bluuebunny/crossref_metadata_2025 huggingface dataset:
The Composition of Strong Phosphoric Acids
Authors: Ohashi Shigeru , Sugatani Hiroko
Published: July 2006

The strong phosphoric acids in the range from 67 to 80 wt. % phosphorus (V) oxide were analyzed by the anion-exchange chromatography combined with the usual molybdenum-blue colorimetry. The so-called “ 300°C-strong phosphoric acid” which has been used for many analytical purposes in the authors’ laboratory is composed of 44.4 wt. % orthophosphoric acid, 39.8 wt. % pyrophosphoric acid, 12.3 wt. % tripolyphosphoric acid, and 3.6 wt. % tetrapolyphosphoric acid. It was found that the relation of mole fractions of middle PO4 units, end PO4 units, orthophosphoric acid units, and unreacted water molecule units versus the mole ratio H2O/ P2O5 agrees with the reorganization theory for the strong phosphoric acids, presented by Parks and Van Wazer.
Polarographic Studies of Metallic Complexes. I. Oxalato-ammine, Glycinato-ammine and Ethylenediamine-ammine Series of Cobalt (III) Complexes
Authors: Maki Nobufumi , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

The ions [Co oxn(NH3)6−n](2l−3)−, [Co glyn(NH3)6−n](3−l)+,[Co enn(NH3)6−n]3+, [Co en2 gly]2+ and [Co en2 ox] + were all reduced irreversibly in two steps at the dropping mercury electrode.

The first diffusion current corresponds to the reduction, CoIII→CoII and the second to the reduction, CoII→Co0. The diffusion current and the concentration were linearly related.

The half wave potential of the first wave of the cobalt (III) complexes shifts to negative direction in the following order of the ligands: ox2−, gly−, NH3, en.
A New Synthesis of Threonine
Authors: Sato Mikio , Okawa Kenji , Akabori Shiro
Published: July 2006

A new method is described for the synthesis of threonine from acetaldehyde and copper glycinate. This method gives a mixture of allo-threonine and threonine in a high yield (64%).
Studies on Serine Peptides. III. Synthesis of l-Seryl- l-Histidine, l-Seryl-l-Histidyl-l-Leucine and Carbobenzyloxy-Glycyl-O-Benzyl-Dl- Serine Ethyl Ester
Authors: Okawa Kenji
Published: July 2006

l-Seryl-l-histidine and l-seryl-l-histidyl-l-leucine have been synthesized in good yields by Sheehan’s dicyclohexylcarbodiimide method. In the removal of protecting groups of O-Bz-serine derivatives by Ben-Ishai’s method, dioxane must be used as the solvent in place of glacial acetic acid. O-Bz-l- and Dl-serine ester was synthesized the mild esterification condition.
Benzylation of Allylbenzene. Formation of 3,4-Diphenyl-1-butene and 3-Benzyl-3,4-diphenyl-1-butene
Authors: Ando Teisuke , Tokura Niichiro
Published: July 2006

When allylbenzene was treated with the same moles of sodium amide and benzyl chloride in liquid ammonia, one or two benzyl radicals were introduced into allylbenzene to produce 3,4-diphenyl-1-butene and 3-benzyl-1-butene.

The reaction is similar to the well-known reaction of benzyl cyanide and benzyl chloride in liquid ammonia and that of 2-phenyl-1-ethanol and benzyl chloride in benzene.

Two forms of 2,3-diphenylpropionic acid were isolated and their I. R. spectra were measured. Different curves were obtained in KBr disks, while the identical curves were obtained carbon tetrachloride solution.

Infrared absorption spectra were measured by Professor Kinumaki and his associates of this Institute and the elementary analyses were performed in the laboratory of Shionogi and Company, Ltd., to whom the writers are deeply indebted.
Ring Cleavage in Liquid Sulfur Dioxide. I. Cleavage of Cyclic 1,2-Diketone Monoximes
Authors: Murakami Daisaburo , Tokura Niichiro
Published: July 2006

1,2-Diktone monoximes were subjected to treatment with thionyl chloride in liquid sulfur dioxide to obtain cyano carboxylic acids in good yields.
Phase Transition of Li2O–Fe2O3 System. I. Thermal and Electric Properties of Lithium Ferrite LiFeO2
Authors: Kato Eizo
Published: July 2006

The measurements of differential thermal analysis, thermal expansion and d.c. electric resistance for lithium ferrite were performed in relation to the orderdisorder transition. Conclusions are described as follows;

(1) The endothermic reaction and the anomalous expantion take place during the transition.

(2) The value of the transition temperature is determined as 660±2°C. by means of dilatometry.

(3) The existence of electrolytic conduction is qualitatively recognized.

(4) It is verified that the transition is very sluggish.
Phase Transition of Li2O–Fe2O3 System. II. Thermal and Electric Properties of Lithium Ferrospinel LiFe5O8
Authors: Kato Eizo
Published: July 2006

The measurements of differential thermal analysis, thermal expansion and d. c. electric resistance for lithium ferrospinel were performed ; the results were discussed in relation to these for the lithium ferrite. Conclusions are as follows;

(1) Anomalous changes in the thermal and the electric properties take place during the transition and the hysteresis loops are observed.

(2) The transition temperature for LiFe5.86.O8, 745±1°C., is obtained from both thermal and electric measurements. The true transition temperature is determined to be 750±1°C. for the stoichiometric specimen.

(3) It is verified that the transition velocity is more rapid than that of lithium ferrite.

