligands coordinated to it. In this paper, the effects of ligands have been kinetically and spectrophotometrically determined and discussed from the view-point of the ligand field theory.

(1) The reaction generally proceeds linearly with time after a certain induction period, and the rate depends upon the pH of the solution.

(2) The reaction rate varies with the kind of the ligand and with its concentration. When [L]/[Fe3+] is equal to unity, the rate decreases in the order: en>dien∼(H2O)∼ea>trien>tetraen∼dip∼phen.

(3) The apparent activation energy of the reaction exhibits a maximum, except in the cases of trien and phen, at the concentration ratio [L]/[Fe3+]=1, and the values of the activation energy at this concentration ratio are in the order: dien∼trien>tetraen>en>ea>(H2O)>phen.

(4) The true activation energy of the reaction catalyzed by the pure iron-complex is calculated from the observation of the stability constants to be in the order: dien>trien>en>(H2O)>ea, which completely coincides with the order of the activation entropy.

(5) The visible and ultraviolet absorption spectra of Fe-phen32+ and Fe-phen33+ as catalysts in the working state were observed, and it was found that there takes place a redox cycle, Fe3+\ightleftarrowsFe2+, during the reaction and that phen molecules are gradually decomposed at the same time.

(6) In the course of the reaction, the peaks of the ultraviolet absorption of Fe-phen32+ and Fe-phen33+ bring about a slight red shift, which is caused by the coordination of HO2 to the iron ion.

(7) Judging from a comparison between the activation energy of the reaction and the spectrochemical series of ligands and from the calculation of the stabilization energy due to the ligand field theory, the reaction proceeds through an SN1 mechanism under the iron (III) oxidation state in the case of strong field complexes and through an SN2 mechanism under the iron (II) state in the case of weak field complexes.

(8) The reaction is retarded and the activation energy is raised by the addition of the CN− ion, which strongly coordinates with iron and forms a very strong field complex.
Studies on Amino-hexoses. VII The N-Deacetylation of Methyl N-Acetyl α-d-Glucosaminide
Authors: Fujinaga Mamoru , Matsushima Yoshio
Published: July 2006

Methyl N-acetyl-α-d-glucosaminide has been found to be well N-deacetylated by hydrazine treatment. The methyl α-d-glucosaminide thus produced shows so much stability with regarded to hydrazine and to barium hydroxide that these reagents provide a convenient means of preparing anomerically-pure methyl d-glucosaminide and its hydrochloride. The free base of methyl α-d-glucosaminide has been obtained crystalline for the first time.
Sesquiterpene Constituents of the Essential Oil of Hinoki (Chamaecyparis Obtusa (Sieb. et Zucc.) Endl.)
Authors: Hayashi Schûichi , Yano Katsumi , Matsuura Tamon
Published: July 2006

d-Longifolene and calamenene have been newly identified from the essential oil of Hinoki. Cadinene and cadinol, which had been formerly reported, have been confirmed to be d-γ-cadinene and l-α-cadinol respectively.
Stability Constants of Palladium, Copper, Nickel, Zinc and Manganese Complexes of 3-Hydroxy-3-phenyl-1-p-chlorophenyltriazene
Authors: Purohit D N , Sogani N C
Published: July 2006

Stabilities of palladium, copper, nickel, zinc, and manganese chelates of 3-hydroxy-3-phenyl-1-p-chlorophenyltriazene have been determined in 70% v/v dioxan-water mixturre by employing Bjerrum-Calvin pH titration technique. The titration medium was maintained at a constant ionic strength (0.1 m, potassium chloride) and at a temperature, 25±0.5°C. Log K, palladium 20.95, copper 20.65, nickel 14.58, zinc 13.53, and manganese 10.50.
Electron Paramagnetic Resonance Studies of Titanium(III) Ions with Complexing Compounds
Authors: Fujiwara Shizuo , Codell Maurice
Published: July 2006

The EPR spectra of a number of titanium(III) complex compounds have been obtained at room temperature and in aqueous solutions ; these compounds show either a hyperfine structure alone or a mixture of hyperfine and simple structures. The g values for the various complexes have been determined and compared. This technique should provide a simple method for studying the state in solution of the complexes of several other metals and their isotopes.
Flash Photolysis of Methylene Blue. I. Reversible Photolysis in the Absence of a Reducing Agent and in the Presence of Certain Kinds of Reducing Agents
Authors: Matsumoto Shiro
Published: July 2006

