bluuebunny/crossref_metadata_2025 huggingface dataset:
Syntheses of Tetracyclohexylsilane and Methylcyclohexylsilanes
Authors: Kanazashi Motonori , Takakusa Michio
Published: July 2006

For new organosilicon compounds containing cyclohexyl group were prepared by hydrogenation of corresponding phenylsilanes. They are: trimethylcyclohexylsilane, dimethyldicyclohexylsilane, methyltricyclohexylsilane, and tetracyclohexylsilane. Physical constants and infrared absorption spectra of these compounds were measured and discussions on the steric hindrance were done with Stuart models.
The Densities of Polyvinyl Alcohol Film at Moist States
Authors: Tadokoro Hiroshi , Seki Syuzo , Nitta Isamu
Published: July 2006

(i) The densities of PVA film at moist states were measured at 25°C. with flotation method by using carbon tetrachloride-benzene mixtures. The density against water content curve shows a conspicuous maximum at about 1.5% water content.

(ii) The water desorption expriment was carried out using the same specimen. The pore size distributions of PVA film and regenerated cellulose fibers were calculated by the Foster method from our desorption date and Hermans’ data, respectively.

(iii) The results are discussed and compared with those of other investigators obtained with native and regenerated cellulose.
On the State of Pentosan in Wood Pulps
Authors: Matsuzaki Kei , Hatano Akira , Abe T\={o}ru , Sobue Hiroshi
Published: July 2006

1. The pulps from the red pine and beech were hydrolyzed with boiling 4n hydrochloric acid solution for 1–7 hours and a part of the hydrolyzed pulps was treated with boiling 1% sodium hydroxide solution for half an hour to eliminate recrystallized particles. The pentosan content decreased as a function of the pulp yield. The degrees of polymerization of these samples were determined.

2. The pulps from the red pine and beech were treated with 4-17.5% sodium hydroxide solution for half an hour at 20° and this procedure was repeated. A part of the samples treated with the alkali was hydrolyzed with 2.5n sulfuric acid solution for one hour at 95–100°. The pentosan contents of these samples were determined.

3. The results show that it is difficult to reduce the pentosan content of wood pulp to under 0.5% by intermicellar reactions such as acid-hydrolysis or dilute hot alkaline refinement, whereas by intramicellar reactions such as cold concentrated alkaline refinement, it is easy to reduce the pentosan content to under 0.5%. The resistant pentosan seemed to be built in the crystalline region of wood cellulose.

4. It has no good effect for pentosan removal to eliminate the recrystallized particles produced by acid hydrolysis with dilute alkali, while acid treatment after cold alkaline refinement gave good result for pentosan removal.
Molecular Structural Studies on Compounds Containing C–O Bond by Electron Diffraction. II. The Molecular Structure of Anhydrous Oxalic Acid
Authors: Shibata Shuzo , Kimura Masao
Published: July 2006

The molecular structure of anhydrous oxalic acid was studied by electron diffraction method. The interatomic distances and valency angles were found as follows: C=O 1.22 Å, C–O 1.37 Å, C–C 1.54 Å, ∠O=C–O 125°, and ∠O=C–C 122° with possible errors within 0.02 Å, 0.02 Å, 0.06 Å, 3° and 5° respectively. The molecule takes planar trans configuration. From these data the following conclusions were derived. The central C–C bond seems to have a small degree of double bond character with no appreciable conjugation between two carbonyl groups. The molecule takes the planar trans configuration in spite of the small degree of double bond character in the C–C bond. This fact in connection with the data of other compounds seems to suggest the possibility of the existence of intermolecular hydrogen bonds in a free oxalic acid molecule. Our data of oxalic acid in the gaseous state were compared with the data of oxalic acid in the crystalline state from x-ray diffraction. Significant differences was found between the results on molecular dimensions, especially in hydroxyl C–O bond lengths. From these fact it was inferred that the structure of a molecule (or a carboxyl group) is affected by the molecular environment such as hydrogen bond formation between molecules.
Polarographic Diffusion Current Observed with Square Wave Voltage. II. Basic Theory for a Reversible Electrode
Authors: Kambara Tomihito
Published: July 2006

By means of the principle of superposition and of the Laplace transformation, the differential equation of diffusion is integrated, and the result thus obtained gives the fundamental theoretical expression for the electrolysis with a square wave voltage.
Errors in Measuring the Wave-Height of Polarogram. II. Practical Errors of Graphical Construction
Authors: Yasumori Yoshikazu
Published: July 2006

When the construction of tangent η on the curve just after the wave in a poralogram is more difficult, but the construction of other tangents are less difficult, it is concluded as follows.

In the case that the construction of η is a little more difficult, a polarogram with high sensitivity is desirable in order to minimize the relative error in measuring the wave-height. And here low span voltage is, to some extent, effective, but a polarogram too enlarged in abscissa is ill-conditioned. Next, in the case of the very difficult construction of η, the relative error of waveheight is minimum, when a polarogram is taken with lowered span voltage, in which the slope of a tangent is tan 45°. Here the error is not always minimum if the polarogram is recorded with lowered sensitivity.
Antituberculous Compounds. IV. Thiosemicarbazones and Related Compounds
Authors: Nishimura Tamio
Published: July 2006

1) Semicarbazones and guanylhydrazones of 4-nitrocinnamaldehyde, 4-nitrobenzalacetone, α-bromo-4-nitrocinnamaldehyde, and 1-(4-nitrophenyl)-2-bromo-1-buten-3-one, nitromethane derivatives of 4-nitrobenzaldehyde, 4-nitrocinnamaldehyde, and α-bromo-4-nitrocinnamaldehyde, and thiosemicarbazones of 4-amino, 4-acetamido-, and 4-nitroacetophen-ones were prepared for evaluation of their antibacterial activity.

