bluuebunny/crossref_metadata_2025 huggingface dataset:
Adsorption of Hydrogen on Copper-Magnesia Catalysts
Authors: Takeuchi Toyosaburo , Sakaguchi Masakazu
Published: July 2006

(1) The adsorption of hydrogen on a copper catalyst containing 1% magnesia sintered at various temperatures has been investigated at 100° and 160°C, and compared with that on copper alone. The addition of magnesia increases markedly both the surface area and the rate of adsorption. The latter increase, however, is far beyond the increase in surface area.

(2) The hydrogen adsorption per unit area of the copper magnesia catalyst is less than that on pure copper, and decreases with increasing heat treatment. The adsorption of hydrogen on magnesia powder is immeasurably small. The heat curves on differently heated catalysts do not agree with each other, but approximately do so if the effective area for hydrogen adsorption is taken into consideration. The adsorption heat for a low coverage is certainly greater on the magnesia added copper than on copper alone.

(3) By aid of the electron diffraction study, it is concluded that the magnesia in the catalysts exists on the surface and forms microcrystal particles. Presumably, copper in the magnesia added catalyst is modified by the oxygen of the magnesia and irregular defects are formed on the surface in the presence of magnesia.
Photochemical Reactions between Methylene Blue and Tri-, Di- and Monomethylamine. II
Authors: Obata Hiroshi , Koizumi Masao
Published: July 2006

The effects of various factors upon the photobleaching of methylene blue in the evacuated aqueous solution by means of mono-, di- and trimethylamine, were studied experimentally, and the result were analyzed by the rate formula presented in the preceding paper on the basis of the following scheme;

(Remark: Graphics omitted.)

The results obtained can be summarized as follows: k1 is written in the form; k1=k10[OH−][TA]I0. k2 and k3 are also proportional to [OH−] and they both increase monotonously with the light intensity and amine concentration.

In addition, the photobleaching was examined in the presence of Fe+++ and Cu−−. It was found that in the case of Fe+++, k3 is much decreased while k1 and k2 are scarcely affected. The absorption spectra of the intermediate were observed more prominently than when no Fe+++ was present. From these results it was concluded that Fe+++ stabilizes the intermediate. In case of Cu++ some induction period was observed during which Cu precipitates, and its duration was found to be proportional to the concentration of Cu++. From these results it was tentatively concluded that Cu++ attacks the intermediate.
The Surface of Copper-Nickel Catalyst. II. Adsorption of Hydrogen on Copper, Nickel, and Copper-Nickel Catalysts
Authors: Takeuchi Toyosaburo , Sakaguchi Masakazu
Published: July 2006

(1) The adsorption of hydrogen on copper, nickel and copper-nickel (containing 1% nickel) catalysts, prepared from the nitrates of copper and nickel were observed in the range of 100° to 130° or 120°C.

(2) The shrinkage of surface with increase of reduction temperature was smaller for copper-nickel catalyst than for pure copper catalyst.

(3) The rates of adsorption of hydrogen on copper and copper-nickel catalysts were far smaller than that of nickel; and the adsorption amount per unit area was the greatest for copper-nickel catalyst, while that of nickel catalyst was the smallest among the three.

(4) The differential heats of adsorption of hydrogen at near zero coverage were given as 10.6kcal. both for copper and copper-nickel catalysts, and 24.2kcal. for nickel catalyst.

(5) On the basis of the coincidence of the adsorption heats of copper and copper-nickel catalyst, it is suggested that the nickel paarticles supposed to exist on the surface of the copper-nickel catalyst may be covered with copper atoms.
Chemical Studies on Wood Hemicelluloses. I. On the Hemicellulose of Japanese Beech Wood. I
Authors: Machida Seishi , Inano Mitsumasa , Matsumura Yasuo
Published: July 2006

1. A suitable method of analysing wood hemicelluloses by paper chromatography was studied.

2. The behavior of hemicellulose in Japanese beech wood (Fagus crenata Blume) during the chemical pulping processes was studied; the state of the hemicelluloses in wood pulp was investigated.
The Separation of α-Glycerophosphoric Acid from its β-Isomer by Paper Chromatography
Authors: Urakami Chieko , Kakutani Yoshiko
Published: July 2006

The behaviors of α- and β-glycerophosphoric acids, their alkaline metal and ammonium salts on alumina impregnated paper, developed with a mixed solvent of methanol and ammonia (60:5), have been described. It has been demonstrated that a mixture of the sodium salts of the two acids may be completely separated in this way without hydrolysis or migration of the phosphoryl group. The method also affords a distinct separation of α-glycerophosphoric acid from a mixture of the inorganic phosphates, the β-glycerophosphates, and the glucose 1- and 6-phosphates; and also of the β-glycerophosphates from a mixture of the inorganic phosphates, the glucose 1-and 6-phosphates. The mechanisms possibly involved have been discussed.
Dipole Moment and Bond Character of Propargyl Halides and Mono- and Di-chlorobutynes
Authors: Chiba Takehiko , Shimozawa Takashi , Miyagawa Ichiro , Morino Yonezo
Published: July 2006

The dipole moments of propargyl chloride, bromide and monochlorobutyne in the gaseous state are measured to be 1.65D,1.52D and 2.17D respectively. The moment of propargyl chloride and bromide are considerably smaller than the saturated one even though the correction of C≡C—C skeletal moment is taken into account. This is consistent with the —CH2Cl group moment of dichlorobutyne obtained in the preceding work. These results are inconsistent with the resonance scheme presented by Pauling et al. for propargyl halide. The anomaly is considered as a characteristic feature of the molecules having triple bonds of this kind. By taking all of the moments of dichloro- and monochlorobutynes and propargyl chloride into account, the bond moments, the induction moments and the direction of the resultants, are predicted as shown in Fig. 1.
Studies on the Dipole Moments of Acenaphthene and its Derivatives
Authors: Ishiguro Tetsuro , Chiba Takehiko , Gotoh Nobuyuki
Published: July 2006