(4) The thermal properties change at the magnetic Curie point, ca. 635°C.
Diamagnetism of Azeotropic Binary Liquid Mixtures
Authors: Venkateswarlu K , Sriraman S
Published: July 2006

An exhaustive study of the diamagnetic susceptibilities of the two types of azeotropic binary mixtures has been made with a view to find out any correlation between the magnetic data and the azeotropic behavior of the mixtures. The results obtained in the case of seventeen mixtures show that in almost all the cases additive law is obeyed even at the azeotropic concentrations. The small deviation from additivity observed in the case of ethanol-ethyl acetate mixture is explained on the basis of the formation of hydrogen The bonds. The magnetic data are not affected by the azeotropic nature of the mixtures.
Activation Analysis of Manganese in Ferromanganese Alloy Using Radium-Beryllium Neutron Source
Authors: Kusaka Yuzuru
Published: July 2006

A method was developed to determine macro-amounts of manganese in ferromanganese by radioactivation, using 50 mg. radium - beryllium as thermal neutron source. By activation of a sample (6 g.) for 18 hours and directly counting the activity with an end-window G. M. counter, the induced radioactivity was found to be entirely due to the 154.8 min. 56Mn radioisotope. The amount of radioactivity was approximately proportional to the manganese content, but with samples of higher manganese content the self-shadowing phenomenon was recognized. By this method, it was possible to determine the manganese content in ferromanganese with a mean error of 2.5% without chemical procedures.
On the Mechanism of the Coalescence of Drops at an Oil-Water Interface
Authors: Watanabe Takehiko , Kusui Makoto
Published: July 2006

The stability or persistency of drops at an oil-water interface in the presence of emulsifier has been studied. The behavior of drops at an oil-water interface has been observed using colored drops to interpret the process of the coalescence.

A mechanism, which explains the coalescence of drops at an oil-water interface more reasonably, was proposed as follows: the main process of the coalescence of drops at an oil-water interface is the formation of a defect in the emulsifier layer around the drops at the portion in contact with the plane interface.

The stability or persistency of emulsions may be estimated qualitatively by the values of T obtained in the present investigations.
Studies on Sarkomycin–Optically Active 2-Methylenecyclopentanone-3-carboxylic Acids
Authors: Toki Katsuyuki
Published: July 2006

d- and l-2-Methylenecyclopentanone-3-carboxylic acid were synthesized starting from optically active cyclopentanone-3-carboxylic acid obtained by resolution of the racemic acid with brucine, and both d- and l-isomer, thus obtained, showed the same infrared absorption as natural sarkomycin (Hooper).
Benzylation of Acetylene. II. On the Structure and Oxidation of 3-Benzyl-3,4-diphenyl-1-Butyne
Authors: Ando Teisuke , Tokura Niichiro
Published: July 2006

The equimolar reaction between benzyl chloride and sodium acetylide in liquid ammonia resulted in the formation of 3-benzyl-3,4-diphenyl-1-butyne in addition to 3,4-diphenyl-1-butyne and 3,4-diphenyl-1,2-butadiene. This compound resisted various oxidative reagents except potassium permanganate. 2-Benzyl-2,3-diphenylpropionic acid was obtained in two polymorphs.
Determination of Small Quantities of Acetone in Methyl Methacrylate Monomer
Authors: Takayama Yuzi , Tokiwa Fumikazu
Published: July 2006

The method described here is based on the utilization of the iodoform reaction. The essential point of this method consists in the complete shaking of the methyl methacrylate monomer with sodium hypoiodate solution. The methyl methacrylate monomer is water-insoluble and iodoform reaction proceeds in an aqueous medium. As a result, it was confirmed that methyl methacrylate monomer does not affect this reaction substantially and one ml. sample makes it possible to determine small quantities (0.001%) of acetone in the sample monomer. This method is more sensitive than the hydroxylamine hydrochloride method previously used.
Dielectric Properties of Starch. II. High Frequency Loss Process
Authors: Ono Sôzaburo , Kuge Takashi , Koizumi Naokazu
Published: July 2006

Dielectric measurements have been made on α- and β-modification of potato starch containing 0.0–17.7% sorbed water in the frequency range from 2kc. to 3 me. and temperature range from room temperature to −70°C. The dielectric relaxation process found has been attributed to the hindered rotation of the hydroxyl groups of starch and sorbed water. The heat of activation for this process is about 11 kcal./mole as a mean. The free energy of activation and the mean relaxation time of this process are lowered as the sorbed water is increased. The variation of the dielectric loss curve with the sorbed water has been discussed. Both modifications show similar dielectric behavior qualitatively, except in the case of the temperature dependence of ε″max value. The variation of the ε″max value with temperature for β-modification suggests that the arrangement of the hydroxyl group would be considerably well-ordered in the micell of starch granule.
Isolation of Agarobiose Derivative from the Mucilage of Gloiopeltis Furcata
Authors: Hirase Susumu , Araki Choji , Ito Toshiya
Published: July 2006

1. The mucilage of Gloiopeltis furcata has been subjected to partial methanolysis, which resulted in the isolation of methyl d-galactoside, 3,6-anhydro-l-galactose dimethylacetal, methyl d-xyloside and agarobiose dimethylacetal.

2. Since the agarobiose derivative was obtained in a good yield, it has been concluded that the disaccharide represents the chief repeating unit of the mucilage molecule, if the sulfate residues present in the mucilage are left out of consideration.

