bluuebunny/crossref_metadata_2025 huggingface dataset:
Physicochemical Studies of Stearic Acid Monolayer-Aluminum Ion Interaction. I. The Surface Pressure
Authors: Motomura Kinsi , Matuura Ryohei
Published: July 2006

In order to throw light on the interaction of the stearic acid monolayer with aluminum ion in underlying solutions, surface pressure measurements were carried out on (1) the stearic acid monolayer spread on 10−4mol./l. aluminum chloride solution, (2) the aluminum distearate monolayer spread on distilled water, and (3) the aluminum distearate monolayer spread on 10−4mol./l. aluminum chloride. It was found that their pressure-area curves were all solid expanded films over characteristic pH ranges, with the curve of 1 especially analogous to that of 3. In the limiting area-pH curves, there seemed to be a little partial disagreement between them which would not be essential. From these results it was concluded that the monolayer of stearic acid interacting with aluminum ion might be analogous to the two-dimensional polymeric aluminum distearate adsorbing aluminum ion.
Physicochemical Studies of Stearic Acid Monolayer-Aluminum Ion Interaction. II. The Surface Viscoelasticity
Authors: Motomura Kinsi , Matuura Ryohei
Published: July 2006

By using the ring torsion pendulum method and applying the correct mathematical analysis, surface viscoelasticity measurements were carried out on the monolayers of (1) stearic acid on a 10−4 mol./l. aluminum chloride solution, (2) aluminum distearate on distilled water, and (3) aluminum distearate on a 10−4 mol./l. aluminum chloride solution. It was found that the rheological behavior of 1 and 2 could be analyzed in terms of the four-parameter model and of 3 by the three-parameter model or elasticity. Also, with regard to the values of viscoelasticity, it was shown that at large areas 1 was smaller than both 2 and 3, and at small areas 1 approaches to 3. From the viewpoint of these results, it was concluded that the interacted monolyer of stearic acid with aluminum ion in an underlying solution might be analogous to the monolayer of aluminum distearate with a short chain length adsorbing basic aluminum ion.
The Very Weak Visible Absorption Band of p-Benzoquinone
Authors: Kuboyama Akira
Published: July 2006

The very weak absorption bands at the long wavelength sides of the n→π* singlet-singlet absorption bands of p-benzoquinone and its derivatives were examined with regard to the solvent effect, the substitution effect and the temperature - dependency. From the obtained results, this absorption band is reasonably assigned to the n→π* singlet-triplet absorption band. As for its absorption curve, a distinct difference between the structure where the two carbonyl groups of p-benzoquinone are equivalent and that where the two carbonyl groups are not equivalent is observed.
Infrared and Raman Spectra of Ethylidene Dialkyl Ethers
Authors: Nukada Kenkichi
Published: July 2006

Infrared spectra of three kinds of ethylidene dialkyl ethers (CH3OCH(CH3)OCH3; EDM, CH3OCH(CH3)OC2H5; EME and C2H5OCH·(CH3)OC2H5; EDE), of vapor at various temperatures, and of carbon tetrachloride and acetonitrile solutions are presented.

From a comparison of the spectra obtained, it has been concluded that rotational isomerism could at least exist in EME and EDE.

Raman spectra of pure liquid have been obtained, together with the degree of depolarization.

The assignment of these spectra is given by referring to those of the homologues, such as dialkoxy methanes.
The Reaction of Hydrogen and Oxygen through a Silent Electric Discharge. I. The Formation of Hydrogen Peroxide
Authors: Morinaga Kihei
Published: July 2006

1) The reaction between hydrogen and oxygen in a silent electric discharge of high frequency was investigated. The product, in the course of reaction, is solely hydrogen peroxide and water.

2) The linear relationship, independent of the frequency of the current, between the rate of formation of hydrogen peroxide or of water and the pulse current was established.

3) The composition of the hydrogen peroxide-water solution is constant so long as the gap length is constant.

4) The flow rate and the said composition relation were measured.

5) The reaction pattern in the discharge zone was briefly discussed.
De-localization of Bond Eigenfunctions in π-Electronic Systems. II. Non-Empirical Calculation of the π-Electronic States of the trans-Butadiene Molecule
Authors: Takekiyo Shozaburo
Published: July 2006

An approximate method, proposed in Part I, has been applied to the non-empirical calculation of the π-electronic states of the trans-butadiene molecule. All the higher orders of overlap and exchange integrals have been considered. Slater 2pπ-orbitals have been used through out. The values of the energy levels obtained are −51.099 eV. (1Ag),−45.237 eV. (1Ag), and −41.429 eV. (1Bu). The π-electron densities for the ground state are Da=Dd=0.988, and Db=Dc=1.012. These results agree quantitatively with those evaluated by the ASMO SCF CI method.
Cationic Polymerization of Isobutene in Liquid Sulfur Dioxide. Role of Water of Cocatalyst
Authors: Tokura Niichiro , Matsuda Minoru , Shirai Isoo
Published: July 2006

Polymerization of isobutene was carried out in liquid sulfur dioxide with stannic chloride as catalyst containing water or heavy water. It was confirmed with the aid of infrared spectrometry that in liquid sulfur dioxide water was playing a part as a cocatalyst when water was present in a comparable amount.
Anionic Polymerization of Vinylidene Chloride. III. Copolymerization Initiated by n-Butyllithium
Authors: Konishi Akio
Published: July 2006

The copolymerization reaction of vinylidene chloride with methyl acrylate, styrene and vinyl chloride initiated by n-butyllithium has been studied. The monomer reactivity ratios have been found to be distinctly different from those of the radical copolymerizations. The results clearly showed that the nature of the polymerization of vinylidene chloride initiated by n-butyllithium is anionic, in accordance with the prediction from the q-ε or the Q-e map.
A Systematic Ion Exchange Separation of Metallic Elements. I. Group Separation of Metallic Elements by Anion Exchange with Hydrochloric Acid
Authors: Yoshimura Jun , Waki Hirohiko
Published: July 2006

1) As the first stage in the systematic separation of metallic elements by ion exchange, a group separation on an ordinary scale was tried using an anion exchanger “Dowex 1-X8”, with hydrochloric acid, a method based on Kraus’ method.