2) Condensation of the acetophenones with thiosemicarbazide was found to proceed smoothly at pH 3.2 but not at pH 7.
Enzymatic Microdetermination of Nitrate
Authors: Egami Fujio , Iida Katsuhira , Dôke Tatsumasa , Taniguchi Shigehiko
Published: July 2006

1) On the principle of the colorimetry of nitrite produced by enzymatic reduction, a method of microdetermination of nitrate was established.

2) This method can be applied to 10–100μm/1. nitrate solution. 2 ml. of the solution (1.2–12μg. NO−3 or 0.28–2.8μg. nitrate-n) is sufficient for an analysis.

3) This method is successfully applied to the estimation of nitrate in human urine, horse serum, spinach leaf extract, sea water and rain water.
Diphenylcarbazone as an Internal Indicator in Volumetric Analysis. Part I. Determination of Ferrocyanide by Lead Nitrate
Authors: Deshmukh G S
Published: July 2006

A simple and direct method of estimating ferrocyanide by standard lead nitrate with diphenylcarbazone as an internal indicator has been described. The results are accurate and compared favorably with those obtained by other classical procedures.
Enzymatic Reduction of Aromatic Nitro Compounds
Authors: Yamashina Ikuo
Published: July 2006

1) The enzyme “nitro-reductase”, which activates aromatic nitro-compounds and accelerates their reduction, was extracted from a halotolerant bacterium.

2) The reduction proceeds by the mechanism analogous to that of nitrate reduction, namely, by the system consisting of nitroreductase, intermediary hydrogen carrier, dehydrogenase and hydrogen donator.

3) Oxazine dyes such as nile blue and brilliant cresyl blue are the only effective hydrogen carriers so far examined for the reaction.

4) Various aromatic nitro compounds can be reduced to amino compounds by the enzyme system. Some kinetic studies were performed.

5) The relation between nitro-reductase and nitrite reductase, the identity of which was suggested formerly, was reinvestigated. The competitive inhibition of nitro reduction by nitrite was confirmed, but taking into consideration various experimental evidences, it may be concluded that the two enzymes are not identical.
Microscopic Studies on Fused Catalysts for Ammonia Synthesis. IV. Decomposition of Ammonia over Two Different Constituents
Authors: Osumi Yoshio
Published: July 2006

An unreduced iron synthetic ammonia catalyst promoted with potash or potash and alumina was separated into two different sorts of powders (A and B). Some of their properties were mentioned in the previous reports. Their catalytic activities for decomposing ammonia mixed with hydrogen were studied at atmospheric pressure by a specially devised flow method. The results are:

1. Between about 400°C and 500°C and for the gas mixtures of several compositions, A powder is more active than B.

2. The actions of the gas mixture laden with water vapour over ice kept in a −7°C bath and of that with 0.4A% carbon monoxide are much the same in the rate and extent of poisoning as well as in the rate of recovering when the admixing of the poisoning gases is discontinued. As to the liability to the effects, one sort of powder scarcely differs from another.

3. Heating at 740°C for one hour has no effect. Heating at 830°C for one hour makes B powder less active and A powder also less active at first, but its activity before heating is soon recovered in the course of a run.

4. The activity of a potash-free alumina-promoted catalyst is not affected by adding before reduction a small amount of potashrich B powder.
A Rapid Determination of Nitrogen in Organic Compounds by the Iodic Acid Decomposition Method
Authors: Ohashi Shigeru
Published: July 2006

A new method has been developed to permit the rapid determination of nitrogen in organic compounds. The sample is decomposed with iodic acid-strong phosphoric acid reagent in a glass reaction vessel, and the liberated nitrogen is collected in an azotometer filled with potassium hydroxide solution by the flow of pure carbon dioxide. From the volume of the nitrogen thus collected the percentage of the nitrogen in the sample can be readily determined. This method is, so to speak, the wet modification of the Dumas method.

For various types of compounds containing nitrogen, ammonium salts, amine, azo-compound, pyrrol, thiazole, etc., satisfactory results were obtained by means of this method. The nitrogen in a 10 to 50 mg. sample can be determined for thirty to forty minutes with a simple and inexpensive apparatus.

But volatile compounds, nitro- or nitroso-compounds, compounds having purine, pyridine, quinoline, and other complicated rings, etc., can not give good results.
A Note on Some Alkoxydisilanes
Authors: Okawara Rokuro , Tanaka Toshio , Maruo Keiichi
Published: July 2006

1) Hexamethoxy-, hexaethoxy- and hexaisopropoxy-disilane were prepared and characterized.

2) Dehydrochlorination at an elevated temperature was not suitable for the preparation.

3) A trace of chlorine compound contaminated in the product could be completely taken off by dry ammonia or pyridine.

4) Alkoxydisilanes could not be prepared by using pyridine throughout the reaction as an acid acceptor.