3. Xylose has been identified for the first place so far as the Gloiopeltis mucilage is concerned. But the yield was so low that the sugar might be possibly derived from a contaminating xylan.
Studies on Explosive Reaction of Ethylene Mixed with Oxygen or Air. I. Explosion Limit at Low Pressure
Authors: Suga Masao
Published: July 2006

The explosion limit of ethylene mixed with oxygen or air was determined at lower pressure than atomospheric pressure by the statical constant volume method known as the “admission method”. Isochors, isotherms and isobars of the explosion limit have been shown. The colors of ignition flames change in the order of blue, yellow and blue with the decrease in the percentage of ethylene. In addition, the explosion peninsula was recognized at a definite condition in the mixture range 2.5∼30% ethylene in oxygen. The results of ethylene wiyh oxygen and ethylene with air were equivalent to each other, so far as the partial pressure of nitrogen was neglected. Induction periods were also taken into consideration and the apparent activation energy was estimated to be about 30 kcal./mol.
Polymerization of Olefins with Trialkylboron Catalysts. II. Polymerization of Styrene
Authors: Ashikari Nobuyuki
Published: July 2006

Styrene was polymerized with tri-iso-propylboron and tri-iso-butylboron prepared by the reaction of Grignard reagents and borontrifluorides. In regard to the rate of polymerization in bulk- and emulsion system, that in the latter was much larger than that in the former. Moreover, in the emulsion system, a very highly polymerized product was easily obtained.

Some properties of the polymer prepared with tri-iso-propylboron were studied in comparison with ordinary polymer. The solubility in methyl-ethyl-ketone and the infrared spectrum closely resembled those of ordinary polymers. On the X-ray diffraction pattern, a little difference was observed. But, it is not evident whether the crystalline structure exists or not.
Ring Enlargement of Croconic Acid
Authors: Yamada Kiyoyuki , Hirata Yoshimasa
Published: July 2006

The reaction of croconic acid with diazomethane gives instead of its simple methylated product, a compound with an enlarged ring. Trimethoxy-p-benzoquinone was synthesized from pyrogallol, and was identified with the compound obtained from croconic acid.
The Synthesis of Carvone from α-Terpinyl Acetate
Authors: Suga Takayuki
Published: July 2006

(1) Oxidation of dl-α-terpineol with tert-butyl chromate yeilded 8-hydroxypiperitone, which has not previously been described, 8-hydroxycarvotanacetone and homoterpenyl methyl ketone. In this case the oxidative fission of the double bond in the ring took place to a remarkable extent.

(2) Oxidation of dl-α-terpinyl acetate with tert-butyl chromate gave 8-acetoxypiperitone, 8-acetoxycarvotanacetone, (neither have previously been described) and homoterpenyl methyl ketone. In this oxidation the cleavage of the ethylenic linkage was suppressed, and the yield of 8-acetoxycarvotanacetone was relatively good.

Moreover, the effects of the solvent, acetic acid, benzoyl peroxide, air and the reaction temperature, on the yield of 8-acetoxycarvotanacetone wre investigated.

(3) 8-acetoxycarvotanacetone was converted into dl-carvone when acetic acid was eliminated by pyrolysis.

(4) The synthesis of carvone from α-terpinyl acetate was attiained through the intermeidate of 8-acetoxycarvotanacetone The overall of carvone from α-terpinyl acetate was 28% mole%.
Refining of Low Temperature Cresol No. 1
Authors: Yamada Keisho
Published: July 2006

Low temperature cresol No. 1 has an offensive smell, and its spontaneous coloration is remarkable. It was treated with an oxidizing agent and active clay for the purpose of refining, and then washed with sodium bicarbonate solution in order to remove carboxylic acids which give a strong peculiar smell. Refined cresol which has no more offensive smell and shows a little spontaneous coloration, was obtained.

The impurities in the low temperature cresol No. 1 and in the refined cresol were measured, and it was found that in the refined cresol every impurity was decreased; especially unsaturated carboxylic acids, carbonyl compounds and basic oil were diminished. In the strong acid oil were detected, propionic, iso-butyric, n-butyric, iso-valeric, n-valeric acids and catechol, in the weak acid oil, p-cresol, 2,4- and 2,5-dimethylphenols, in the neutral oil, n-propyl methyl ketone, mesityl oxide, n-amyl methyl ketone, iso-butyl methyl ketone, o-hydroxybenzaldehyde, benzaldehyde, 4-methylcyclohexanone, acetophenone, p-xylene, mesitylene and naphthalene and in the basic oil, 2-, 3-, 4-methylpyridines, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-dimethylpyridines, 4-ethylpyridine and 2,4,6-trimethylpyridine, respectively.

Sulfur compounds were measured in accordance with chemical forms, and it was found that free sulfur and mercaptans are contained as the predominant components, and alkyl disulfides as the next; a little hydrogen sulfide, alkyl sulfides and thiophenes are also present.

Coal tar contains many components, and two hundred and eighty-two, or three hundred and ninety-four components have already been reported in the literature of the subject.

But n-propyl methyl ketone, mesityl oxide, n-amyl methyl ketone, iso-butyl methyl ketone, o-hydroxybenzaldehyde, benzaldehyde and 4-methylcyclohexanone, that have been identified in this study, are not found in literature. Among those substances listed above, many have strong peculiar smell, and exhibit spontaneous coloration.

The refined cresol, which was treated with the oxidizing agent, active clay and sodium bicarbonate solution, scarcely has any offensive smell and exhibits only a slight spontaneous coloration. Measurement of the impurities in the refined cresol shows that almost all the above mentioned substances have been removed. Thus it is concluded that an offensive smell and spontaneous coloration of the low temperature cresol No. 1 arise, at least partially, from these substances.
On the Cooking Mechanism of Wood. XVII. Further Investigations on the Conductometric Titrations of Lignin Models with Phenolic Hydroxyl Groups and a Brief Theory of the Conductometric Titration of Phenols
Authors: Mikawa Hiroshi , Sato Koichiro
Published: July 2006

1. Conductometric titrations of the model compounds IV, V, VI and VII provided reconfirmation of the previously reported findings that simple guaiacol-type phenolic hydroxyl group I was conductometrically titratable, while non-guaiacyl phenolic hydroxyl group belonging to type II was conductometrically untitratable.