The dipole moment of acenaphthene (I) was measured in the gaseous phase as 0.93D. Measurement in benzene solution at 25°C gave the following moment values: acenaphthene (I) 0.85D; 5-chloroacenaphthene (II) 2.50D ; and 5,6-dichloroacenaphthene (III) 3.85D. By the comparison with the moments of naphthalene derivatives it was shown that the moments of (II) and (III) are approximately equal to the sums of the moment of (I) and the moments arising from one and two C–Cl bonds, respectively.
Hydrogen Exchange and Isotope Effect on the Vinylation of Acetic Acid
Authors: Yamada Noboru
Published: July 2006

The mechanism of vinylation reaction of acetic acid was studied by the use of deuterium. The exchange of deuterium was found to occur between acetylene and acetic acid-d on zinc acetate-charcoal catalyst. The deuterium isotope effect of the reaction rate was also found, and the rate ratio, kD/kH, was 1.6 at 160°C. A mechanism of the reaction which contains a pre-equilibrium of intermediate ion formation, CH≡CH+H \ightleftarrows CH2=CH, CH2=CH+CH3COO−→CH2=CH·OCOCH3, was proposed and discussed.
Effects of Mercerization on the Lateral Order Distribution of Cellulose
Authors: Tsuda Yoshizo , Mukoyama Sadataka
Published: July 2006

Lateral order distributions of native and mercerized celluloses were compared and then the variation of distribution in the process of mercerization was investigated. It was concluded that mercerization generally induces broadening of distribution, and cotton linters pulp shows almost the same lateral order distribution after mercerization as those of wood pulps. The authors are grateful to Dr. K. Hoshina for permitting this publication.
Studies on the Organic Phosphorescence. IV. Quenching by Inorganic Salts
Authors: Kato Shunji , Kimura Ko , Koizumi Masao
Published: July 2006

The effects of the addition of inorganic salts upon trypaflavine-silica gel phosphor were studied, and it was found that decay curves are not affected much by any of the metallic ions except cupric ion. On the contrary, the intensity of pure fluorescence (IL–IP0) was reduced more or less by many metallic ions. From these results, it was concluded that many metallic ions chiefly affect S′-state but not T- and M-state.

The result for cupric chloride was somewhat anomalous on the point that a cupric ion affects both S′- and T-state.

A general survey on the quenching action of various substances upon adsorbed trypaflavine phosphor was given.
Synthesis of dl-Sarkomycin (2-Methylenecyclopentanone-3-carboxylic Acid)
Authors: Toki Katsuyuki
Published: July 2006

dl-Sarkomycin (2-methylenecyclopentanone-3-carboxylic acid) was synthesized in a four-stage process starting from ethyl cyclopentanone-3-carboxylate, prepared by Kay’s procedure. Namely, ethyl cyclopentanone-3-carboxylate was converted into ethyl 2-(dialkylaminomethyl)-cyclopentanone-3-carboxylate and thence to ethyl 2-methylenecyclopentanone-3-carboxylate. The ester was hydrolyzed to 2-methylenecyclopentanone-3-carboxylic acid with diluted hydrochloric acid. The final product was a pale yellow oil and was effective in inhibiting the growth of Ehrlich carcinoma of mice.
Coprecipitation of a Trace Amount of Cesium with Thallous Salts
Authors: Yamagata Noboru , Yamagata Toshiko , Watanabe Sadakata
Published: July 2006

The possibility of coprecipitation of a trace amount of cesium with various thallous salts has been studied. The following salts were proved to be efficient: dipicrylaminate, cobaltinitrite, chloroplatinate, phosphotungstate and copper ferrocyanide; of those the dipicrylaminate method was recommended.

Only partial coprecipitation of cesium took place with thallous silicotungstate, phosphomolybdate, chloride, bromide, iodide and sulfide.
Carrier-free Separation of Cesium from Fission Products by the Use of Coprecipitation with Thallium (I) Dipicrylaminate
Authors: Yamagata Noboru , Watanabe Sadakata
Published: July 2006

A procedure has been presented for the separation of carrier-free cesium from the fission products. The method makes use of coprecipitation with thallium(I) dipicrylaminate followed by solvent extraction with methylisobutyl ketone in the presence of hydrochloric acid and an oxidizing agent. The recovery of active cesium is about 90% and the gross decontamination factor is more than 104.
A Phase Transition Study on the Mercerization of Cellulose
Authors: Tsuda Yoshizo
Published: July 2006

The phase transition ranges were obtained at 20°C and 45°C for the linters pulp, the sulfate pulp and the sulfite pulp. It was concluded that the resistance of the linters pulp against the mercerization is higher than those of the wood pulp, where as no difference is observed between the sulfate and the sulfite pulp. It was suggested also that the visual estimation of the X-ray diffraction diagrams may transition range.
Microscopic Studies on Fused Catalysts for Ammonia Synthesis. V. Conversion Test with A and B Constituents and Some Studies on “M” Type Crystal
Authors: Osumi Yoshio , Inoue Makoto
Published: July 2006

Iron synthetic ammonia catalyst (No. II-4)promoted with aluminium oxide, potassium oxide and calcium oxide was separated magnetically into two different sorts of powder, “A” with magnetite structure and “B” with “M” type structure. As to their catalytic activities for normal and high pressure conversion at temperatures between 400 and 520°C, it was found that “B” was less active than “A” particularly for the low temperature conversion. Some other properties of these powders are as follows:

(1) “B” powder becomes unstable when heated above 1000°C and changes into magnetite. Powder with the lattice structure of “M” type can be synthesized by sintering iron oxide at about 900°C with a sufficient amount of potassium nitrate or hydroxide, but it is completely non-magnetic.