5) The volume of hydrogen evolved by the fission of alkoxydisilanes varied with the reagents.
Studies on Molecular Structure by the Measurement of the Dielectric Constants of Gases and Vapors. I. Construction of an Apparatus and the Dipole Moment and the Molecular Structure of 1, 1-Dichloroacetone
Authors: Chiba Takehiko
Published: July 2006

An apparatus for the measurement of dielectric constant in the gaseous state is constructed. The electrical circuit is a heterodyne double-beat type, the oscillators with a remarkably high frequency stability are constrcuted. By testing several types of gas cell, it was found that one of them (cell D) can be used satisfactorily for the present purpose. For the gas filling system, a modification of Groves’ method is employed. Using this apparatus dielectric constant measurement with an error of less than 0.5 per cent can be obtained. The dipole moment of 1,1-dichloroacetone was measured in this apparatus. The moment was found to increase with temperature. This increase is attributed to the increase of the more polar isomer (b), which coexists with the form (a). The energy difference of the two isomers was found to be about 800 cal./mole. This value is smaller than that of monochloroacetone, and the lowering of ΔE was considered to be due mainly to the reduced moment of the C-Cl bonds by mutual induction. It was thereby concluded that the energy difference in these molecules is electrostatic in nature rather than steric.
On the Specific Coloration of the Benzylamine Type Compounds in the Ninhydrin Color Reaction. I
Authors: Takagi Eiichi , Mangyo Mitsuo , Sawai Masanobu , Ensaka Isao
Published: July 2006

The specific coloration of the benzylamine type compounds in the ninhydrin color reaction is extended to other kinds of compounds. Alloxan resembles ninhydrin in its behaviour as reagent. The fact that the specific coloration reaction seems to be common to the benzylamine type compounds, is verified.

However a few exceptions are observed as in the case of benzylaniline (17) and p-dimethylaminobenzylamine (18). The fact that the color change of these compounds in the usual paper chromatography is due to moisture in the air, is confirmed.
Acetylation of Holocellulose in Fibrous State
Authors: Fujimura Toshikazu
Published: July 2006

Acetylation in fibrous state of holocellulose, its alkali-refined product, rayon pulp and Bemberg rayon was undertaken to disclose the effect of pentosan and the structure of holocellulose.

1) Acetylation of air-dried holocellulose is roughly controlled by surface resistance regardless of various ratios depending on conditions of acetylation and degree of refining. The rate of pretreated sample seems to be determined by internal diffusion.

2) The birefringence decreases at first abruptly and then increases and finally decreases again. The final higher birefringence compared to acetic acid content may be ascribed to acetolysis. Definite amorphous portion is acetylated easily at the initial stage and lost, so that residual crystallinity, and also birefringence, increase.

3) By alkali-refining, acetylation is retarded and initial abrupt change, which is caused by the amorphous portion is diffused. There is optimum point in the concentration of refining alkali, probably relating to hornification, loss of amorphous portion, transformation of crystal form and hindrance by residual pentosan layer. The refining temperature affects the acetylation slightly.

4) Pentosan in product is not reduced apparently, probably due to oxymethylfurfural yielding and poor solubility of acetate. Also pentosan may not be entirely accessible at initial stage.
Studies on A.C. Polarography. I. Theoretical Treatment
Authors: Tachi Isamu , Kambara Tomihito
Published: July 2006

At first the rigorous and orthodox treatment of the polarographic electrolytic current due to the superposition of an alternating voltage upon a constant voltage is shown and the earlier polarographic studies, in which an alternating voltage is employed, are discussed. Next it is shown that in order to treat the a.c. polarography theoretically, we can profitably assume that the superimposed sinusoidal a.c. voltage is equivalent to the square-wave voltage of the same frequency. In a case when an a.c. voltage, is superimposed upon the usual d.c. voltage, the resulting current becomes a very complicated function of time. It can be shown, however, that the current is the algebraic sum of a.c. component and d.c. component, the latter of which is Fournier’s polarogram and the former Breyer’s polarogram. Some outstanding characteristics of both components are satisfactorily cleared up, and it demonstrated that in such a manner a rational and systematic explanation of a.c. polarography is given.
Formation and Aging of Precipitates. III. Electron Microscopic Studies on Barium Sulfate Precipitates in Aqueous Alcohol
Authors: Suito Eiji , Takiyama Kazuyoshi
Published: July 2006

1. The solubilities of barium sulfate in aqueous alcohol were measured.

2. The barium sulfate particles precipitated in aqueous alcohol became smaller with the increasing concentration of alcohol; namely, with the decreasing solubility of barium sulfate.

3. In the case of the aqueous alcohol of the certain percentage (for a definite solubility of barium sulfate) the precipitated particles became larger with the decreasing total concentration of barium sulfate.

4. The barium sulfate precipitates prepared in the aqueous alcohol were practically diamond shaped; and spindle, hexagonal and sphere particles were also found. The shape of the precipitated particles seemed to depend on the induced period of the precipitation.

5. The electron micro-diffraction method was applied to analyze the crystal structure and, of course, the patterns obtained from various types of crystals agreed with those of barium sulfate.
Potentiometric Titration of Thorium and Cerium Nitrates with Glass Electrode
Authors: Pan Kuan , Hseu Tong Ming
Published: July 2006

1) Thorium nitrate was potentiometrically titrated with sodium and ammonium oxalates by using glass electrode as an indicator electode. Four inflections were found in the titration curves of the thorium-oxalate system. The first steep inflection, corresponding to the precipitation of thorium dioxide, was found at the mole ratio of C2O42− to Th4+, viz., the “R” value, 1.9 and at pH 4.3. The second the third and the fourth inflections, corresponding to the formation of thoroxalate complexes were found at the approximate R value of 3.4, and 6, and at pH values ranging from 5.4 to 6.3.