2. It was thus further confirmed, that the separate estimation of both type-I and -II phenolic hydroxyl groups of lignosulfonic acid by the method of conductometric titration is possible in combination with the ultraviolet absorption spectra taken simultaneously with the conductometric titration without any dilution of the solution.

3. As we have now considerable accumulation of facts supporting the existence of o,o′-diphenol type phenolic hydroxyl group in lignin, three water-soluble model compounds VIII, IX and X were titrated conductometrically. Phenolic hydroxyl groups of IX and X were found to be conductometrically titratable. Of the two phenolic hydroxyl groups of the model compound VIII only one was found to be titratable.

4. A brief theoretical consideration of the conductometric titration of extremely weak acid (phenol) having pK values larger than 9 were made. As is evident from Fig. 12, which shows theoretical conductometric titration curves of phenols having pK values 9∼12, one can calculate the equivalence-point in so far as the pK values of the phenols are smaller than 10; it is, however, impossible to find the equivalence-point when pK values are larger than 10. As the calculated titration curve for pK 12 is nearly linear, it is expected that the pK value of phenolic hydroxyl group of type II is 12 or larger.
Stability of Cobalt (III) and Chromium (III) Ammine Complexes in a Strongly Alkaline Solution
Authors: Yoneda Hayami
Published: July 2006

The rate of decomposition of the cobalt (III) and chromium (III) hexammine and monoaquopentammine complexes in an alkaline solution was measured. The activation energies of the decomposition were found to be 36, 32, 31 and 31 Kcal/ mole for [Co(NH3)6]3+, [Co(NH3)5H2O]3+, [Cr(NH3)6]3+ and [Cr(NH3)5H2O]3+ respectively. At the same time the infrared absorption spectra of these complexes were also measured. The frequencies of the rocking vibration of the coordinated ammonia were found to be 815, 853, 744 and 747 cm−1 for [Co(NH3)6]3+, [Co(NH3)5H2O]3+, [Cr(NH3)6]3+ and [Cr(NH3)5H2O]3+ respectively. From these results it was concluded that the decomposition of the cobalt (III) ammine complex was not a mere replacement of the coordinated ammonia by hydroxyl ion, but a reaction through the proton dissociation step as exemplified in the following scheme

[Co(NH_3)_6]^3++OH^-→[Co(NH_3)_5NH_2]^2++H_2O,

while, in the chromium (III) ammine complex, the decomposition was inferred to proceed through a substitution of hydroxyl ion for the coordnated ammonia.
The Separation of Tellurite, Selenite and Sulfite Ions by Anion-Exchange Resins
Authors: Iguchi Akira
Published: July 2006

1. The distribution coefficients of tellurite, selenite and sulfite in neutral nitrate solution and alkaline hydroxide solution were measured and the results suggest the presence of an acid salt ion HXO3− in neutral solution.

2. By the addition of ammonia to the eluant solution, the distribution coefficient of these salts in nitrate solution was increased, but in hydroxide solution it was decreased.

3. By the addition of ethanol to the eluant solution containing nitrate and ammonia, the distribution coefficient of sulfite increased, but that of tellurite and selenite remained constant even up to 75%. On the contrary, in the addition of ethanol to the hydroxide solution, the distribution coefficient of sulfite decreased, while that of tellurite and selenite increased at first and then decreased.

4. By using these results a complete separation of tellurite, selenite and sulfite was accomplished by the anion exchange chromatographic method using an alkaline eluant.
Ultraviolet Absorption Spectra and the Electronic Structure of Metallic Complexes. II. Cyanide Complexes
Authors: Kida Sigeo , Fujita Junnosuke , Nakamoto Kazuo , Tsuchida Ryutaro
Published: July 2006

The energy levels of the cyanide complexes–hexacyano chromium (III)

[Cr(CN)6]3−, hexacyno cobalt (III)

[Co(CN)6]3−, tetracyano nickel(II)

[Ni(CN)4]2−, and tetracyano copper (I) [Cu(CN)4]3 ions have been calculated by the semi-emprical M.O. method taking π-orbitals of the ligands into consideration. The ionization potentials used have been determined so that the calculated charge distribution does not contradict that obtained from Pauling’s neutrality principle. The stability and the magnetic property of these complexes have been well interpreted by our calculation. The results have revealed that the first and the second bands of hexacyano chromium (III) [Co(CN)6]3− and hexacyano cobalt (III) [Co(CN)6]3− are attributable to f′2g→ e′g transitions which are of the similar character to the first and the second bands of hexammine cobalt (III) [Co(NH3)6]3+, although the ground level, f′2g combines strongly with the π-orbitals of the ligands. In tetracyano nickel(II) [Ni(CN)4]2−, the “second band” is hidden by the allowed transition. For tetracyano copper (I) [Cu(CN)4]3−, there is no band corresponding to “the first and the second band”.
The Ignition of Hydrogen-Oxygen Mixture by Shock Wave. I. The Condition for Shock Ignition for Hydrogen-Oxygen Mixture
Authors: Suzuki Momotaro , Miyama Hajime , Fujimoto Shiro
Published: July 2006

Using the shock tube, the authors measured the minimum ignition pressure P1 of the reservoir for the hydrogen-oxygen mixture of various pressures (P0) and various compositions, and obtained the following results.

1) The higher the value of P0, the easier the ignition.

2) The concentration range of hydrogen in the gaseous mixture for shock ignition is 4∼94%, and the minimum value of P1⁄P0 was found in the gaseous mixture of about 40∼50% hydrogen, when P0 is over 200 mmHg.