2) Most metallic elements usually treated in the chemical analysis can be separated into four groups by the elution through a 40 ml. column using 11 m, 6.5 m and 3 m hydrochloric acid as elutriant. Satisfactory results were obtained on analysis for a mixed solution.

3) These classifications may be explained in terms of the formation of a chloro-complex of a metal, not only in the solution phase but also in the resin phase.
The Mannich Base of Troponoid and its Application. VII. The Synthesis of 5-Formyl Derivative of 3-Isopropyltropolone
Authors: Ogura Kyozo
Published: July 2006

3-Isopropyl-5-bromomethyl-7-bromotropolone and 3-isopropyl -5- formyl -7- bromotropolone were synthesized from 3-isopropyl-5-piperidinomethyl-7-bromotropolone, and some 5-substituted 3-isopropyl-7-bromotropolones were derived from the bromomethyl derivative.
O→N-Acetyl Shift of O-Acetylserine and O-Acetylthreonine. An Approach to the Separation of Serine and Threonine Fraction from Amino Acid Mixture
Authors: Fujiwara Sadao , Morinaga Shigeru , Narita Kozo
Published: July 2006

The reaction rate of O→N-acetyl shift of O-acetylserine was compared with that of O-acetylthreonine, and it was found that the latter was greater than the former. By utilizing the difference of the rates of the reaction of these amino acid derivatives, an attempt to separate serine and threonine from their mixture was unsuccessful owing to the fact that the shift reaction was affected by many factors, i. e., the ionic strength of inorganic salts present, pH of the reaction medium and the reaction temperature. Serine and threonine were isolated from the acid hydrolyzate of casein through their O-acetylation and subsequent O→N-acetyl migration with 80∼90% yield.
Studies on Solid Carbons. I. The Formation of Solid Carbons
Authors: Sakaguchi Masakazu
Published: July 2006

The pyrolysis of six different pure organic compounds (benzene, toluene, naphthalene, ethylene, n-hexane and methane) has been studied to discover the relation between the starting materials and the carbon produced. The B.E.T. area, micro-pore size distribution, particle shape, and degree of crystallization have been measured in the carbon produced. The carbonization has been carried out by pyrolyzing the material by means of the flow method at the two temperatures of 800 and 1100°C, keeping the flow rate constant at 2.5 cc./hr. and the vapor pressure at 83 mmHg.

The order of the B.E.T. areas, A, of the carbons produced by pyrolysis is as follows: at 800°C, A(hexane), 49.0>A(toluene), 44.0>A(methane), 11.5, and at 1100°C, A(hexane), 4.7>A(toluene), 2.9>A(methane), 1.9 respectively.

The peak radii, R, of the micro-pore size distribution curves are not changed by the raising of the reaction temperature (800, 1100°C) ; the order of the radii is R(methane), 18>R(toluene), 12>R(hexane), 9. Notwithstanding the fact that the peak radii are not changed by the reaction temperature, the micro-pore volumes diminish remarkably.

Electron microscope observation has shown that the shape of the particle is affected by the physical state of the starting material during pyrolysis. If the material is gaseous, plate-like carbon is obtained. If the material is liquid, spherical carbon is obtained.

X-Ray diffraction has shown that the degree of crystallization is not affected by the kind of material. When the temperature of pyrolysis is raised from 800 to 1100°C, the crystallization advances markedly.
Studies on d-Glucosamine Derivatives. VIII. 1-C-Substituted-1-anilino-1-deoxy-d-arabitols
Authors: Yoshimura Juji
Published: July 2006

In the reaction of 3,4; 5,6-di-O-isopropylidene-N-phenyl-d-glucosaminonitrile and Grignard reagents or alkyl lithiums, the nitrile group was substituted for alkyls to yield each pair of diastereoisomers of the 1-C-substituted-1-ailino-1-deoxy-d-arabitols. The levo-rotating diastereoisomer was, moreover, exclusively predominant in the former case, and the dextro-rotating one in the latter

The reaction mechanism for the above asymmetric induction was discussed.
Spectral Response of Photoconductivity in Polycyclic Aromatic Compounds
Authors: Sano Mizuka , Akamatu Hideo
Published: July 2006

The spectral responses of the photoconductivity of perylene, pyranthrene, violanthrene, anthanthrone, violanthrone and indanthrazine, as well as the optical absorption spectra of these aromatic solids, have been investigated. Associated with the surface-type cells, when the aromatic films are thin enough, the response curves reproduce the absorption spectra. It has been concluded from this that the photoconductivity is the intrinsic property of the compound and that the lowest excited states are responsible for the electrical conduction.