(2) “A” and “B” powder showed almost equal rate of weight decrease when reduced in hydrogen gas or treated with acid solutions.

(3) The BET measurement carried out with “A” and “B” powder reduced in hydrogen revealed that the total specific surface area is almost equal for both “A” and “B” whereas the portion occupied by alkali molecules is larger for “B” powder.
Spectrochemical Study of Microscopic Crystals. XV. Structure and Light Absorption of Bis- (dimethylglyoximato) gold (III) Dichloro-aurate(I)
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Dichroism of [Au(dgH)2][AuCl2] has been determined in the visible and the ultraviolet region by the microscopic method. For the absorption band at about 60−70×1013/sec., absorption has been found to be about four and a half times as strong along the complex plane as along the direction normal to the plane.

From discussion on the result of the dichroism measurement, it has been concluded that the metal-to-metal interaction does not exist between the Au(I) and Au(III) ions in this crystal.
Measurements of the Amounts of Bound Water by Ultrasonic Interferometer. III. Application to Organic Electrolyte
Authors: Ito Koin , Shiio Hazime
Published: July 2006

1. The previously introduced theory on the amount of bound water and the compressibility of solute has been tested with the solutions of organic electrolytes.

2. The proposed procedure was found to be satisfactory and gave separately the values of the amount of bound water and the compressibility of solute in each case. These results appear to be proper compared with others.

3. The compressibility of the solute could be neglected in aminoacid solutions by the same reason as in the case of glucose where the solute is of low molecular weight.

4. It is shown that the amount of bound water of gelatin varies very little as pH of solution goes apart from the isoelectric point where the compressibility of gelatin molecule has a minimum value, as had been expected.
Studies on the Organic Reagents for the Inorganic Analysis. I. Phenylfluorone as Sensitive Reagent for Colorimetric Determination of Zirconium
Authors: Kimura Kenjiro , Sano Hirotoshi
Published: July 2006

Methods reported in the literature for the determination of zirconium are generally designed for relatively large amounts of this element, in spite of the fact that a procedure using colorimetric reagent for the determination of trace amounts is desirable. The systematic studies on the organic reagents for the spectrophoto-metric determination of several metals led us the phenylfluorone as one of the most sensitive reagents for the colorimetric determination of zirconium. The phenyl-flurone method recommended here, which is carried out in 0.1 n hydrochloric acid solution, shows the about forty or fifty times sensitivity of Alizarine Red S method and the several times of Quercetin method reported later as a sensitive reagent for zirconium. The solution becomes stable enough to carry on the colorimetric determination by adding some cyclohexanol and ethyl alcohol, although it is not true solution but colloidal.

On the other hand the investigation to find a phenylfluorone derivative to make a soluble complex with metals has succeeded recently. The new reagent, 2,3,7-tri-hydroxyl-9-(4-dimethylaminophenyl)-fluor-one, synthesized by the authors and Miss M. Asada give a soluble colored complex with germanium and make colorimetric procedure very convenient. This new reagent also forms a soluble intense colored complex with zirconium. This detailed investigation will be published before long.
On the Aggregation of Calf Thymus Histone
Authors: Ui Nobuo
Published: July 2006

The aggregation reaction of histone I, i. e., the main fraction of calf thymushistone, was studied by means of sedimentation, diffusion, viscosity measurement and electrophoresis. The aggregation was found to proceed usually at a temperature higher than 20°C, although it occurred at pH’s above 7 even at 0°C. High temperature, pH, ionic strength or protein concentration promoted the reaction. It was also found that sulfate ion was an effective aggregating agent.

The aggregation was not reversed by lowering the temperature, but disaggregation occurred when the ionic strength of the solution containing the aggregate was reduced by dialysis.

The aggregate was rather large in size. It consisted of about 30 molecules of his-tone I under certain aging conditions (pH 5.0) and had nearly the same frictional ratio as that of the monomer. Electro-phoretic mobility slightly increased with aggregation at pH 5.0.

On the basis of the data presented, a possible mechanism in forming the aggregate was discussed.
Spectrochemical Study of Microscopic Crystals. XVI. Structure of Cupric Formate, Acetate and Propionate
Authors: Yamada Shoichiro , Nakamura Hiroji , Tsuchida Ryutaro
Published: July 2006

Dichroisms in the visible and the ultraviolet region have been determined by the microscopic method with cupric formate tetrahydrate, cupric acetate monohydrate, anhydrous cupric propionate and its mono-hydrate.

The cupric formate shows an absorption band at about 38–391013/sec. which is considered to be due to the copper ion in combination with the ligands. For this band, electric vector is much more strongly absorbed along the plane of the complex than in the direction normal to the plane. The dichroism and the absorption spectrum of the cupric formate are of the same type as those of most cupric complexes involving no special effect upon the complexes.

Cupric acetate monohydrate, anhydrous cupric propionate and its monohydrate show an absorption band of a new kind at about 80×1013/sec., in addition to a band at about 43×1013/sec. which corresponds to the band at about 40×1013/sec. of the cupric formate. The polarization for the band at 80×1013/sec. is the reverse of the polarization for the band at 43×1013/sec. From the appearance of the new band at 80×1013/sec. and the reversal of the polarization property with this band, it has been concluded that the cupric compounds examined in this work, except the formate, consist of dimeric molecules having a structure similar to that of cupric acetate monohydrate.