3) The ignition is easier by the use of a shock tube with a conical end rather than that with a plane end.
Surface Films of Physically and Chemically Treated Ovalbumin (Dynamic Studies on Monolayer. II)
Authors: Kashiwagi Maresuke
Published: July 2006

Monolayer properties of acid, alkali and heat-treated ovalbumin are investigated from the measurements of surface pressure changes with time and surface pressurearea diagrams.

These treated specimens are found to be characteristically different from the untreated native protein in their surface behavior. The process of surface denaturation is also discussed.
Phase Relationship in the System 3CaO·P2O5–MgO·2SiO2–SiO2
Authors: Sata ToshiyuKi
Published: July 2006

The phase relationship in the system 3CaO·P2O5–CaO·MgO·2SiO2–SiO2 was investigated by the usual quenching method. The two partial systems 3CaO·P2O5–SiO2 and CaO·MgO·2SiO2–SiO2 have already been reported by previous investigators. Another partial system 3CaO·P2O5–CaO·MgO·2SiO2 seems to be approximately binary, whose eutectic is located at 39% of 3CaO·P2O5 and 61% of CaO·MgO·2SiO2, and at 1311±4°C. In the region rich in 3CaO·P2O5, it was observed that the crystallization velocity of diopside is rather slow under the solidus temperature, that the transition temperature of tricalcium phosphate is considerably increased with diopside content, and that β-tricalicium phosphate apparently makes solid solution with diopside (19 wt.%).

The system 3CaO·P2O5–CaO·MgO·2SiO2–SiO2 is of a perfect ternary one, whose eutectic is at 36% of 3CaO·P2O5, 59% of CaO·MgO·2SiO2 and 5% of SiO2, and at 1277±3°C. Its isotherms of the liquidus surface were approximately represented.
Kinetics of the Acid-Catalyzed Peroxide Oxidation of 4-Hydroxybenzaldehyde in Acetic Acid
Authors: Ogata Yoshiro , Tabushi Iwao
Published: July 2006

The sulfuric acid-catalyzed oxidations of 4-hydroxybenzaldehyde with hydrogen peroxide in aqueous acetic acid were kinetically investigated at 15° and 20° by iodometric estimation of the peroxides. The rates of peroxide consumption were found to be proportional to the product of the concentrations of hydroxybenzaldehyde and peroxide, when the aldehyde was added after the equilibrium between hydrogen peroxide and peracetic acid was attained. The rate constant is a linear function of Hammett acidity function h0.

Hydrogen peroxide itself reacts slowly with the aldehyde, but it reacts more easily through the formation of peracetic acid. A mechanism involving a ratedetermining attack of protonated and free peracetic acid was postulated and discussed.
The Kinetic Study of Surface-chemical Reactions at Extremely Low Pressures. IV. The Thermal Reaction between Water Vapor and a Tungsten Filament. Part IV
Authors: Hamamura Takuya
Published: July 2006

1) Reaction product vaporizes from the filament as tungsten trioxide and its colorless deposit is reduced with hydrogen liberated by the reaction. Consequently, the blue deposit having the mean apparent composition of WO2.80 can be obtained.

2) The WO3 deposit is reduced readily with atomic hydrogen down to WO2.80, but the reduction rate becomes appreciably slower at the lower oxidation state.

3) Oxygen is not contained in hydrogen. This suggests that WO3 is not formed by a reaction of tungsten with gaseous oxygen liberated by thermal decomposition of water vapor, but is formed directly by a reaction of tungsten with water vapor.
Polymerization of Methyl Methacrylate Initiated by Phenylazo p-Tolyl Sulfone
Authors: Uehara Ryoichi
Published: July 2006

The effects of phenylazo p-tolyl sulfone upon the polymerization of methyl methacrylate were examined. In the solutionpolymerization in benzene, the initial rate of polymerization was linearly dependent respectively upon the square root of the concentration of phenylazo p-tolyl sulfone and upon the concentration of methyl methacrylate. A unimolecular first order decomposition of phenylazo p-tolyl sulfone is suggeted as the initiating reaction of the polymerization. Dimethylaniline acted as an accelerator for this polymerization. In this case, the initial rate of polymerization was linearly proportional to the square root of each of the concentrations of phenylazo p-tolyl sulfone and dimethylaniline. A bimolecular reaction between phenylazo p-tolyl sulfone and dimethylaniline has been proposed for the acceleration of the polymerization.
π-Electronic Structures of o-Quinones
Authors: Kuboyama Akira
Published: July 2006

Electronic structures of o-benzoquinone, β-naphthoquinone and phenanthrenequinone were studied with the simple MO method, using the same integral values as those adopted in the self-consistent MO calculation for o-benzoquinone. As for charge distributions, the negative charges of oxygen atoms slightly increase in the order of o-benzoquinone, β-naphtho-quinone, and phenanthrenequinone. The calculated dipole moments (6.6, 9.5 and 8.4 D for o-benzoquinone, β-naphtho-quinone and phenanthrenequinone, respectively) seem a little greater than the experimental values. As for bond orders, reasonable results were obtained. The calculated results predict the existence of a doublet with a large splitting constant (ca. 4.5 gauss) in the hfs of the electron paramagnetic resonance absorption of β-naphtho-semiquinone ion. Three problems concerning the near UV absorption bands [1) the similarity among the π–π transition bands of the three o-quinones, 2) the relative magnitude of the n–π transition energy of o-benzoquinone, β-naphtho-quinone, and phenanthrenequinone, 3) the effect of the electron-donating group on the π–π transition bands of o-benzoqui-none and β-naphthoquinone] can be clearly explained by the calculated results, as in the cases of the p-quinones.
Photochemical Reactions between Methylene Blue and Tri-, Di- and Monomethylamine. III. The Behavior of Methylene Blue in the Presence of Oxygen
Authors: Obata Hiroshi , Kogasaka Kenichi , Koizumi Masao
Published: July 2006

In connection with the reversible photo-reduction of methylene blue in vacuo published already, the rate of the consumption of oxygen in the irradiated solution of methylene blue containing three kinds of amine was measured. In addition, the irreversible photoöxidation of the aqueous methylene blue solution was studied, particular attention being paid to the effect of oxygen pressure and pH on the rate. The following conclusions were drawn from the above two series of experiments.