The thresholds for photoconductivity are rather vague. In some cases, however, extra bands are found in the photoconduction spectra outside the main bands. These extra bands locate in the energy regions which correspond to the triplet states of the molecules and are coincident with the thermal energy gaps for the semiconduction.
Studies on Solvent Extraction using Radioactive Isotope. X. Solvent Extraction of Zirconium-95 and Niobium-95 with Acetylacetone
Authors: Suzuki Nobuo , Omori Takashi
Published: July 2006

The extraction of 95Zr and 95Nb with an acetylaceton-echloroform mixture was investigated. The percentage extraction of 95Zr with a 20% acetylacetone solution was 98% at pH valves ranging from 3 to 8, and that of 95Nb was 90% at pH values from 2 to 5. The extraction ratio of 95Nb was lowered by the extension of the shaking time. As an diluent, chloroform and methylene chloride were recommended. Phosphate, oxalic acid, citric acid and EDTA interfered remarkably. Sulfuric acid was most efficient for the back extraction. A high purity of 95Zr was obtained by using hydrogen peroxide as a masking agent. The yield was satisfactorily high.
Vinyl Copolymerization. II. Copolymerization of Acrylonitrile with Styrene and Vinyl Acetate
Authors: Suzuki Momotaro , Miyama Hajime , Fujimoto Shiro
Published: July 2006

Rates of copolymerization of AN-St and VA-AN for various mixing ratios of the two monomers were measured by the thermistor method. The heat of copolymerization, which was obtained by comparing the results of the thermistor method with those of the usual analytical method, agrees very well with Alfrey’s equation. Also, the non-constancy of φ in the AN-St system can be explained by Arlman’s theory; it is concluded that the termination constants for mixed radicals are larger than those for homogeneous radicals and, furthermore, that the ratio of a normal cross-termintion constant to a constant of the cross-termination having a penultimate unit is 20.

However, in the VA-NA system, the application of Arlman’s equation was impossible because the large difference between the reactivity ratios of the two monomers causes a large error limit in the calculated values of φ.
The Reaction of Hydrogen and Oxygen through a Silent Electric Discharge. II. The Effect of Packings on a Peroxide Formation
Authors: Morinaga Kihei
Published: July 2006

By applying several packings in the discharge gap space, the peroxide formation through a silent discharge was studied. The peroxide concentration was higher in a void discharge tube or in a boric acid (boric oxide) packing-filled discharge tube and lower in the case of the soda glass and the ceramic packing containing titanium(IV) oxide. This was explained by the insufficient destruction of HO2 and H2O2 on the boric acid surface, and by the great destruction on the surface of the packing consisting of soda glass and ceramics. A kind of aging phenomena observed in the boric oxide packing was tentatively explained.
Hot-Atom Chemistry of Halogens in Cobaltammine Complex Salts. II. Hot-Atom Chemistry of Radiobromine in Pentammine Cobalt(III) Bromides and Bisethylenediamine Cobalt (III) Bromides
Authors: Saito Nobufusa , Tominaga Takeshi , Sano Hirotoshi
Published: July 2006

The fate of energetic radiobromine atoms arising from the (n, γ) reaction on bromine in solid complex salts, the formulas [Co·(NH3)5X]Br2,3 and [Co(en)2X2]Br1,3,, was investigated. The fraction of the total radiobromine produced finally retained in ligands (ligand yield) was found to increase with a Function of the mass of the donor atom in ligand X. Therefore, it was suggested that the kinetic processes might play an important role in recoil reaction in the solid complex salts.
Studies of the Cage Effect of Solvent. I. Photolysis of Azomethane in n-Hexane
Authors: Kodama Sukeya
Published: July 2006

Azomethane in n-hexane solution has been decomposed by irradiation of 366 mμ over the temperature range −75 to 80°C, in order to study the effect of the solvent cage on the photolysis. The main products have been found to be nitrogen, methane and ethane. The yield of methane increases, but that of ethane, which amounts to 88% of nitrogen at −75°C, decreases with the rise in temperature. The addition of styrene as a scavenger for methyl radicals in an increasing amount suppresses the formation of methane almost completely, while that of ethane is not affected, indicating that ethane is exclusively formed by the cage combination of an azomethane molecule. The formation of methane is explained by the abstraction of the hydrogen atom from a solvent molecule by methyl radicals that have escaped the original cage. The material balance represented as ((1/2)CH4+C2H6)/N2 is nearly 100% below room temperature, but it falls off slightly at higher temperatures; this may be ascribed to addition reactions of methyl radicals. The quantum yield of photolysis is apparently smaller than unity and falls off with a lowering of the temperature; this probably arises from the cage recombination of the initially formed pair of radicals CH3N2 and CH3, though the former radical is very short-lived.
Studies of the Cage Effect of Solvent. II. Photolysis of Azomethane in Various Solvents
Authors: Kodama Sukeya
Published: July 2006

The photolysis of azomethane in n-octane, toluene, ethyl acetate and ethanol has been investigated over the temperature range from about −80 to 100°C. The results obtained are very similar to those previously obtained with n-hexane and show that, also in these solvents, the ethane, one of the main products, exclusively results from the combination in the solvent cage of a pair of methyl radicals formed from an azomethane molecule. For all the solvents investigated, the temperature dependence of the yield of ethane referred to nitrogen formed, C2H6/N2, can be represented by an empirical expression, 1–C2H6/N2=Aexp(−E⁄RT), with constants A and E, whose values are rather insensitive to the nature of the solvent. From the reduction of the yield of methane in the presence of styrene, the activation energy of the addition of methyl radicals to styrene molecules is estimated as 4.9 kcal./mol. Apparent quantum yields obtained by comparing the rates of formation of nitrogen fall off with a lowering of the temperature in all the solvents investigated.
Reactions of Iminocarbonates with Acids
Authors: Mukaiyama Teruaki , Fujisawa Tamotsu , Hyugaji Teruo
Published: July 2006

Iminocarbonates, whose chemical properties have been little investigated, were prepared from sodium alkoxides and corresponding imidophosgene.

Diethyl N-phenyl iminocarbonate gave urethan and esters by reaction with acids, such as hydrogen chloride, carboxylic acids and diethyl phosphate. β-Acyloxyethyl N-phenyl cabamates were prepared from the reactions of ethylene N-phenyl iminocarbonate with carboxylic acids.