It has also been shown that the water of crystallization has very little effect upon the linkages within the complex molecules. The cupric compounds, except the formate, show in organic solvents a band at 80×1013/sec., involving the dimeric molecules in solution.
The Vapor Pressure of Germanium Dioxide
Authors: Shimazaki Eiichi , Matsumoto Noboru , Niwa Kichizo
Published: July 2006

The apparent vapor pressure of solid germanium dioxide, or the dissociation pressure for the reaction GeO2(c) = GeO(g)+1/2 O2(g), was measured over the temperature range 1,040 – 1,100°C by the Knudsen’s effusion method; the results are expressed by equation (4).

From the free energy equation, the heat of reaction, the free energy and the entropy change of the reaction were calculated as ΔH298=121.7±0.3kcal./mol., ΔG298=101.7kcal./mol. and ΔS298=67.3 e.u., respectively. The heat of reaction is in good agreement with the value calculated from accessible thermal data. The normal entropy of solid germanium dioxide was calculated as S298=10.8±1.0 e.u., which is in agreement with the computed value obtained by Bues and von Wartenberg.
Rapid Separation of Radioactive Strontium by Solvent Extraction with TTA-Hexone
Authors: Kiba Toshiyasu , Mizukami Shigeru
Published: July 2006

Radioactive strontium in mixed fission products could be rapidly separated by the two-step extraction deviced by the authors. The solution of the material was first adjusted to pH 7 and extracted with 0.05 m TTA-benzene. By this treatment rare earths and yttrium were made to go into the organic phase out of the solution. The remaining aqueous phase was transferred into another separatory funnel, adjusted to pH 8, and extracted with 0.05 m TTA-hexone. In this case the radioactive strontium was completely extracted into the organic phase. Only less than 5% of ruthenium present in the solution was extracted at the same time. Detailed data of the experiments on the extraction involving the determination of distribution coefficient, and the equilibrium constant were tabullated.
Electronic Structure of Phenol
Authors: Nishimoto Kichisuke , Fujishiro Ryoichi
Published: July 2006

The electronic structure and spectra of phenol was studied from the semi-empirical point of view, using the LCAO-ASP-CI-MO method. The excitation energies and oscillator strengths of transitions to lower excited states were calculated. The agreement between the calculated and the observed values is very good. The charge distribution, bond orders and the π-electronic dipole moment are also calculated.
Studies on the Thermal Decomposition of Cellulose Nitrate by Means of the Recording Thermal Balance
Authors: Abe Takehiro , Tobisawa Sh\={o}taro , Nomura Y\={o}kan
Published: July 2006

(1) The cellulose nitrate containing 10.6% of nitrogen decomposes above about 160°C. There appear distinct breaking points on the decomposition curves at constant temperatures slightly above the decomposition point. The higher the constant temperature of reaction, the greater becomes the decomposition loss in weight.

(2) The thermal decomposition after preheating at a temperature slightly below the decomposition point for an hour or so gives a greater loss of decomposition than that without preheating.

(3) The cellulose nitrate kept previously under a reduced pressure of about 10−2mmHg yields a greater decomposition loss in weight than that without any treatment.
Studies on the Separation of Alkaline Earth Elements. V. Coprecipitation of Radium in the Induced Precipitate of Lead Sulfate
Authors: Shinagawa Mutsuaki , Murata Toshifumi
Published: July 2006

A solution of pH 5.50 composed of 0.096 m lead nitrate, 2.07 m ammonium acetate, 1−5×10−4  m barium and 5–50 μC radium per liter, produces an induced precipitate of lead sulfate in proportion to the amount of 0.5 m sulfuric acid added. Under the same conditions, in the absence of barium, a lead sulfate precipitate is obtained in proportion to the amount of sulfuric acid added. But the required amount of sulfuric acid to obtain the same amount of precipitate is larger in this case than that in the case of induction by barium.

In both of the above cases, the ratio of the amount of the radium coprecipitated to the original amount of radium in sample solution is almost constant, i. e. 92–97%, irrespective of the amount of lead sulfate precipitate or of sulfuric acid added. This tendency is the same as in the case of coprecipitation of barium with the induced precipitate of lead sulfate as shown in the previous paper. More than 90% of radium is carried down by a precipitate of lead sulfate of 8–20% of lead. Such an extent was not found in the case of the ordinary precipitation of lead sulfate, i. e. in the absence of the masking agent, ammonium acetate for lead ions.

In conclusion, the induced precipitation of lead sulfate by barium can be made use of as an efficient method of separation or concentration of radium. For a practical usage of this method, more detailed examination according to each sample should be conducted.
On the Ring Opening Reaction of ε-Caprolactam Derivatives
Authors: Yumoto Hirosuke , Ida Kenzaburoh , Ogata Naoya
Published: July 2006

The ring-chain equilibria,

(Remark: Graphics omitted.)

were investigated experimentally for ε-caprolactam derivatives and their results could be analyzed by the method similar to that for ε-caprolactam. For the monomethyl derivative the equilibrium shifts to the ring-form and ΔH has been estimated to be 2.3 kcal/mol. which is smaller than ΔH(=3.5 kcal/mol.) for the unsubstituted. For dimethyl and N-methyl or -methylol derivatives equilibria shift too much to the ring-form to give polymers at high temperatures. The average unit of the Brownian motion of polymer chain molecules, i. e. the segment, for the monomethyl derivative is 13.3 skeleton atoms which is smaller than 19 skeleton atoms for unsubstituted polycapramide; the substitution makes it easier for chain molecules to be kinky.
Study of Nickel Oxide-Kieselguhr Catalyst. IV. The Effect of Temperature upon the Initial Rate of Polymerization and the Amount of Initial Adsorption of Propylene
Authors: Kawaguchi Shinichi
Published: July 2006