2) Thorium and cerium nitrates were potentiometrically titrated by sodium hydroxide in dilute solutions with glass electrode. By reducing cerie to cerous ions in a solution containing thorium ion, and by titrating the resulting solution with sodium hydroxide solution, two steps of inflection corresponding to the precipitation of thorium and cerous hydroxides, were found respectively, in the titration curve. In applying this method to the determination of thorium and cerous ions in the presence of one another, however, the experimental results obtained from the titration curve must be multiplied by the experimental factors which are both greater than unity for accuracy.
On the Oxidation of Cellulose. II. On Celluronic Acid Prepared by a Simple Method
Authors: Machida Seishi , Inano Mitsumasa
Published: July 2006

Cellulose was conveniently oxidized by concentrated phosphoric acid added with sodium nitrite ; that is, the cellulose was not apt to be hydrolyzed heavily and the oxidation proceeded smoothly.

It was found that carboxyl groups of the oxidized cellulose were largely of the glucuronic type.

The oxidized cellulose, whose carboxyl content was more than 8%, was almost soluble in dilute caustic soda solution ; and the mean degree of polymerisation of such oxidized cellulose was nearly two-thirds of that of the untreated cellulose.

Some properties of the alkaline solution of the oxidized cellulose were investigated.
Cathodo-luminescence as Applied to the Detection of Rare Earths Contained in Some Natural Calcareous Substances
Authors: Iwase Eiichi
Published: July 2006

Specimens of reef corals, stalactite, molluscan fossil and calc-sinters were converted to the form of oxide, in which rare earths, if present in the original specimens, would be concentrated by chemical means. Luminescence spectra given by these samples of calcium oxide were investigated under the cathode-ray bombardment and the presence of minute amounts of rare earths could be confirmed; dysprosium, praseodymium, samarium and terbium in a stalactite from Akiyoshi, dysprosium, praseodymium and presumably samarium in reef corals from Miyako Main Isle, and dysprosium and praseodymium in a molluscan fossil from Hiroshima. Not even slight traces of rare earths were perceived in calc-sinters from several springs, so far as this detecting method was concerned. Two kinds of specimens of reef corals from the same locality gave a remarkable difference in the rare-earth content and this observation may be explained by the different conditions of the surfaces found in these reef corals, during the growth of which the assimilation of the rare earth ions from sea water were possibly much more disturbed by the existence of an organic membrane covering the surface of one specimen as compared with another lacking such a membrane.
Reactions of Bis-alkylsulfonylmethanes and Their Halogen-substituted Derivatives
Authors: Oae Shigeru
Published: July 2006

Bis-alkylsulfonylmethane did react with alkyl p-toluenethiosulfonate giving bis-alkylsulfonyl-alkylmercaptomethane. Bis-alkylsulfonyl-halogenomethane was found to react with metal alkoxide giving original bis-alkylsulfonylmethane. It was also found that bis-alkylsulfonyl-dibromomethane readily reacts with silver nitrate giving the monobromo-compound while its dichloro-analog resists in the same condition.

The mechanisms of these reactions were discussed.
On the Rate of the Sluggish Inversion of Silica Stone Kinetics of the Polymorphous Transition of Silica
Authors: Tokuda Taneki
Published: July 2006

(1) It was found that the soluggish inversion of silica stones of different geological origins, from quartz to cristobalite, was the primary reaction when fired in air, in steam or in reducing atmosphere of carbon monoxide.

(2) Effect of firing atmosphere on the conversion rate of silica stone was investigated.

(3) Influence of grain size on the rate of conversion was investigated, and it was found that Jander’s, relation k∼1⁄δ2 was not applicable to the conversion of silica stone.

(4) Irreversible thermal dilatation of anisotropic aggregates was examined, and the necessary correction to determine the conversion rate by determination of the density was devised.
Alkaline Iodine as an Oxidant for Uranium. IV
Authors: Deshmukh G S , Joshi M K
Published: July 2006

A new method for the determination of uranium based on the reduction of U(VI) to U(IV) and re-oxidation of the latter by alkaline iodine is described. The excess iodine is titrated with standard Na2S2O3 or As2O3 and the results are found to be accurate and reproducible.
A New Method of Drawing the Potential Energy Surface
Authors: Sato Shin
Published: July 2006

A new method of drawing the potential energy surface has been devised and compared with Eyring’s semi-empirical method. The points different from the latter method are that an appropriate function for the anti-bonding state of a diatomic molecule is assumed and the overlap integral is not ignored. The so-called Coulomb fraction in Eyring’s method is not used and the London equation has been slightly modified.

As an example the activation energy of hydrogen atom-molecule reaction has been calculated. So far as this reaction is concerned, the present method gives more reasonable value than Eyring’s method.
Spectrochemical Study of Microscopic Crystals. VIII. Absorption Spectra of Dicyclopentadienyl-compounds of Iron and Cobalt
Authors: Yamada Shoichiro , Nakahara Akitsugu , Tsuchida Ryutaro
Published: July 2006

Dichroisms of dicyclopentadienyl-iron (II) and dicyclopentadienyl-cobalt (III) perchlorate in the crystalline state have been quantitatively determined. For the two compounds, the common rules on the dichroism have been obtained. (1) For the two bands at the longer wave-length, absorption perpendicular to the pentagonal rings is very hyperchromic to absorption parallel to the rings. (2) For the specific band, absorption perpendicular to the rings is slightly bathochromic to absorption parallel to the rings.