1) In the irradiated aqueous solution of methylene blue containing trimethyl-amine, oxygen does not affect the T state of dye and attacks only the leuco form, reproducing the dye molecule. Oxygen reacts almost instantaneously with the leucodye as soon as the former is produced.

2) In the aqueous solution of methylene blue (with no amine added) the reactivity of T state against oxygen is about one order less than that of eosine in the analogous condition. The deactivation of T state by oxygen in case of methylene blue is about 10−7 times greater than that by water.

3) Comparison of the above results 1 and 2 (taking into account of the result that in the evacuated state the reactivity of T state against OH− and amine is much less than the deactivation by water) leads to the conclusion that the deactivation of T state by oxygen is almost completely suppressed by the addition of amine.

4) The rate of irreversible photoöxida-tion increases with the alkalinity of the solution. But in the buffer solution containing N-compound like veronal, a competitive reaction somewhat like that between methylene blue and amine occurs. It is pointed out that enough caution must be taken for such a possibility when the buffer solutions are employed.
Heats of Combustion and Formation of Lower Members of Methyl-and Etnyl-methoxypolysiloxanes
Authors: Tanaka Toshio
Published: July 2006

1. The heats of combustion of lower members of methyl- and ethyl-methoxy-polysiloxanes have been measured at 20°C and constant volume, and the corresponding heats of combustion and formation in isobaric process have been calculated.

2. The bond energy term in structural unit of (Remark: Graphics omitted.) has been calculated from the heat of formation, and it has been found that its value increases with the polymer sizes of the members. Finally, the (Remark: Graphics omitted.) has been compared with that expected from the additive law of bond energy, and the lowering of bond energy in these molecules has been discussed in view of the resonance effect.
Studies on the Cobalt(III) Complexes of Monothiophosphate Ion
Authors: Hidaka Jinsai , Fujita Junnosuke , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

Two new complexes, sodium di-monothiophosphato-bis-ethylenediamine cobaltate(III) octa-hydrate and monothiophosphato-bis-ethylenediamine-cobalt(III) dihydrate, have been synthesized by the reaction of trans-dichloro-bis-ethylenediamine cobalt(III) chloride with anhydrous sodium monothiophosphate in cold aqueous solution. The infrared and the visible and ultraviolet absorption spectra of these compounds and of the corresponding thiosulfato-Co(III) complexes have been measured and discussed in relation to the structures of the complexes.
Characteristics of Alginic Acid as a Cation Exchanger and its Application to the Separation of Thorium(IV) and Cerium(III) Ions
Authors: Takahashi Takeo , Miyake Shingo
Published: July 2006

The apparent dissociation constant of alginic acid was measured by means of the neutralization with 0.1 n potassium hydroxide in 1 n potassium chloride solution and found to have a value of 3.1. This value is between that of IR-120 and of IRC-50, which is obtained by the same manner of measurement. The values of Kd for thorium(IV) and cerium(III) ions in regard to these three exchangers were measured, showing that the value in regard to alginic acid is also situated between the other two.

The application of alginic acid to the fractional separation of thorium(IV) and cerium(III) ions gave a satisfactory result.
The Fundamental Conditions for Countercurrent Distribution Studies of Clupeine
Authors: Sawada Fumio
Published: July 2006

The conditions and solvent system suitable for C.C.D. of clupeine sulfate, were systematically studied and the following results were obtained.

1. In the solvent system consisting of n-butanol and aqueous hydrochloric, acetic or picric acid, the partition coefficient (K) of clupeine sulfate was almost zero.

2. In the system consisting of n-butanol and aqueous dichloroacetic, trichloroacetic or p-toluenesulfonic acid, the K-value increased with the increase of the acid concentration at a constant solute concentration. In the last system, at a constant acid concentration, the K-value decreased with the increase of the solute concentration.

3. The system consisting of n-butanol and an equal volume of aqueous solution containing 0.12 m sodium p-toluenesulf onate and 0.40 or 0.48m sodium chloride was found to satisfy all the conditions necessary for the C.C.D. of clupeine sulfate.
Wet Grinding on Kaolin Minerals
Authors: Takahashi Hiroshi
Published: July 2006

The effects of wet grinding on kaolin minerals were examined by X-ray diffraction method, differential thermal analysis, electron microscopy and density measurement. The effects of wet grinding of kaolin minerals are different from those of dry grinding, particularly at the early stage of grinding. It has been considered that the force of dry grinding acts as fracturing and cleaving forces, while the force of wet grinding acts as a weak cleaving force for kaolinite and as a weak fracturing force for halloysite in the early stage of grinding. It has been revealed that the effects of wet grinding depend on the shape of crystal in the original kaolin mineral in the early stage of grinding, and beyond a certain stage of grinding, they depend on the structural per-fectness of the kaolin layer, that is, the internal degree of crystallinity of the original kaolin mineral.
Rapid Analysis of Gamma-Emitters Using Gamma-Ray Scintillation Spectrometer. II. Determination of 137Cs in Fission Products
Authors: Aoki Fumio , Yajima Seishi , Kurosawa Toshio
Published: July 2006

A method for the rapid determination of 137Cs in fission products has been studied. Simple and reliable analysis is possible by combining oxalate- and carbonate-form anion exchange resin and a gamma-ray scintillation spectrometer as follows.