The catalytic polymerization of propylene over a nickel oxide-kieselguhr catalyst was studied at constant volume and at 0, 20, 80, 100, 110.6 and 140 °C. The pressure-time curve was analyzed by means of the Zeldowitch type equation. The initial rate law, R0=k(v–v0), can again represent the data at 0 and 20°, but the ineffective amount of initial adsorption, v0, becomes zero at higher temperatures, resulting in a simple first-order rate law, R0=kv. The activation energies obtained between 0 and 20°, and among higher temperatures are 8.7 and 0.86 kcal./mole, respectively. The isosteric heats of initial adsorption are 7–8 and 1.9 kcal./mole in the respective temperature regions. The elementary process whose initial rate was measured is considered again to be slow chemisorption of propylene from the van der Waals layer onto the active site of the catalyst.
The Dielectric Properties of Thiacyclohexane
Authors: Kondo Seiichi , Matsumoto Masaru
Published: July 2006

1) The molecules are in the rotational states in the solid phases II, III and liquid phase, and not in the phase I.

2) There is an order-disorder transition in phase II which may have its origin in the molecular dipole rotation.

3) The dielectric behavior in phase III is similar to that of other polar plastic crystals.
Solvent Effects on the Fluorescence of Some π-Electron Systems Naphthylamine and Naphthol
Authors: Mataga Noboru
Published: July 2006

The enhancement or quenching of fluorescence intensity of naphthylamines and naphthol caused by hydrogen bonding with acetic acid esters or pyridine has been measured. By means of detailed analyses of the experimental results, it has been established that the shift of hydrogen bonding equilbrium toward the side of association is realized during the lifetime of excited state.

The cause of the shift has been interpreted on the basis of the theory of electron migration, and an evidence supporting the interpretation has been provided by measuring the solvent shift of fluorescence spectra. The mechanism of the fluorescence quenching has been discussed as due to the delocalization of π-electrons through the hydrogen bond.
Structure of Croconic Acid
Authors: Yamada Kiyoyuki , Mizuno Nobuhisa , Hirata Yoshimasa
Published: July 2006

The structure of croconic acid in solution and in the solid state has been studied. The undissociated molecule is represented by structure I and the ion by structure IV.
Capture of Radioactive Cesium onto a Phosphomolybdate Precipitate Layer and its Determination
Authors: Hara Tadashi
Published: July 2006

(1) Up to 500 μg. cesium dissolved in less than 2 liters of solution is quantitatively captured on the precipitate layer by filtering the cesium solution through it.

(2) The activity on the precipitate is proportional to the amount of cesium-137 present in the solution and consequently, the quantity of cesium-137 is easily determined.

(3) The mechanism of capturing cesium on the precipitate layer is believed to be due to the ion exchange phenomenon.

(4) Determination of the radioactive cesium by this method is not interfered with by the presence of a large amount of various substances except rubidium, cesium, thallium, tungstate and nitrite. Radioactive strontium and rare earth elements also interfere, but their interference may be prevented by pretreatment.

(5) Recovery of the radioactive cesium dissolved in one liter of either river or sea water are about 93%.
The Formic Acid Rearrangement of 2-Cyclohexyl-3-butyn-2-ol
Authors: Takeshima Tatsuo , Wakamatsu Kazuo , Furuhashi Akira
Published: July 2006

The formic acid rearrangement of ethynylcarbinols has been extended to 2-cyclohexyl-3-butyn-2-ol(II), a model carbinol in which the tertiary carbon atom and the methyl group are adjacent to the carbon atom attached to the hydroxyl group. The major rearrangement product consisted of a mixture of 3-cyclohexylidene-2-butanone(III) (ca. 28% yield) and a new aldehyde, 3-cyclohexyl-2-butenal(IV) (ca. 12% yield). The latter was hydrogenated to give 3-cyclohexylbutyraldehyde(V). These compounds were isolated and characterized.
Studies of Aggregation of Dodecylammonium Carboxylates in Carbon Tetrachloride by Infrared Absorption Spectra and Thermistors
Authors: Kitahara Ayao
Published: July 2006

Measurements of infrared absorption spectra and of vapor pressure depressions using a couple of matched thermistors were carried out with carbon tetrachloride solutions of dodecylammonium carboxylaf at varying concentrations. The absorption bands at 1710 and 1640 cm−1 were assigned to the carbonyl group of the monomer molecule which is formed by hydrogen bonding between amine and acid, and to the NH3+ group of ammonium salt resulting from the aggregation, respectively. The equation which was derived from the Beer’s law and the aggregation equilibrium made it possible to calculate the true aggregation number λ using the values of absorbance at each absorption band.

Alternatively, the λ was calculated by means of the Kreuzer’s equation from the apparent mean aggregation number Z which was obtained using thermistors. The agreement between the λ’s obtained by the spectral and thermistor methods was satisfactory as for the order of magnitude. The cmc was tentatively estimated by both spectral and thermistor method.

The agreement between the cmc’s obtained by these independent methods was good. But these cmc’s did not show good agreement with those obtained from solubilization.
Synthetic Amphoteric Polypeptide. III. A Water-Soluble Amphoteric Polypeptide
Authors: Yuki Heimei , Okawa Kenji , Tani Hisaya
Published: July 2006

1. Preparation of four copoly-(l-glutamic acid, Dl-serine), the molar ratios of the two amino acid residues were 4:1, 3:2, 2:3 and 1:4, by debenzylation of the corresponding four copoly-(γ-benzyl l-glutamate, O-benzyl Dl-serine), was attempted.