Consideration of the results has led us to the conclusion that the cyclopentadienylradicals in these compounds may be different from the π-electronic systems of ordinary benzene rings, suggesting that the π-electrons would be greatly attracted toward the metal atom to form co-ordinate linkages.
On the Color-reactions of the Condensed Polycyclic Aromatic Hydrocarbons and their Related Quinones in the Solutions of the Concentrated Sulfuric Acid
Authors: Handa Takashi
Published: July 2006

The basicity of the condensed polynuclear aromatic hydrocarbons and their related quinones with higher molecular weight have been measured after the method of L. P. Hammett and J. Dyrup, and it is approximately estimated in terms of pKB. In dibenzopyrene molecule two values of pKB have been found. The larger seems to correspond to that of the smaller molecules such as hexamethylbenzene, tetracene. The smaller one seems to be equivalent to that of ovalene, anthanthrene etc. approximately, with which molecules the larger pKB value seems to be unable to be found, owing to the unstability or the low-solubility of them in the sulfuric acid in the present method of measurement. The relatively large difference of pKB between monoketones and quinones seems to be explained on the same considerations as above. The relatively small difference of pKBseems to be dependent on the molecular structure as in the case of azaaromatic hydrocarbons such as pyridine, quinoline and acridine. From the results of such series of molecules as violanthrene, mesonaphhtodianthrene, zethrene, compared with the series of circulartype of molecules such as ovalene, anthanthrene, it is suggested that the proton is more easily attached to the molecule which seems to have localized π-electron in some sense.
Estimation of the Geologic Age of Radioactive Sediment Containing Radium Isotopes
Authors: Sakai Hitoshi
Published: July 2006

Under some assumptions, three methods for the estimation of sedimentation rate as well as sedimentation intensity of radioactive sediments are proposed. These methods are based on the time variation of the abundance ratios of radium isotopes in the sediments. The rate of sedimentation of a radioactive sediment, Hokutolite, is estimated for two samples by these methods. The result is 0.25mm./ year for one sample for which the observed value is known to be 0.15 mm./ year. For the other sample of unknown age, the rate is estimated to be 0.09 mm./ year.
Influence of the Addition of High Molecular Electrolyte upon the Absorption Spectra and Fluorescence of Organic Dyestuffs. IV
Authors: Mataga Noboru , Koizumi Masao
Published: July 2006

The relative intensity of fluorescence and the change of absorption spectra were examined when chitosan hydrochloride and other amine hydrochloride were added to the aqueous solution of uranine, eosine and erythrosine, which are all acidic and have no tendency to associate.

It was found that in the case of uranine, the interaction between amino group and the dye ion is so strong that it directly influences the absorption band remarkably, and thence the interaction is commonly observed irrespective of whether the molecular weight of electrolyte is high or low. In the case of eosine and erythrosine there exists no such strong interaction between amino group and dye ion because the amino compound of low molecular weight produces no marked change in either fluorescence or absorption; a quite notable change is observed in the case of the amino compounds of high molecular weight; thus for example, the fluorescence at first drops and then recovers as the concentration is increased. The phenomena were interpreted as due to the concentration effect of dye ions gathered around the electrolyte ion by weak attraction. This interpretation is quite analogous to that already applied for basic dyes.

There appeared, however, no metachromasy band and this was ascribed to the fact that the acidic dyes have scarcely any tendency to associate; thus our opinion put forth for the case of basic dyes, that the change of aggregation of dye ions is mainly responsible for metachromasy, was confirmed once more in the case of acidic dyes.
The Michael Addition of Diethyl Malonate to Ethyl Crotonate-(carbonyl-C14)
Authors: Simamura Osamu , Inamoto Naoki
Published: July 2006

The Michael addition of diethyl malonate to ethyl crotonate-(carbonyl-C14) was carried out with one equivalent of sodium ethoxide.

The addition product, diethyl α-ethoxycarbonyl-β-methylglutarate, was hydrolyzed to the corresponding acid. It was decarboxylated by heating to give β-methylglutaric acid, which was found to contain most of the radioactivity originally present in the ethyl crotonate. Thus, it was demonstrated that the migration of an ethoxycarbonyl group did not take place in contrast to the case with diethyl methylmalonate. The mechanism is discussed.
New Derivatives of Levulinic Acid. I. Synthesis of 2,3-Epoxy-3-Methyladipic Esters
Authors: Maekawa Eturô , Mizoguchi Masako , Ishii Yoshio
Published: July 2006

Levulinic and monochloroacetic esters are condensed by sodium amide or potassium tert.-butoxide to give the corresponding 2, 3-epoxy-3-methyladipic esters.n-Butyl (B), 2-ethylhexyl (O), and lauryl (L) alcohols were used as alcoholic components of these starting esters. Although the yields were poor, nine new esters, namely the B-B, B-O, O-B, B-L, L-B, O-O, O-L, L-O,and L-L 2, 3epoxy-3-methyladipates were obtained.

As for condensing agents, potassium tert.-butoxide was the most excellent, and sodium amide gave also good results, while sodium ethoxide and methoxide gave no desired ester.

These new esters would be able to be utilized as a stabilizing plasticizer for poly-vinyl chloride.
Dielectric Studies on Colloidal Solutions. I. High-frequency Conductivity of Aqueous Solutions of Paraffin-chain Salts
Authors: Shirai Michio , Tamamushi Bun-ichi
Published: July 2006

The high-frequency conductivity of solutions of sodium dodecyl sulphate, sodium oleate, and dodecyl amine hydrochloride was measured at frequencies of 15 and 30 Mc./sec. The high-frequency effect remarkably appeared at the concentration corresponding to the critical micelle concentration and the effect can be interpreted in terms of Debye-Falkenhagen’s theory of strong electrolytes.