These reactions were applied to the syntheses of polymers, and the alternating poly (urethan/ester)s were obtained.
The Reactions of 1, 2-Cyclopentanedione Dioxime and of 1, 2, 3-and 1,3,5-Cyclohexanetrione Trioximes in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Shirai Isoo , Sugahara Tokuji
Published: July 2006

1, 2-Cyclopentanedione dioxime (II), 1, 2, 3-cyclohexanetrione trioxime (III) and 1, 3, 5-cyclohexanetrione trioxime (IV) were treated with reagents and exhibited different and characteristic behaviors in liquid sulfur dioxide. The formation of 5, 6-dihydro-4H-cyclopenta-[c] furazan (V) from II with thionyl chloride by a condensation reaction and of γ-cyanobu-tyric acid (VI) from II with sulfur trioxide by a cleavage reaction were observed. 7-Hydroxi-rnino-4, 5, 6, 7-tetrahydrobenzo[c]furazan (VII) was found in the the reaction mixtures from III and thionyl chloride and from III and bromine, accompanied by large amounts of resinous matter.

Mono-deoximation by sulfur trioxide was suggested. 1, 3, 5-Cyclohexanetrione trioxime (IV) gave only black tarry matter, which may be attributable to the instability of IV.
The Cobalt(III) Complexes of Ethylenediaminediacetic and Ammoniadiacetic Acids
Authors: Mori Motoshichi , Shibata Muraji , Kyuno Eishin , Maruyama Fukun
Published: July 2006

The cobalt (III) complexes containing ammoniadiacetate group (ada) and ethylene diaminediacetate group (edda) have been prepared:

1) K[Co(ada)2]·4H2O Red-violet

2) K[Co(edda)(CO3)]·H2O Red-violet

3) [Co(edda)(OH2)2]ClO4 Violet

4) K[Co(edda)(NO2)2]·H2O Yellow-brown

The visible and the ultraviolet absorption spectra as well as the infrared spectra of these complexes have been measured and discussed in relation to the structures of these complex ions.
Thermal Decomposition of Acetaldehyde in the Presence of Hydrogen Sulfide. II. Effects of Chain-inhibitors
Authors: Imai Naomi , Yoshida Yasuo , Toyama Osamu
Published: July 2006

The effect of propylene, isobutylene and nitric oxide as inhibitors on the thermal decomposition of acetaldehyde in the presence of hydrogen sulfide has been investigated over the temperature range of 380 to 494°C. Of the three inhibitors, which are all effective in reducing the rate of decomposition, isobutylene is slightly more efficient than propylene, and nitric oxide is far more efficient than the other two. With propylene and isobutylene, the rate of decomposition is reduced with the increasing amount of the inhibitor until a constant rate is reached, while with nitric oxide the rate passes through a minimum value and then increases again in proportion to the pressure of the inhibitor. The residual rate of the maximally inhibited decomposition is almost the same for the three inhibitors and is represented by –d[CH3CHO]/dt=ki[H2S] [CH3·CHO]. A comparison of the above results with those of the decomposition in the absence of an inhibitor suggests that the residual decomposition remaining after being fully in-hibited is a molecular process catalyzed by hydrogen sulfide.
Studies on Foams. IX. Foaminess and Foam Stability of Polyvinyl Alcohol Solutions
Authors: Nakagaki Masayuki , Goto Kazu
Published: July 2006

The foaminess and foam stability of six polyvinyl alcohol solutions, GH–20, GM–14, GL–05, NH–20, NM–14 and NL–05, were measured by the pour test; the foaminess was represented by the height of the foam zone after 1 min., and the foam stability was represented either by the lingering fraction after 35 min. or by the half life of the foam.

The foaminess of the partially saponified polyvinyl alcohols was greater than that of the perfectly saponified ones of the corresponding molecular weights. Comparing specimens of the same degree of saponification, the foaminess was the greater, the greater the molecular weight. The foaminess was also the greater, the greater the concentration, except for NH, the fomianess of the latter showing a maximum at about 0.2 g./100 ml.

The foam stability of NH and NM was very large, but that of NL was small and showed a maximum at 0.1 g./100 ml. The foam stabilities of GH, GM and GL were small. Comparing the foaminess and the foam stability, these two quantities varied in a parallel manner in the cases of NH, NM, low concentrations of NL, and high concentrations of GM and GL, but in other cases they varied conversely.
Studies of the Cage Effect of Solvent. IV. Dependence of the Cage Combination of Methyl Radicals on Solvent and on Temperature
Authors: Kodama Sukeya
Published: July 2006

Experimental results for the cage combination of methyl radicals, obtained by the photolysis of azomethane in various solvents, have been discussed with reference to the effects of solvent and temperature. An attempt to interpret the results by treating both the cage combination and the escape of methyl radical from the cage as though they were elementaly processes has been found to be not very successful, probably owing to the over-simplification involved in such a treatment. Another attempt to apply Noyes’s theory, that assumes diffusion in the viscous continuum, has been found to be rather satisfactory. However, a comparison of the theory with the experimental results indicates that the molecular structure of the medium, as well as the structure and property of individual molecules of the solvent, need to be taken into account for a better description of the matter.
Thermal Decomposition of Dimethyl Ether in the Presence of Hydrogen Sulfide and Nitric Oxide
Authors: Imai Naomi , Toyama Osamu
Published: July 2006

Dimethyl ether has been decomposed in the presence of hydrogen sulfide and nitric oxide over the temperature range 440∼520°C. On increasing the amount of nitric oxide, the rate of decomposition decreases rapidly but after passing through a minimum value it increases linearly with the pressure of nitric oxide. The minimum value of the rate, which is reached in the presence of a small percentage of nitric oxide, is only a fraction of the uninhibited rate, irrespective of the presence of hydrogen sulfide. The rate of decomposition after being maximally inhibited, which is probably molecular in character, is represented by the equation −d[CH3OCH3]⁄dt=k[H2S][CH3OCH3]+k′[NO]·[CH3OCH3], indicating that the inhibited decomposition is catalyzed by hydrogen sulfide and by nitric oxide independently. Arrhenius expressions k=1014.7exp(−43600⁄RT) and k′=1013.4exp(−40500⁄RT)mol−1cc. sec−1 have been obtained.
A Semi-empirical Theory of the π-Electronic Spectra of Aromatic Derivatives
Authors: Nishimoto Kichisuke , Fujishiro Ryoichi
Published: July 2006