2. The inter- and/or intra-molecular ester-linkages, formed during the debenzylation reaction between hydroxyl group of serine residue and carboxyl group of glutamic acid residue, was broken by treating with aqueous triethylamine without accompanying racemisation or hydrolysis of the peptide bond.

3. Copoly-(l-glutamic acid, Dl-serine) became freely soluble in water when the content of serine residue was more than about 50 mole per cent.

4. Copoly-1:1:2-(l-glutamic acid, l-lysine, Dl-serine), prepared by debenzylation from the parent copolymer, was soluble in water over a whole pH range, and the pH dependence of viscosity and of optical rotation was measured on its solutions. It was found that these properties are very similar to those of natural albumins.
The Ignition of Hydrogen-Oxygen Mixture by Shock Wave. II. Measurement of the Pressure and the Volocity of Shock or Detonation Wave
Authors: Suzuki Momotaro , Miyama Hajime , FujiMoto Shiro
Published: July 2006

We have carried on a series of experiments on the shock ignition of a gaseous mixture 2H2+O2 by using a shock tube equipped with pick-ups, which can be used for measuring the pressure and the velocity of shock or detonation waves. The results are summarized as follows:

1) When the pressure P0 of a gaseous mixture is higher than 200 mmHg, the ignition starts between the membrane and the first pick-up along the test chamber and the detonation becomes stable before the detonation wave arrives at the first pick-up.

2) In case P0 is lOO mmHg, the detonation is initiated by an incident shock wave in some cases and by a reflected one in other cases.

3) When P0 is higher than 200 mmHg, the pressure of the detonation wave initiated by shock ignition increases along with the increase of P0 but its velocity decreases with a similar increase.
Dielectric Contribution to Miscibility in the Ternary System 1-Propanol-Water-Toluene
Authors: Somasundaram K M , Suryanarayana C V
Published: July 2006

In place of the familiar equation \undersetkΣPkxk=P1,2···k, which does not hold good in many-cases, we have formulated alternatively the equation \undersetkΣPkxk=P1,2···k where L is volume polarization. This equation has been applied to the ternary system 1-propanol-water and toluene just at the point of miscibility, when to a given ratio of toluene and water addition of an optimum amount of 1-propanol results in the disappearance of the phases. Also the new equation has been applied to two fully miscible binary systems 1-propanaol-water and 1-propanol-toluene. It has been concluded that the new equation gives a condition concerning the dielectric contribution of the components to miscibility in the ternary system.
Studies on the Interaction of Surface Films with Solute in Solution. II. Sorption of Dye on the Built-up Film of Stearic Acid and Barium Stearate
Authors: Muramatsu Mitsuo
Published: July 2006

The amounts of dyes sorbed on the built-up films of stearic acid and of barium stearate were measured, under varying pH of the dye solutions into which the films were immersed. It has been observed in general that the amount of sorption was greater when the molecular weight of dye became greater. Nonionic attraction such as van der Waals’ force, which is considered to be a cause of interaction between dye molecules themselves, and aggregate formation among them may also be responsible for the interaction between dye and built-up film. Such an interaction may be favored by the decreasing ionic charges of the same sign existing on dye molecule and film.

Acid dyes proved to be increasingly sorbed with decreasing pH until the aggregates of dye grew so large that they fell from the interface as a precipitate. The difference in detailed behaviors for sorption of several acid dyes could be explained by the difference in the strength of repulsive force of dye ions, suppressing the attraction, as well as of van der Waals force which was considered to be largely affected by molecular weight.

In the case of basic dyes, ionic attraction is additionally taken into account to explain their sorption on the film of stearic acid. This has been suggested by the correlation between the degree of ionization and sorbed amount of chrysoidine, and supported by the fact that the built-up film of barium stearate took up less crystal violet than that of stearic acid did.

In the case of the sorption of amphoteric dyes, a maximum was observed in general in a pH range which is roughly in agreement with an isoelectric region of dye. Tentative explanations have been made for this phenomenon, taking account of a change in the dissolved state of dyes.
Kinetics of the Reaction between Copper(II)-Ethylenediaminetetra-acetate Complex and Cyanide
Authors: Tanaka Nobuyuki , Kamada Minoru , Murayama Teisuke
Published: July 2006

The reaction between copper(II)-ethylenediaminetetra-acetate complex and cyanide ion has been investigated by measuring the change of the polarographic diffusion current of the complex as a function of time after the initiation of reaction.

The rates of the reaction obtained with various concentrations of Cu(II)-EDTA complex, cyanide and unchelated EDTA showed that the reaction is of second order on the concentration of the Cu(II)-EDTA complex, fourth order on that of the cyanide and first order on the reciprocal of that of the unchelated EDTA. The reaction mechanism proposed is

(Remark: Graphics omitted.)

and the rate of the reaction is expressed as

(Remark: Graphics omitted.)

The value of k1k3/k2 was determined to be 6.8×107 1.4 mole−4sec.−1 in a carbonate bicarbonate buffer of pH 10.0, at ionic strength 0.5 and at 25°C.
Studies on the Mannich Reaction. II. On the Formation of Piperidine Derivatives (2)
Authors: Uchino Norito
Published: July 2006

1) The mechanism of the reaction of phenyl vinyl ketone with β-benzoylethylamine hydrochloride was discussed.

It was concluded that the β-carbon atom of phenyl vinyl ketone combined with β-benzoylethylamine hydrochloride on attacking the lone pair of electrons which appeared in consequence of prototropy, and gave the same products as those in the Mannich reaction.

2) In the Mannich reaction, piperidine bases are found to be produced.