The appearance of maximum and gradual decrease in high-frequency effect may be explained by the shortening of the relaxation time or by the reduction of the electrostatic interaction due to the change of micelle structures with the increase of concentration.
The Interaction of Gelatin Molecule with Surface Active Ions
Authors: Tamaki Kunio , Tamamushi Bun-ichi
Published: July 2006

The action of dodecyl amine hydrochloride and sodium dodecyl sulphate on gelatin was studied at various hydrogen ion concentrations of the mixed solution, once by determining the combined detergent ions to the precipitated gelatin and then measuring flow properties of mixed solutions.

The determination of the combined deter-gent ions showed that the complex formation between detergent and gelatin should have taken place according to the mechanism proposed by Pankhurst and his co-workers.

The non-Newtonian flow character of gelatin solution at pHs on both sides of the isoionic point, was greatly influenced by the addition of detergent cations or anions and the flow of the mixed solutions directly before the precipitate formation or after the precipitate dissolution became approximately Newtonian, which suggested that the gelatin molecule would have been brought into a more folded state by the successive combinations of detergent ions.

The viscosity coefficient as well as yield value of the gelatin solution at the isoionic point were found to increase by the addition of detergent cations or anions. This suggested that the folded isoionic gelatin molecule would have been expanded by the combination with either one of the detergent ions.
The Crystallinity of Solid High Polymers. I. The Crystallinity of Polyvinyl Alcohol Film
Authors: Tadokoro Hiroyuki , Seki Syûzô , Nitta Isamu
Published: July 2006

i) Densities, sorption of water vapor and infrared absorption spectra were measured on four kinds of PVA films, which were prepared from the same PVA powder specimen and subjected to different heattreatments.

ii) It was found by the present investigation that the 1146 cm−1 (8.74μ) band is the so-called crystallization-sensitive band.

iii) Since the degrees of crystallinity determined by these methods went in parallel, it was found that they may be used as relative measures for the crystallinity.

iv) Samples subjected to the heat-treatment at about 193°C, behave abnormally from the other three groups of samples. This deviation was found to be due to chemical changes occurring in the heat-treatment. This was confirmed by the measurement of ultraviolet absorption spectra.
Studies on Several Phosphates from the View-point of Analytical Chemistry. IV. A Radioactive Paper Chromatography on Several Meta- and Poly-Phosphates labelled with P32
Authors: Shinagawa Mutsuaki , Takanaka Junichi , Kiso Yoshiyuki , Tsukiji Aiko , Matama Y\={o}ko
Published: July 2006

1) To separate various meta-and poly-phosphate ions respectively, pyridine-water (1:1) was found to be the most desirable developing solvent. Especially, both trimeta- and hexameta-phosphate ions can be separated from the ortho-, pyro-, and tripoly-phosphate ions, but the latter were not completely separated. The authors plan to separate them after further study of solvents.

However, by using labelled radioactive substances, it may possible to detect the impurity in synthesized phosphate or the traces of other phosphates in the main component. If the radioactive dilution method should be applied, this method may be used in determining nonactive substances. No special care was necessary in this case concerning the atom-exchange of phosphorus between active phosphate ions and non-active.

2) As shown in Fig. 4 it may be possible to determine hydrolysis products by the present simple method.

3) There is a certain regular relationship between the ionic structures and their Rf’s. That is to say, Rf’s will decrease in proportion to the increase of the number of phosphorus atoms contained in each kind of ions with chain structure, while trimetaphosphate having a cyclic structure has greater Rf value than others with chain structure.
The Effect of Pressure on the Semi-conductivity of Isoviolanthrone
Authors: Inokuchi Hiroo
Published: July 2006

The electrical resistivity of isoviolanthrone (C34H16O2) and violanthrene (C34H18) decreased with compression. The resistivity of isoviolanthrone was lowered to 1/500 of its value (5×109 Ω .cm.) at an ordinary pressure, that is, 8.4×107 Ω.cm. at 4.2×103 kg./cm2 and 1.2×107 Ω.cm. at 8.4×103 kg./cm2 at 15°C. Further it is possible to suppose that the observed decrement of electrical resistivity is an intrinsic one, due to elastic deformation of crystals.
The Structure of Chamenol
Authors: Nozoe Tetsuo , Kitahara Yoshio , Arai Tomio
Published: July 2006

The structure of chamenol, a phenolic substance isolated from the acid fraction of the essential oil of Chamaecyparis taiwanensis, was proved to be 2-methoxy-5-isopropylphenol.
Cathodo-luminescence of Samarium as Applied to the Structural Studies of Alumina. II. On the Alumina Produced from Hydrous Alumina Gels
Authors: Iwase Eiichi , Nishiyama Seijiro
Published: July 2006

Hydrous alumina gels were prepared from both solutions and crystals of a number of aluminium salts, in the former case by precipitation with ammonia and in the latter by direct immersion in concentrated ammonia liquor. Samarium ions were impregnated in these hydrous alumina gels or in their transition phases resulting from the previous thermal treatment of various temperatures. The feature of the cathodo-luminescence spectrum was investigated on the samarium-bearing alumina produced from the above-mentioned samples by a final heat treatment.