A semi-empirical theory of the π-electronic spectra of aromatic derivatives based on anti symmetrized molecular orbital method is given and is applied to the calculations of the singlet π-electronic states of hydroquinone and of phloroglucinol. In the theory the core integrals over AO’s of heteroatoms are expressed as the functions of the core integrals over carbon atom 2pπ AO’s. The calculated excitation energies for these molecules agree satisfactorily with the observed ones. In addition, our calculations give some informations with respect to the nature of their electronic state and their first ionization potentials.
Absorption Spectra of Dyes. VII. Some Steric Effects and Auxochrome-Effects on Complex Formation
Authors: Kobayashi Teruaki , Saito Kenzo , Tanizaki Yoshié , Ando Noboru
Published: July 2006

1. The absorption spectra of the dyes prepared by coupling disazotized 2S-, H-, chromotropic, NW-, γ- and J- acid with dianisidine, and of their copper derivatives were observed in aqueous solutions of the binary mixture with Chrysophenine G, and were compared with the sum curves of the component absorption spectra.

2. The order of the equilibrium constants for a 1:1 complex formed between the dyes not containing copper and Chrysophenine G was parallel to the respective values of the difference in wave number (Δν cm−1) between maximum positions in the region of 390∼420 mμ of the curve simply added and that observed with the equimolar binary mixture of about 1×10−5mol./1.; it was also parallel to those of the decreasing ratio in optical density (ΔD⁄D) of the mixed system at the first maximum position of the sum curve.

3. Under the same conditions as above, Δν and ΔD⁄D were also determined for the mixture of the copper derivatives and Chrysophenine G. In this case, the copper derivatives of 2S-, H-, and chromotropic acid, in the presence of effective auxochromes, still revealed large values of Δν (ca. 1000 cm−1) and ΔD⁄D (ca. 15%), while the values for the rest of the derivatives were almost zero.

4. Discussing the above results, it was shown that in order to display a spectral change due to the formation of a 1:1 complex in a binary mixture with Chrysophenine G, it is necessary that the partner dye has effective auxochromes (amino, hydroxyl) as terminal groups of a conjugated system. It was also shown that the sulfonic groups which are attached to the terminal naphthalene nuclei act on the structure of the dye itself as a steric factor rather than as an electric effect (repulsion) between the ionic charges in the groups and those of Chrysophenine G, and that the more planar structure, resulting in a smaller steric effect, produces more complex.
Neutron Irradiation of Acetoxime and Acetaldoxime
Authors: Tachikawa Enzo , Tsuchihashi Gen-ichi
Published: July 2006

The neutron irradiation of acetoxime and acetaldoxime was studied. Degradation of the products obtained from the neutron irradiation of acetoxime shows that the distribution of carbon-14 activity deviates a little from the statistical behavior on account of steric and other effects.

However, the yields of “synthesis” product are found to be proportional to the number of hydrogen atoms available for their formation. Also there seems to be a linear relationship between the yields of “re-entry” or “synthesis” products and the number of atoms available for formation. The present results suggest that the main process forming the “synthesis” products is simple methylation by 14C-methyl or 14C-methylene radicals, while that giving the “re-entry” products is a “knock on” reaction of carbon-12 by carbon-14.
Study on Nickel Oxide-Silica-Alumina Catalyst for Ethylene Polymerization. I. Catalyst Activity for Ethylene Polymerization and Selectivity in the Formation of Butene-Isomers
Authors: Uchida Hiroshi , Imai Hisao
Published: July 2006

The activity for the ethylene polymerization per unit mass of the catalyst has been found highest for the catalyst with the Al/(Al+Si) ratio of 0.05. The high activity is ascribed to the high specific activity per unit surface area as well as to the large specific surface area of the catalyst. The pore sizes scarcely produce any effect on the catalyst activity.

Even at a very short reaction time, the three isomers of n-butene are produced simultaneously. The ratios both of cis- and of trans-2-butene to 1-butene increase with the reaction time more or less according to the aluminum content, whereas for all the catalysts the ratio between the two 2-butene isomers is kept at values approximate to 1. At the zero extent of reaction, the former ratios, given as a function of the aluminum content, show an increase with the progressively increasing content up to the highest value at the Al/(Al+Si) ratio of 0.1, while the latter remains nearly constant throughout all the catalysts.

For the sake of a convenient explanation of the change in the selectivity as well as in the activity related to the aluminum content of the present catalysts, two kinds of acid sites are suggested as possibly present.
The Infrared Spectra of Carbonyl Compounds in Alcohols
Authors: Minato Hiroshi
Published: July 2006

The infrared spectra of some esters, lactones, carbonates, ketones and aldehydes in methanol and t-amyl alcohol have been determined. With few exceptions, they showed either two carbonyl peaks separated by 15∼27cm−1 or a broad carbonyl peak shifted by 9∼19cm−1from the wave number as determined in carbon tetrachloride. The relative intensities of the two bands are independent of the concentration. Some possible explanations for this phenomenon have been discussed, and as a result these doublet carbonyl bands have been attributed to the mono-hydrogen-bonded carbonyl and the di-hydrogen-bonded carbonyl.
The Phase Transition of Crystalline Potassium Thiocyanate, KSCN. I. Thermal and Infrared Studies
Authors: Sakiyama Minoru , Suga Hiroshi , Seki Syûzô
Published: July 2006