It was concluded that the phenyl vinyl ketone, which was produced by decomposition of the products in the Mannich reaction, was concerned with the formation of these piperidine bases.
Analytical Chemistry by Means of Organic Compounds. XXV. 1-Hydroxyacridine as a New Reagent (Neo-oxine) (1)
Authors: Ishibashi Masayoshi , Yamamoto Yuroku , Yamada Hirohiko
Published: July 2006

The absorption spectra of 1-hydroxyacridine were obtained both in aqueous and chloroform solution, and the pKa and the pKb were determined. The pKa is slightly greater than that of oxine, and it is suggested that the stability of metal chelate with 1-hydroxyacridine will have values of the same or larger order as that of oxine chelate, because there is a direct relation between the basicity of a chelating agent, as measured pKa values, and the stability of the chelates it forms, as cited in the literature of Morrison and Friser.

The various aspects of solvent extraction using chloroform were then investigated. The optimum pH range on extraction for each element was determined and it was found that the range is narrow as compared with that of the oxine chelate. The per cent extracted was determined and it was found that copper, nickel, cobalt and zinc were almost completely extracted under the conditions investigated.
Enzymic Preparation of Guanosine-2′,3′-cyclic Phosphate, Inosine-2′,3′-cyclic Phosphate and Xanthosine-2′,3′-cyclic Phosphate
Authors: Sato-Asano Kimiko , Fujii Yoshiko , Egami Fujio
Published: July 2006

By RNase T1 digestion, guanosine-2′,3′-cyclic phosphate was obtained with good yield from yeast RNA, and two new compounds, inosine-2′,3′-cyclic phosphate and xanthosine-2′,3′-cyclic phosphate were obtained from deamino-yeast RNA. The properties of the new compounds were studied.
Polymerization of Methyl Methacrylate Initiated by a Combined Action of Di-p-tolylsulfonylhydroxylamine and Oxygen in Air
Authors: Uehara Ryoichi
Published: July 2006

The polymerization of methyl methacrylate is initiated by a combined action of di-p-tolylsulfonylhydroxylamine and oxygen. The polymerization is accelerated with dimethylaniline and retarded with hydroquinone. The initial rate of polymerization is linearly dependent upon the square roots of concentrations of di-p-tolylsulfonylhydroxylamine and dimethylaniline in air. The reciprocal of the average degree of polymerization of the polymethyl methacrylate formed by means of the present initiating system is proportional to the square root of the initial concentration of di-p-tolylsulfonylhydroxylamine.A copolymer (1 : 1) is obtained from an equimolar mixture of styrene and methyl methacrylate. These facts suggest that the polymerization is initiated by a radical produced from the initiating system.
Polarographic Studies on the Rare Earths. II. Europium
Authors: Misumi Seizo , Ide Yasushi
Published: July 2006

The double reduction waves of pure aquo tripositive europium ion, under various conditions, at dropping mercury electrode were studied. The effects of the variations in pH, the concentration of europium ion, the anion species of supporting electrolytes, and the concentration of gelatin as maximum suppressor, etc. were examined. The electrode reaction of the first wave was irreversible and one electron reduction, and that of the second wave was the irreversible or quasi reversible two electrons reduction. The half-wave potentials of the first wave and the second wave at pH 2.95 were as follows. (E_1)_1/2: -0.767 V. vs. S. C. E.(E_2)_1/2: -1.971 V. vs. S. C. E.where concentration of Eu3+ ion : 1.104 mm in 0.1 m LiCl and 0.01% gelatin medium.
Analysis of Non-Newtonian Flow by Falling-Sphere Method
Authors: Hirota Sadao , Takada Masao
Published: July 2006

A procedure to obtain a general flow curve by falling-sphere method is presented. The shear stress SR and shear rate (du/dr)R at the equator of the sphere are given as

& S_R=RΔρg/3

& (du/dr)_R=(3U_0/2R)

&  ×[1+2.5(dlogU_0/dlogR-2)

&  -(3/4)(dlogU_0/dlogR-2)^2]

where Δρ is the density difference between sphere and fluid, R the radius and U0 the falling velocity of the sphere.
Dielectric Constants of Binary Mixtures; 1,2-Dichloroethane and Nonpolar Solvents
Authors: Fujishiro Ryoichi , Kimura Ko
Published: July 2006

The dielectric constant for the mixture dichloroethane-carbon tetrachloride was calculated by making use of a model proposed by Onsager, Fujishiro and Schlote. The calculated values agree rather well with the experimental. The higher the temperature is, the better is the agreement. The dielectric constants of other mixture such as dichloroethane-cyclohexane, dichloroethane-benzene and dichloroethane-carbon disulfide were also measured only at 25°C and compared with one another. The coincidence of the theoretical values with the experimental was obtained in the following order; carbondisulfide, benzene, carbon tetrachloride and cyclohexane.
The Silver Catalyzed Oxidation of Arsenious Acid by Persulfate
Authors: Gupta Yugul Kishore , Misra Deen Dayal
Published: July 2006

The kinetics of silver catalyzed oxidation of arsenious acid has been followed by estimating the acid with the permanganate. The results are reproducible only with the same stock solution of arsenious acid. This oxidation is much faster than other silver catalyzed oxidations, such as those of Cr3+, VO2+, Mn2+, Ce2+, etc. The oxidation is of the first order in persulfate and independent of the concentration of the acid. The entropy of activation has been calculated and a mechanism has been suggested. No conclusion regarding the salt effect could be obtained due to the specific effect of the ions. K+, Na+, NH4+ and Mg2+ inhibit in the order given. Nitrate ion accelerates the rate and sulfate ion seems to have no effect.
Polarographic Studies of Metallic Complexes. IV. Bisethylenediamine Series of Cobalt (III) Complexes
Authors: Maki Nobufumi , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

1. Most of the cobalt (III) complex ions of bisethylenediamine series, [Co en2X2](3−2n)+ or [Co en2Y](3−m)+ are reduced irreversibly in two steps at the dropping mercury electrode. The first diffusion current corresponds to the reduction, Co(III)→Co(II) and the second to the reduction, Co(II)→Co(0). The second step always exhibits the maximum wave.