Take several samples of equal quantity from a given fission products solution. Add various known quantities of pure 137Cs to them respectively. Extract the bulk of uranium with T. B. P. in diethyl ether. Treat them through a mixed bed of carbonate- and oxalate-form anion exchange resin. Measure each aliquot using a gamma-ray scintillation spectrometer. Plot the real peak height of the 0.66 MeV gamma vs. the added 137Cs quantity, and determine the straight line by the method of least square. Find the intersection of the straight line and the abscissa.

The quantity in question is given by the length of the abscissa between the intersection and the origin.
Studies on the Sapogenins of Dioscorea tokoro Makino. I. The Structure of Tokorogenic Acid
Authors: Morita Katsura
Published: July 2006

(1) Oxidation of tokorogenin by means of chromic anhydride in acetic acid, periodic acid in ethanol and lead tetraacetate in aqueous acetic acid led to the conclusion that tokorogenin must have a glycerol moiety in ring A of the steroid nucleus.

(2) Tokorogenic acid, an oxidation product from tokorogenin, forms an anhydride by heating with acetic anhydride and gives rise to a monomethyl ester (α-monoester) by treatment with methanol and hydrogen chloride, while alkaline hydrolysis of the dimethyl ester of the acid furnishes a different monomethyl ester (β-monoester). The same α-monoester also results from tokorogenic anhydride by the action of alkali in a methanol solution.

(3) On the basis of the theoretical considerations and the afore-mentioned observations in the tokorogenic acid series compared with those in the camphoric acid and etiobilienic acid series, it is concluded that tokorogenic acid has to be defined as 1,3-seco-2-nor-spirostan-1,3-dioic acid (II) and hence tokorogenin as spirostan-1,2,3-triol (I).
Phenothiazine Derivatives. VI. Reactions of Some Substituted Phenothiazines with Thionyl Chloride
Authors: Fujimoto Manabu
Published: July 2006

Some phenothiazine derivatives including dyes and drugs were treated with thionyl chloride and five new polychlorinated products and six known were obtained.
Analysis of Organic Compounds by Flame Spectrometry. I. Determination of Chlorine in Organic Compounds by Band Spectra of Cuprous Chloride
Authors: Maruyama Masao , Seno Setsuya
Published: July 2006

Examinations were made on the band spectrum of cuprous chloride based on the Beilstein’s reaction in oxy-hydrogen flame. Determination of chlorine in organic chlorine compounds was attempted by using dimethylformamide containing copper as a solvent and a band peak of 435.4 mμ of cuprous chloride.

In order to decrease the effect of C2-Swan band that is produced on combustion of organic compounds, and to increase the sensitivity of cuprous chloride band spectrum, combustion gas was maintained at high oxygen pressure; 1.76 kg./cm2 (25 1b./in2 gauge), and low hydrogen pressure ; 1st, 0.035 kg./cm2 (0.5 1b./in2 gauge), 2nd, 10 cm. water column.

γ-BHC was used as the standard and determination was carried out on 11 kinds of organic chlorine compounds, and good results were obtained with samples other than liquid, metal salts, and hydrochlorides. The determinable range for chlorine is 0.005∼3.1 m concentration.
Confirmation of the Formation of Colloidal Particles in Aqueous Cobalt Salt Solution by Radiotracer Electrodialysis
Authors: Sasaki Tsunetaka , Osaka Katsuyoshi
Published: July 2006

(1) Dissolved state of cobalt ions in 10−3 molar aqueous solution of cobaltous chloride, varying in pH, was studied by a radiotracer electrodialysis coupled with an ordinary filtration.

(2) Formation of colloidal particles permeable to filter paper but not permeable to cellophane membrane were confirmed in the solution, in the region of pH from 6 to 10.

(3) Macroscopic precipitates of cobaltous hydroxide began to form at about pH 8 and practically all cobalt ions were precipitated at a pH greater than 10.

(4) The value of pH of insoluble cobaltous hydroxide formation in aqueous 10−3 molar cobalt salt solution calculated from the solubility product of cobaltous hydroxide was found to be situated between the pH of the initiation of colloidal particle formation and the pH of the initiation of macroscopic agglomerate formation.
Hydrogen Peroxide Oxidation. I. A New Selenium Dioxide-Catalyzed Synthesis of Carboxylic Acids from Aliphatic Ketones Accompanied by Rearrangement of Alkyl Groups
Authors: Sonoda Noboru , Tsutsumi Shigeru
Published: July 2006

1) Selenium dioxide catalyzed oxidation of aliphatic ketones with hydrogen peroxide gave carboxylic acids which were produced by the rearrangement of the alkyl group as shown by equation 5.

2) Acetone, methyl ethyl ketone, methyl n-propyl ketone and diethyl ketone were selected as starting materials. The main rearrangement observed is due to the migration of the alkyl group having a smaller number of carbon atoms to the α-carbon atom of the larger alkyl group, and the migration of the alkyl group with a larger number of carbon atoms to the smaller one also occurs in some degree.

3) The yield of the generated acids were about 30∼40% of the theoretical amounts based on the ketones used. Small amounts of cleavage products were obtained as the by-products in all cases. Both of the cleavaged groups from a ketone were oxidized to acids in these reaction systems.