The phase transition of the potassium thiocyanate crystal at ca. 140°C has been studied by thermal and infrared methods. The transition is of a higher-order type, accompanied by an entropy change of 1.30±0.05 e. u., which is nearly equal to R ln 2. The infrared band due to the in-plane bending vibration of a thiocyanate ion shifts to lower frequencies in the course of the phase transition. From these results, it has been concluded that the phase transition is connected with the dynamical disordering of the direction of thiocyanate ions in crystal, a disordering which is mainly brought about by the frequent excitation of the out-of-plane torsional oscillation and the flipping motion.
Kinetics of the Reaction of N-Arylpyridinium Chloride with Anilines
Authors: Oda Ryohei , Mita Shinji
Published: July 2006

The rates of the reaction of 2, 4-dinitrophenylpyridinium chloride with ring-substituted anilines in methanol have been estimated by the gravimetry of the produced glutacondialdehyde dianil. The rates have been found to be second-order with aniline and first-order with pyridinium salt. The electron-withdrawal groups in pyridine accelerate the reaction. These facts suggest a mechanism involving a nucleophilic attack of the molecules of aniline on a complex consisting of 2 molecules of aniline and a pyridinium ion. The products of the reaction of 2, 4, 6-trinitrophenylpyridinium chloride with aniline were 2, 4, 6-trinitrodiphenylamine and the dianil.
The Ion-exchange Equilibrium between Cesium and Phenol-sulfonic-acid-type Cation Exchange Resin
Authors: Tsubota Hiroyuki
Published: July 2006

1) In the Cs+–(NH4++NH3) exchange system, the distribution coefficients of cesium can be approximately expressed as follows:

logKd=pH−1.6log[NH4++NH3]−8.8

2) In the Cs+–Na+ and Cs+–K+ exchange systems, the distribution coefficients of cesium can be expressed with a good approximation by:

logKd=0.25log[OH−]−0.90log[Na+]+2.4

and

logKd=0.25log[OH−]−0.90log[K+]+1.7

In the Cs+–NH4+ exchange system, the distribution coefficients of cesium can be expressed by:

logKd=−1.1log[NH4+]+0.62

3) The specific adsorption of cesium by the active phenolic groups is observed when the pH value of the outer solution is above 12, and high selectivity is obtained above 13 for the Cs+–Na+ exchange system. For the Cs+–(NH4++NH3) exchange system, the specific adsorption of cesium is observed above pH 11, and an extremely high selectivity can be obtained when the total concentration of the outer solution is below 1 mol./l.
Magnetic Study of Nitro Group
Authors: Sriraman S , Sabesan R , Srinivasan S
Published: July 2006

The magnetic susceptibilities of several disubstituted aromatic nitro compounds were determined by Curie retorsion method. The contribution of the (NO2)1+ to the diamagnetic susceptibility was evaluated by the method suggested by Yang, taking Angus’ modified ionic values.
The Crystal Structure of Tetramethylenediammonium Chloride
Authors: Ashida Tamaichi , Hirokawa Sakutaro
Published: July 2006

The crystal structure of tetramethylenediam-monium chloride has been determined by the two-dimensional Fourier method. The crystal belongs to the monoclinic system, with a=10.73Å, b=8.35Å, c=4.60Å and β=92.5°, and the space group is P21/a. The tetramethylenediammonium ion has been found to possess a center of symmetry of the unit cell, and the carbon and the nitrogen atoms in the ion, make a coplanar (trans-) zigzag chain. Thus, the tetramethylenediammonium ion has been found to have either a trans- or a gauche-configuration, depending on the structures of the crystals. There are four short approaches between nitrogen and chloride ions with lengths of 3.19∼3.28Å ; three of them have been concluded to be hydrogen bonds. These hydrogen bonds make two-dimensional networks of the ions perpendicular to the c-axis. The structure of this crystal is similar to that of ethylenediam-monium chloride, and some comparisons between them have been given.
The Electronic State and Dipole Moment of Diazine Mono-N-oxide
Authors: Kubota Tanekazu , Watanabe Haruyuki
Published: July 2006

The dipole moments of pyrazine 1-oxide, 4-methylpyrimidine 1-oxide and pyridazine 1-oxide have been measured in benzene solutions and found to be 1.66, 3.72, and 5.21 D respectively. A comparison of these values with those obtained by the SMO calculation, in which the necessary parameters have been theoretically evaluated in detail by us in previous papers, shows that the agreement between the observed and calculated values is good.
The Photosensitized Oxidation of Leuco-uranine. III. The Kinetics of an Acridine-sensitized Photoöxidation in an Aerated Solution
Authors: Uchida Kengo
Published: July 2006

The mechanism of an acridine-sensitized photoöxidation of leuco-uranine in an aerated solution has been elucidated. The oxidation takes place in a different manner from that in a deaerated solution. That is, oxygen attacks the triplet state of acridine very rapidly and presumably forms a kind of loosely-bound molecular complex. Most of this decomposes into the original acridine and oxygen, so that oxygen suppresses the oxidation of leucouranine occurring in the deaerated solution. Denoting the rate constants of the reactions between the triplet state of acridine and leucouranine and oxygen, respectively, as k5 and k6, the value of k6/k5 is given as 1.3. On the other hand, the oxidation of leucouranine by oxygen becomes apparent in a high oxygen concentration, such as an air-saturated solution. Namely, the molecular complex consisting of the triplet state of acridine and oxygen reacts with leucouranine, and the oxidation of the latter takes place. If one writes the rate constant of this reaction as k8 and that of the reaction in which the molecular complex decomposes into acridine and oxygen as k7, one can evaluate the ratio of \varphik8/k7 from the experimental results, where the value of \varphi is the transition probability in which acridine goes to the triplet state from the excited singlet state. An irreversible decomposition of the dye also competes with the above reactions. Putting its rate constant as k9, the value of \varphik9/k7 has been evaluated. The variation of the ratios of \varphik8/k7 and \varphik9/k7 with the variation in pH values has been interpreted on the basis that the reactivities of leucouranine are different in each ionic species. With the higher values of pH, the quantum yield becomes greater. The quantum yields of the formation of uranine and the irreversible decomposition of the dye have been evaluated as 0.0070 and 0.0055 respectively, yields which are about one thirtieth that in the deaerated solution. In the region of pH values lower than 8, a promoting action of a certain reaction seems to take part in the reaction and the reaction approaches the zeroth order.
Molecular Vibrations and Structures of High Polymers. V The Infrared Active Normal Vibrations of Isotactic Polypropylene, Poly(propylene-2-d), Poly(propylene-1,1-d2) and Poly(propylene-3,3,3-d3) in the 1500∼650 cm−1 Region
Authors: Miyazawa Tatsuo , Ideguchi Yoshiko
Published: July 2006