Spectrographic measurements of the cathodo-luminescence reveal that the heating of the hydrous alumina gels derived from a solution of aluminium nitrate results in their conversion to the α-alumina, while the heating of those from solutions of aluminium chloride and sulphate does not give the genuine α-modification. This was confirmed by the fact that the most intense band of a particular luminescence prototype III as designated by one of the present authors was observed in the cathodo-luminescence spectra.

The Υ-α transformation of alumina occurs at temperatures far below its transition temperature when a suitable amount of ammonium nitrate, the by-product of the neutralisation reaction, was caused to remain by heating the precipitated hydrous alumina gel, which was derived from a solution of aluminium nitrate at a moderately elevated temperature.

Similar remarkable results were, however, not obtained with hydrous alumina gels derived from solutions of aluminium chloride and sulphate, and also with the gel derived from a solution of aluminium nitrate, if the latter gel had been made free from the reaction by-product. An addition of ammonium nitrate to the purified alumina gels can no more regenerate the ability to accelerate the Υ-α transformation.

It is interesting to note that hydrous alumina gels obtained by immersing crystals of aluminium nitrate enneahydrate, aluminium chloride hexahydrate, aluminium sulphate octodecahydrate and ammonium alum in concentrated ammonia liquor for a sufficiently long time behave themselves, on being heated, in a somewhat similar way to those obtained by precipitation from the solutions of the foregoing aluminium salts.
Chemical Studies on Polyuronides. VI On the Mucilage of Nori-utsugi Plant, Hydrangea Paniculata, Sieb. (1)
Authors: Machida Seishi , Inano Mitsumasa
Published: July 2006

1. The mucilage of the inner bark of the Nori-utsugi plant Hydrangea paniculata, Sieb.) was found to be composed of arabinose, galactose, rhamnose and d-galacturonic acid.

2. When the crude mucilagenous solution had stood for several days, a deposit appeared which might be composed of impurities. The purified mucilage was obtained from the supernatant clear solution. The purified mucilage was a polyuronide composed of galactose, rhamnose and galacturonic acid and it was considered to be the essential part of the mucilage.

3. Degraded mucilage was obtained by heating the crude mucilagenous solution at 120-125°C in an autoclave. It had the same component sugars as the purified mucilage,and represented the main structure of the mucilage.

4. The essential part of the mucilage was to a polyuronide composed of d-galacturonic acid, galactose and rhamnose in the molar raito of 10:7:3: that is,the molecular for mula is [(C6H8O6)10·(C6H10O5)7·(C6H10O4)3]20

5. The solution of the degraded mucilage exhibited the typical electroviscous behavior of polyelectrolyte.
Studies on A.C. Polarography. V. Theory of Reversible Wave
Authors: Senda Mitsugi , Tachi Isamu
Published: July 2006

The electrolytic current due to the superposition of an alternating potential upon a constant potential applied to the electrode is approximately derived for the case of reversible reaction. The parameter which determines the reversibility of the a.c. electrolysis is also given. Using the above derived results, the instateneous electrolytic current as well as current-voltage curves of reversible Breyer’s and Fournier’s polarogram are shown.
On the Main Chemical Components dissolved in the Adjacent Waters to the Aleutian Islands in the North Pacific
Authors: Fukai Rinnosuke , Shiokawa Fumiko
Published: July 2006

The authors carried out the analyses of the main dissolved components of sea water on the samples collected from the Aleutian region in order to examine the local characteristics of the region under study. At the same time the samples collected from the Kuroshio region were analysed to check the systematic errors introduced. The results were expressed in terms of ratios to chlorinity. As a result, the following conclusions have been deduced.

1. The relative decrease in sulfate and sodium equivalents was recognized on the samples collected from the layer of temperature minimum. This seems to relate to freezing phenomena of sea water.

2. A tendency of sulfate increase in the surface samples was noticed.

3. Averaged values for the Aleutian region were in close agreement with those for the Kuroshio region, both having been obtained by the present authors. The values also coincided with those obtained by other workers, except for higher potassium values.

These facts may indicate that although the water masses existing in the Aleutian region are, on the whole, a portion of the oceanic circulation of the Pacific, a slight deviation from the normal composition appears in the main components in some characteristic layers.
Surface Chemistry of High Polymers. VI. The Monolayer of Polyethylene Terephthalate and Poly-N-vinyl Pyrrolidone
Authors: Hotta Hiroshi
Published: July 2006

As the result of the measurements of the interfacial pressure and potential of polyethylene terephthalate and poly-N-vinyl pyrrolidone at the air/water and oil/water interfaces, it is concluded that the ring groups in the main chain make the polymer molecule rigid even at the oil/water interface, while that in the side chain is not essentially different from the chain groups. The film of poly-N-vinyl pyrrolidone is relatively labile on the alkaline substrate.
Tin (II)-Strong Phosphoric Acid. A New Reagent for the Determination of Sulfate by Reduction to Hydrogen Sulfide
Authors: Kiba Toshiyasu , Takagi Tomoo , Yoshimura Yooko , Kishi Ikuko
Published: July 2006

A new reagent, “ Tin(II)-Strong Phosphoric Acid ”, has been prepared to permit a rapid and simple determination of sulfates by reducing to hydrogen sulfide. The reagent is stable at a room temperature but reacts-violently above 120°C. Evolved hydrogen sulfide after the reaction with this reagent is absorbed in zinc acetate-acetic acid solution and titrated iodometrically as usual. 1 ml of 0.02n iodine solution corresponds to 0.9607 mg. of sulfate ion. The apparatus for the preparation of the reagent and reduction of sulfate are illustrated. The determination of sulfur in various sulfates was carried out by this method and satisfactory results were obtained. Moreover, it seems to be an advantage of this method that solid samples can be treated directly in the reaction vessel.