4) The most probable catalytic form seems to be peroxyselenious acid which may be produced by the oxidation of selenium dioxide with hydrogen peroxide (equation 6). Inferential reaction mechanism was discussed.
Indirect Complexometric Titration of Beryllium with Ethylenediaminetetraacetic Acid
Authors: Misumi Seizo , Taketatsu Tomitsugu
Published: July 2006

When Luteo salt was added to beryllium carbonate complex solution, the precipitate [Co(NH3)6] [(H2O)2Be2(CO3)2(OH)3]·3H2O was obtained. In this experiment, the indirect determination of beryllium was tried by the titration of the cobalt content in the precipitate with EDTA. The following procedures were examined mainly; the formation of the precipitate II, the decomposition of the precipitate and titration of cobalt in the presence of beryllium. In the optimum conditions, 0.70 to 3.50 mg. of beryllium were determined quantitatively. This method could be applied to separation and determination of beryllium from iron(III), aluminum and magnesium by using EDTA as a masking agent.
Preparation of Chloropolysilane from the Copper-catalyzed Reaction of Silicon Metal and Hydrogen Chloride
Authors: Shiihara Isao , Iyoda Jun
Published: July 2006

The copper catalyzed reaction of silicon metal powder with hydrogen chloride by flow method was studied in order to find a convenient preparative method of chloropolysilane, and also to elucidate the mechanism of this reaction.

This reaction was found to start at about 170∼230°C, and once the reaction occurred, the contact mass is activated and the reaction takes place even at 170°C. When the most adequate conditions were adopted, chloropolysilanes were obtained in the condensate as efficiently as 30 wt.% yield based on hydrogen chloride.

As to the mechanism of the reaction, it seems to be plausible that the first step of the reaction is an attack of hydrogen chloride on aluminum which is usually present in the commercial silicon metal. The second step is the reaction between silicon hydride, which is derived from the first step reaction upon the silicon contact mass and metallic copper forming the silicon-copper bonding. The third step is the cleavage reaction of copper-activated silicon by hydrogen chloride to produce chlorosilanes under the presence of aluminum chloride. The aluminum chloride is also derived from the first step reaction, and copper is regenerated in metal form which can circulate among the latter two reaction steps as long as the effective silicon component is present.
The Roles of Prolyl Residue in Polypeptide Monolayers. II. On the Surface Viscosity and Types of Monolayers
Authors: Ikeda Shoichi , Isemura Toshizo
Published: July 2006

To investigate the roles of prolyl residue in polypeptide monolayers, surface viscosity was measured for the monolayers of poly-Dl-alanine, poly-l-prolyl-l-leucylglycine and copoly-1:1:1-(l-proline, l-leucine, Dl-alanine).

For the monolayer of poly-Dl-alanine which is of condensed type, the surface viscosity was found to rise at the area larger than the close-packed area and scarcely to be dependent of temperature. This result was correlated with that observed in the glassy state of polymers in bulk and interpreted by assuming that the polypeptide chain is rigid owing to the strong interaction. For the films of the other two polypeptides which are of expanded type appreciable surface viscosities were manifested at the areas much smaller than their close-packed areas and temperature exerted marked influence on surface viscosities. Their chain configurations were considered to be flexible owing to the weak interaction, since the flows in films occur as in melt of polymers in bulk.

Further evidence for this inference was obtained from the results on dependences of surface viscosity on surface pressure and temperature. The dependences were found to follow Eyring’s equation of surface viscosity. It was found that in the monolayer of poly-Dl-alanine a unit of flow is roughly composed of a molecule and its chain is rather coiled at the interface, but the chains of the other two polypeptides are in a regularly folded configuration partly submerged into the aqueous phase when compressed, as they are flexible.

The difference in surface viscosity behavior between poly-Dl-alanine and the other two polypeptides was related to the condensed and expanded nature of films, which is defined by the content and distribution of prolyl residues in polypeptide chains. It was, however, observed that poly-l-prolyl-l-leucylglycine and copoly-1:1:1-(l-proline, l-leucine, Dl-alanine) exhibit the same surface viscosity behavior, irrespective of their different distribution of prolyl residues in chains, while the former has a higher surface pressure than the latter.

All the results obtained were found to confirm the view deduced from the surface pressure and potential measurements.
Role of Dielectric Constant at the Miscibility Point in the Ternary System 2-Propanol-Water and Carbon Tetrachloride
Authors: Suryanarayana C V , Somasundaram K M
Published: July 2006

To understand why a heterogeneous system of two immiscible liquids so exists without mixing we have made a new approach of studying the physical properties of the system just at the transition of the disappearance of the phase boundary after the addition of an optimum amount of a third component which is freely miscible with the two heterogeneous components thus resulting in the formation of a ternary system. At the transition of the disappearance of the phase boundary we have found that \underset3ΣL3x3=L1,2,3, wherein L represents volume polarization and x the mole fraction, holds good. The implications of the validity of the above equation have been discussed.
Stereoregular Polymers. II. Polymerization of Alkenyltrimethylsilanes with Ziegler Catalyst
Authors: Murahashi Shunsuke , Nozakura Shun’ichi , Sumi Masao
Published: July 2006

Vinyl-(I), allyl-(II), and 3-butenyl-trimethylsilane(III) were polymerized at 70°C in n-heptane with the heterogeneous catalyst of Ziegler’s type. The monomer I gave only a small yield of polymer, while the monomers II and III gave moderate amounts of polymers.

The amorphous and crystalline polymers of these monomers were separated by extraction with appropriate solvents. As regards the crystalline polymers, solubility property, density, dilatometrical melting point, and X-ray spectra were described. Glass transition temperatures of the amorphous polymers are also determined.
Formation and Aging of Precipitates. X. An Electron Micro-Diffraction Study on Crystal Habit of Barium Sulfate Precipitates
Authors: Takiyama Kazuyoshi
Published: July 2006

Barium sulfate precipitates in a form of rectangular perfect crystal from a solution of low initial concentration, and in a form of dendrite from a solution of higher initial concentration. They are platelets grown along (100) plane. The short- and long-axes of rectangular crystal are b- and c-axes respectively. The dendrite grows along b- and c-axes, or along the direction perpendicular to the plane of {011} group.