The infrared active normal vibrations of isotactic polypropylene and its deuterated derivatives in the crystalline state have been treated by the general method derived previously. The modified Urey-Bradley force field has been used; the trans- and gauchecoupling potential terms for the H–C–C angles and the angle-interaction terms for the methylene group have been added to the Urey-Bradley force field. A total of 16 potential constants have been adjusted by the method of least squares, and a total of about 100 infrared-active frequencies have been calculated with the r.m.s. frequency deviation as small as 1.1%. The potential energy distributions have been calculated, together with the normal modes, and the nature of the inferred bands observed in the 1500∼650 cm−1 region have been elucidated. Vibrational assignments for the well-defined liquid bands of isotactic polypropylene and its deuterated derivatives have also been made.
The Crystal Structure of Purpureo Salt, [Co(NH3)5Cl]Cl2
Authors: Shigeta Yoshihiko , Komiyama Yoshimichi , Kuroya Hisao
Published: July 2006

The crystal structure of [Co(NH3)5Cl]Cl2 has been determined by the two-dimensional Fourier method. The orthorhombic unit cell has dimensions of a=13.34, b=10.33 and c=6.73 Å, and it contains four formula units.

The space group is Pnma-D2h16.

The shape and the size of a complex ion were found to be approximately similar to those of the crystal of the corresponding rhodium(III) compound.

One NH3 group is co-ordinated to the central cobalt atom in the trans position to the chlorine atom; the Co-N(1) distance is 1.91Å, rather shorter than the four other Co-N distances, 1.97Å.
A Consideration of the Q-e Scheme. IV. A Theoretical Approach to Price-Alfrey’s Polarity Term
Authors: Kawabata Nariyoshi , Fueno Takayuki , Tsuruta Teiji , Furukawa Junji
Published: July 2006

Previously, we pointed out the correlations of the P-, Q- and e-terms with the components of the conjugation-stabilization energy between monomers and attacking radicals. In the present paper, the effect of heteroatoms on the components of the stabilization energy was investigated. For each series of isoelectronic monomers, in which a fixed carbon atom of a reference monomer (ethylene, styrene, butadiene or another neutral monomer) is replaced by a heteroatom (oxygen, nitrogen, etc.), we obtained the relations: lnQ−lnQ0=(Cm⁄RT)(δX)2, P∞exp(Cr⁄RT)(δY)2, eR=−\sqrtC′rm⁄RT(δY) and eM=−\sqrtC′rm⁄RT(δX). Here, Cm, Cr and C′rm are positive constants characteristic of the monomer series, while δX and δY are the Coulomb integral increments of the heteroatoms (relative to a carbon atom) in the monomer X and the radical Y respectively. Q0 is the Q-value of the reference monomer of the series. The e-values of the reference monomers were all assumed to be zero. The opinions of Price and Alfrey that the polarity term is the product of eR and eM and that eR1=eM1 for the radical and the monomer of type 1 seem to be not only convenient but also reasonable for a series of monomers having a same skeletal structure. The π-electronic charges, qR and qM, on the end groups of the radical and the monomer seem to be correlated with eR and eM in such a manner that eR=−(\sqrtC′rm⁄RT⁄CR)qR and eM=−(\sqrtC′rm⁄RT⁄CM)qM Here, CR and CM are negative constants characteristic of the series of monomers. The correlation of the polarity term with the electrostatic interaction between the charges of the radical and the monomer seems to be ascribable to these relations.
Studies on the Absorptiometric Determination of Microamounts of Boron. V. The Necessity of Methyl or Ethyl Oxalate in the Color Reaction of Boric Acid with Curcumin
Authors: Miyamoto Masatoshi
Published: July 2006

The coloration of microamounts of boric acid with an ethanolic solution takes place in the presence of oxalic, but not in that of other acids. Near-ultraviolet, visible, and infrared absorption spectroscopic studies have revealed that the aging reaction of an ethanolic curcumin-oxalic acid reagent solution is simply the esterification of the oxalic acid with the solvent used. The resulting diethyl oxalate is necessary to the color reaction. The role of the ester has not been interpreted yet; however, it is so unique that it can be performed only by dimethyl oxalate, not by the other esters. The esterification of oxalic acid in an acetonic reagent solution may be attributed to the presence of alcoholic impurities present in aceton used. The composition of the colored reaction product, rubrocurcumin, presented by Spicer and Strickland has not been substantiated yet in relation to the necessity of the esters to the color reaction.
The Composition of the Volatile Oil Obtained from the Leaves of Torreya nucifera and the Structure of Torreyol
Authors: Sakai Tsutomu , Nishimura Kiichi , Chikamatsu Hiroaki , Hirose Yoshio
Published: July 2006