The expense of the present research has been paid in part by a Grant for Scientific Research from the Ministry of Education.
Rapid Determination of Sulfur in Organic Compounds by the Tin(II)-Strong Phosphoric Acid Reduction Method
Authors: Ohashi Shigeru
Published: July 2006

1) A new method for the determination of sulfur in organic compounds has been established.

2) This method is based on the utilization of the reducing power of tin(II)-strong phosphoric acid and the oxidizing power of chromium(VI)-strong phosphoric acid.

3) Sulfur in organic compounds is reduced to hydrogen sulfide by heating with tin(II)-strong phosphoric acid directly (Procedure A) or after oxidizing with chromium(VI)-strong phosphoric acid (Procedure B).

4) The liberated hydrogen sulfide is absorbed in zinc acetate solution and estimated by the iodimetry.

5) The analytical results obtained for methylorange, sulfur guanidine, and cystine by the Procedure A and for thiourea, methi-onine, acetylmethionine, and thionalide by the Procedure B were given.
A Quantum-Mechanical Consideration of Chemical Reaction Rates
Authors: Yasumori Iwao , Fueki Kenji
Published: July 2006

The transmission coefficient for the simplified two-dimensional potential barrier has been obtained and its property depending on the curvatures of the barrier and other factors has been discussed. On the basis of this coefficient a quantum-mechanical rate equation has been formulated, the limiting forms of which formally reduce to the ARR equation and to Wigner’s equation including a quantum correction. Then the rate constants given by the equations in the present and the ARR theory have been compared for the reaction H+H2→H2+H.

It has been found, from the above results, that the classical approximations in the ARR theory are generally valid except the reactions involving light particles and a thin barrier at low temperatures.
Studies on the Oxidation of Ferrous Sulfide
Authors: Wada Tsuguyasu , Shiraishi Yutaka , Niwa Kichizo
Published: July 2006

The rate and mechanism of oxidation of ferrous sulfide was studied by means of a spring balance and X-ray diffraction analysis over the temperature range from 500°C to 700°C. The conclusion reached is as follows :

(1) Complete oxidation, in which only the formation of oxides proceeds, begins at 600°C.

(2) At the initial stage of oxidation, a slight increase of weight is found. It was observed by X-ray that the deficiency of cation in ferrous sulfide occurs in this stage. This may be due to the formation of oxide on the surface rather than to chemisorption, which is accompanied by creation of cation vacancies in ferrous sulfide crystal.

(3) Above 600°C, the rate of oxidation does not change with temperature, so the rate-determining factor is diffusion of gas. Since the observed rate of oxidation depends upon the quantity of the sample, the diffusion in the bed of sample may determine the rate.
Characteristic Absorption Bands of Vinyl Ethers
Authors: Mikawa Yukio
Published: July 2006

The infrared spectra of methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-ethylhexyl, benzyl and phenyl vinyl ether and also ethyl vinyl thioether were investigated over the region of 4000-650 cm−1. The assignment of the spectrum of methyl vinyl ether has been made by the aid of the bands contours. The absorption bands of the other were discussed and the characteristic frequencies of vinyl ethers are concluded as follows.

(1) three bands near 3100 cm−1…… CH stretching of vinyl group

(2) 1615±5 cm−1…… C = C stretching

(3) 1321±2 cm−1…… CH in-plane deformation

(4) 1203±2 cm−1…… C-O stretching

(5) 965±5 cm−1…… = CH- out-of-plane deformation

(6) 815±5 cm−1…… = CH2 out-of-plane deformation
Study on Fused Iron Catalyst for Alcohol Synthesis from Water-gas. IV. Reaction Rate and Composition of Product in the Synthesis with Catalyst Promoted by Copper
Authors: Uchida Hiroshi , Kuraishi Michio , Ichinokawa Hideo , Ogawa Kiyoshi
Published: July 2006

The catalyst containing copper as a promoter has produced a good yield of the oxygenates in the small convertor (volume of the catalyst, 60 cc.) as well as in the larger convertor (620 cc). Although the syntheses have been conducted at relatively low space velocity of the synthesis gas as compared with the Synol synthesis, the oxygenates amount to so high a value as half the liquid and solid products and the result may promise the higher yield of oxygenates at the working conditions analogous to those with the Synol synthesis.

From the results of analyses for the reactants and products in the gases withdrawn from seven different heights of the catalyst bed together with the results of the composition of the product at the exit and also with special attention paid to the temperature gradient and flow rate through the catalyst bed, two types of the rate equation have been presented as shown by Eq. (A) and Eq. (B), both of which are similarly applicable to the observed rate.

& φ=kk’P_H_2^2P_CO/(1+k’P_H_2^2P_CO) (A)

& φ=kP_H_2P_CO/(1+k’P_CO)^2,

& φ=kP_H_2^1/2P^CO/(1+k’P^CO)^2 (B)

The equation (A) was once proposed by R. B. Anderson et al. for the synthesis with a cobalt catalyst.

The lateral temperature distribution in the catalyst bed is given by a simplified analytical solution of the W. Broetz’s equation of the heat transfer only when the temperature difference between the wall of the convertor and the catalyst bed is considerably small.