Transient spectra which appear in the flash photolysis of methylene blue in aqueous solvents of various pH values have been surveyed both in the absence and in the presence of a reductant. In the absence of a reductant, the triplet state of the dye has been observed to appear in two forms, with different degrees of protonation. The form found in neutral water seems to be formed directly from the excited singlet state of the dye. The pKA value of the acid-base equilibrium has been found to be approximately 6.8. A second transient has been found to be produced in water and in buffer solutions of a moderate pH value at a later stage of the photolysis. Its formation is more marked in buffer solutions, and it may be supposed to be a sort of charge-transfer complex between an excited dye ion and another dye component. The photolysis in the presence of ferrous ions, p-phenylenediamine or benzohydroquinone is nearly reversible, and the absorption of the original dye is restored after the illumination except in an extremely alkaline solution. The transitory formation of leuco methylene blue has been observed when ferrous sulfate or hydroquinone was used as the reductant below a pH value of 8.4, while that was not the case with p-phenylenediamine. The formation of leuco methylene blue from semiquinone has been found to be a bimolecular dismutation process in an acid medium when ferrous ions are the reductant, but when hydroquinone is used as the reductant at moderate pH values, it also reduces the methylene blue semiquinone. When hydroquinone is used as the reductant in a neutral or alkaline solvent, an increase in absorption is often observed at some longer wavelengths; this has tentatively been attributed to a complex between excited dye ions and reductant molecules. A comparison of the transient spectra obtained in various conditions has shown that the semiquinone of methylene blue exists in variously protonated forms in the following ranges: pH>9, pH=3∼8, in 0.1∼1 n sulfuric acid, and in very concentrated sulfuric acid. The pH dependence of the quantum yield of the photoreduction obtained earlier has been tentatively related to the change in the degree of protonation of the triplet state and the semiquinone.
Flash Photolysis of Methylene Blue. II. Photolysis in an Aqueous Solvent in the Presence of N-Phenylglycines and Photolysis in Organic Solvents
Authors: Matsumoto Shiro
Published: July 2006

The flash photolysis of methylene blue in an aqueous medium with added N-phenylglycines or photolysis in organic solvents results in a more or less apparent bleaching of the dye. In the former case, the general features of the transient spectra are similar to those in the reversible photolysis treated in Part I. An absorption peak at 400 mμ in a solvent with a pH of 8.0 shifts to 430 mμ in a solvent with a pH of 8.8 ; it is to be attributed to the semiquinone of methylene blue. The absorption around 255 mμ increases at a later stage of the reaction, indicating the formation of leuco methylene blue. The photolysis seems to proceed in a way similar to that of the reversible cases. The results of flash photolysis with several derivatives of N-phenylglycine support the general idea of their reactivity obtained in a study with continuous illumination. There is a difference between the ways in which N-p-bromophenylglycine and N-p-methoxyphenylglycine retard the photoreduction, although this may be superficial. In the former case, some early intermediate (probably the triplet state of the dye) is deactivated almost catalyticaly, while in the latter case the deactivation takes place at the stage of a long-lived semiquinone-like intermediate. Peculiar features of photolysis with α-methyl-N-phenylalanine and N-phenyl-β-alanine have also been noted.

The degree of irreversible bleaching in an organic solvent has no regular relation to the ease with which the solvent molecule is dehydrogenated by an ordinary oxidant. The main part of the transient absorption in organic solvents is attributed to the semiquinone of the dye. The peak has somewhat red-shifted compared with that in water. Triplet absorption seems also to appear at an early stage of photolysis. The photolysis in 1- or 2-propanol reveals the reversible feature observed when ferrous ions were used as reductants.
A Convenient Method for the Monobromination of Active Methylene Compounds
Authors: Hata Tsujiaki
Published: July 2006

The monobromination of the active methylene compounds by means of the proportionation procedure between the active methylene compound and its dibromo-derivative has been investigated.

Next, the monobromination of various active methylene compounds by the use of dibromomalonitrile has been tried. The method proved remarkably effective for the synthesis of α-mono-bromoderivatives of active methylene compounds containing a phenyl group.
The Absorption Spectra of Chromium(II) Acetate and Copper(II) Acetate
Authors: Kida Sigeo , Nakashima Yoshiaki , Morimoto Yukiyoshi , Niimi Kiyoshi , Yamada Shoichiro
Published: July 2006

The electronic absorption spectra of chromium(II) acetate have been determined in ethanol and Nujol mull in the region between 10 and 40 kK. Dichroism in that region has also been determined with a single crystal of the compound. A new absorption band, which has not previously been observed, has been found at about 30.77 kK. (logε 2.22), in addition to a band at about 20.58 kK.

The origins of these bands have been discussed in relation to the absorption bands of copper (II) acetate.
The Ultrasonic Velocity and Absorption of Aqueous Solutions of Polyvinyl Alcohol
Authors: Arakawa Kiyoshi , Takenaka Nobuo , Watase Mineo , Kubota Kazunari
Published: July 2006

An ultrasonic pulse technique has been applied to measure the velocity and absorption of the longitudinal sound wave in aqueous solutions of polyvinyl alcohol at ultrasonic frequencies. Two samples of polyvinyl alcohol have been used: sample A, completely saponified polyvinyl alcohol, and, sample B, partially saponified Polyvinyl alcohol (including residual acetate groups by 12.2 mol.%). The following results have been obtained.

1) Ultrasonic velocity and absorption have been measured over the temperature range of 3∼70°C in the concentration range of 5∼15% by weight.

2) For sample A the temperature dependence of velocity is similar to that for pure water, but for sample B the velocity vs. temperature curves have been found to have a broader peak.

3) Concerning the concentration dependence of the velocity, in sample A the sound velocity increases with the increase in the concentration, but in sample B a reverse dependence of velocity on concentration has been found at higher temperatures.

4) The value of M2/ω amounts to about 2∼3 poises on the average for both samples.

5) The compressibility of polymer molecules in solutions has been calculated to be 26.5×10−12 c.g.s.u. on the average for completely saponified polyvinyl alcohol.