2. The polarographic stability of [Co en2X2] type complexes increases in the following order of the ligands;

Br^-, Cl^-<NCS^-<NO_2^-<NH_3<OH_2<CN^-

(Supporting electrolyte; 0.5F K2SO4)

Similarly, the order of the stability of [Co en2Y] type complexes is as follows;

leuc^-<ox^2-<gly^-<SO_3^2-<CO_3^2-<en

(Supporting electrolyte; 0.5F K2SO4)

These orders are independent of the kind of supporting electrolyte such as potassium chloride or potassium sulfate. The orders of the polarographic stability did not agree with that of the spectrochemical series.

3. In perchloric acid the well-defined wave of steep slope was obtained for diaquo-bisethylenediaminecobalt (III) ion, [Co en2(OH2)2]3+, while the ion gave a modified wave in the neutral solution of 0.1F potassium chloride and of 0.5F potassium sulfate. This phenomena was explained as being due to the inhibition of the dissociation and polymerization of the complex in the presence of an overwhelming hydrogen ion. A similar behavior was observed in the aquo-ammine cobalt (III) complexes.
Syntheses of Pyrimidine Derivatives. XVII. On the Reaction Mechanism of Some Pyrimidine Syntheses
Authors: Takamizawa Akira , Tokuyama Kanji , Tori Kazuo
Published: July 2006

The mechanism of the reactions of 2-alkoxymethylene-3-alkoxypropionitrile and 2-dialkoxymethyl-3-alkoxypropionitrile with acetamidine was studied. The results show that these two nitriles react with acetamidine in completely different manners. In the case of the reaction of 2-alkoxymethylene-3-alkoxypropionitrile with acetamidine, the final product (2-methyl-4-amino-5-alkoxymethylpyrimidine) can be obtained directly, while in the case of the reaction of the other nitrile with acetamidine, the intermediate with the absorption maximum at 275 mμ can be detected spectrophotometrically. This intermediate could be identified with 2-acetamidinomethylene-3-alkoxypropionitrile. The difference in the mechanism between these two reactions might be explained by taking into consideration the fact that the intermediate in the latter case can be stabilized by the resonance among the usual structure and the polar structures in which non-bonding electrons on the nitrogen atom of the amino group migrate into C≡N or C=N group.
Synthesis of Sarkomycin. II. A New Synthesis of the Alkyl Cyclopentanone-3-carboxylate
Authors: Toki Katsuyuki
Published: July 2006

Cyclopentanone-3-carboxylate which is the starting material for the synthesis of dl-sarkomycin (2-methylenecyclopentanone-3-carboxylic acid) was obtained by a new route from butadiene and alkyl acrylate through alkyl cyclohexene-4-carbonylate and thence 3-alkoxycarbonyl adipic acid.
Effects of Dry Grinding on Kaolin Minerals. I. Kaolinite
Authors: Takahashi Hiroshi
Published: July 2006

The effects of several-hundred-hour mechanical-mortar dry grinding of kaolinite were studied by X-ray, thermal, electron microscopic and other methods. It has been found that there are two sorts of structural change in the process of dry grinding of kaolinite. One is the production of a non-crystalline substance attended by the disordering of the crystalline part, and the other is the reaggregation process. The process of the reduction in the particle size and the process of the production of the non-crystalline substance are connected to the process of the reaggregation. In a certain stage of the dry grinding, the reaggregates are spherical particles which have a zeolitic structure. As the grinding further progresses, the structure of the crystalline part in this radial particle becomes disordered due to the mechanical stress, and it changes into an amorphous substance at last. Consequently, the effect of dry grinding of kaolin mineral depends on the structural perfectness of alumino-silicate layers of the kaolin mineral, that is, the internal crystallinity of the kaolin mineral.
Effects of Dry Grinding on Kaolin Minerals. II. Kibushi-clay
Authors: Takahashi Hiroshi
Published: July 2006

The effects of several-hundred-hour mechanical-mortar dry grinding of Kibushi-clay which is a kaolin mineral of fireclay type were studied by X-ray diffraction, thermal, electron microscopic and other methods and compared with those of kaolinite. It has been found that the process of a production of a non-crystalline substance attended with a disordering of a crystalline part and the process of a reaggregation are present in the dry grinding of Kibushi-clay as in kaolinite. Finally, Kibushi-clay changes into an amorphous substance as the result of dry grinding. In a certain stage of grinding, a zeolitic structure is formed. As the grinding progresses, the particle size increases owing to reaggregation. When an amorphous substance like silicaalumina mixed gel is produced, the particle size grows irregularly. In Kibushiclay, the time it takes to become amorphous by dry grinding is shorter than in the case of kaolinite. Consequently, the effects of dry grinding of kaolinite and kaolin mineral of fireclay type depend on the structural perfection of unit layers of the original kaolin minerals.
Spectrophotometric Determination of Uranium with Neo-thorone
Authors: Shibata Shozo , Matsumae Teiichi
Published: July 2006

The spectrophotometric method for the determination of microquantities of uranium with Neo-thorone was established. By this method 5 to 40 μg. of uranium in 25 ml. solution can be determined easily and accurately. Interference by a small amount of aluminum, zinc, lead, thorium and iron could be avoided by using sodium ethylenediaminetetra-acetate. Therefore, complete separation of iron, thorium, and aluminum is not necessary.