It was found that the volatile oil from the leaves of Torreya nucifera contains limonene, 41.4% ; α-pinene, 23.0% ; myrcene, 6.8 ; terpinolene, 0.7% ; 3-carene, 0.3% ; γ-terpinene, 0.1% ; citronellol, 0.7%; terpinen-4-ol, 0.4%; α-terpineol, 0.3%; methyl salicylate, 0.2% ; phenylethyl acetate, 0.1%; δ-cadinene, 13.6%; γ-cadinene, 2.0%; β-elemene, 0.8%; torreyol (δ-cadinol), 3.1%; ( + )-cadinenol, 1.2%; nerolidol, 0.6%; small amounts of linalool and geraniol; two unknown sesquiterpenic hydrocarbons, 1.8%; an unknown sesquiterpene alcohol, 1.0%, and three unidentified carbonyl compounds.
The Chromatographic Separation of Polyoxyethylene Nonylphenyl Ether
Authors: Ishiwata Takashi , Nagayama Masuzo , Isa Hiroshi
Published: July 2006

Polyoxethylene nonylphenyl ether can be separated with respect to the unit of the oxyethylene radical by applying the chromatographic method, using silicic acid as the adsorbent and a chloroform-acetone mixture as the eluent. Nonylphenol was allowed to react with ethylene oxide in the mole ratio of 1:2 in the presence of metallic sodium as a catalyst at the three different temperatures of 190, 140 and 100°C.

The chromatographic method was applied to the reaction products, and it was shown that the distribution became somewhat narrower at the lower reaction temperature.

A comparison of these results with the theoretical distributions proposed by Flory and by Weibull indicated significant agreement with the latter but a discrepancy with the former. However, when the temperature was rather high, the agreement with the Weibull formula was not good.

Similarly, polyoxyethylene nonylphenyl ether having more than two oxyethylene units could be separated by this method. When \barP=10.3, 14 peaks was obtained from a chromatogram.

The separation and recovery by this method were considerably better than the distillation method, and a better understanding of the distribution of molecular weights was obtained.
The Rearrangement Reaction of Levulinic Acid in a Selenium Dioxide-catalyzed Hydrogen Peroxide Oxidation
Authors: Sonoda Noboru , Tsutsumi Shigeru
Published: July 2006

The selenium dioxide-catalyzed oxidation of levulinic acid with hydrogen peroxide in t-butyl alcohol gave glutaric acid and methylsuccinic acid as the rearrangement products. The glutaric acid may be formed by the migration of the β-carboxyethyl group to the methyl carbon atom and by the oxidation of the carbonyl group to the carboxyl group, and the formation of methylsuccinic acid may be due to the migration of the methyl group to the methylene carbon atom adjacent to the carbonyl group.
The Spectrophotometric Determination of Titanium with Hydrogen Peroxide and Xylenol Orange
Authors: Otomo Makoto
Published: July 2006

Although almost no color reaction occurs when titanium is treated with a solution of xylenol orange at pH below 2, the addition of hydrogen peroxide as a third reactant yields a new, red complex with an absorption maximum at about 535 mμ. On the basis of the above reaction, a new method for the spectrophotometric determination of titanium has been described. The color stability is affected by the amount of hydrogen peroxide and xylenol orange. When, however, 0.2 to 5 ml. of a 0.3% solution of hydrogen peroxide and 3.5 to 6 ml. of a 1×10−3M solution of xylenol orange are used for less than 70 μg. of titanium and a total volume of 25 ml., the color obtained is stable for at least 30 min. Beer’s law is obeyed over the 7 to 70 μg. range of titanium. The mole ratio method and the two spectrophotometric methods have been employed to determine the composition of the complex. It has been concluded that a 1:1:1 complex is formed under the conditions investigated.
The Complex Formation of Boron Fluoride with Lower Olefin at Low Temperatures. I. The Isotope Effects and Absorption Spectra of Boron Fluoride-Propylene and -Ethylene Systems
Authors: Nakane Ryohei , Watanabe Tsunao , Kurihara Osamu , \={O}yama Toshiyuki
Published: July 2006

The equilibrium constant of the isotopic exchange between boron fluoride gas and boron fluoride in a propylene solution at −112°C has been determined by means of a shaking-type gas-liquid contactor. When the mole ratio of propylene to boron fluoride in the liquid phase was larger than 1, the value of the constant obtained was 1.018. In the boron fluoride-ethylene system, the value of the constant is equal to the vapor pressure ratio of the isotopic boron fluorides, i.e., 1.011.

In the measurement of the absorption spectrum of liquid propylene at low temperatures, two weak absorptions were observed at 43650 and 45000 cm−1. They were assigned to the TR←N transition. When boron fluoride was added to liquid propylene at low temperatures, these absorption bands disappeared, although the V←N bands were still observed.

The above findings lead to the following conclusion: boron fluoride can form stable liquid σ-complexes with polar mono-olefins such as propylene at low temperatures; these complexes are not the intermediate products in polymerization by a boron fluoride catalyst. On the other hand, ethylene, which is a non-polar mono-olefln and which does not polymerized at atmospheric pressure, cannot form a stable σ-complex with boron fluoride, even at low temperatures.

The authors wish to express their deep thanks to Dr. Shizu Tonomura for her kind advice on measuring the absorption spectra.
The Spectrophotometric Determination of Uranium with Xylenol Orange
Authors: Otomo Makoto
Published: July 2006

A new spectrophotometric method for determining trace amounts of uranium has been developed. This method is based on the coloration of xylenol orange with uranium (IV) formed by the reduction of uranium(VI) in the presence of ascorbic acid. The effects of the pH value, reagent and boiling time have been thoroughly investigated, and experimental conditions which make possible the determination of 20 to 100 μg. of uranium have been devised. The mole ratio of the complex between uranium and this reagent has also been discussed.