bluuebunny/crossref_metadata_2025 huggingface dataset:
Phase Relationship in System 3CaO·P2O5–MgO–SiO2
Authors: Sata Toshiyuki
Published: July 2006

The phase relationship in the system 3CaO·P2O5–MgO–SiO2 was investigated by a cooling experiment in the usual manner. The system 3CaO·P2O5–MgO, a side of this triangle, is a simple binary one, its eutectic being located at the composition of 4∼7% by weight of magnesia and 1570±20°C. The system 3CaO·P2O5–2MgO·SiO2 is not binary over the temperature of about 1350°C, below which it is considered as binary. Above 1350°C, nagelschmidtite is formed over the whole composition range and crystallized primarily from liquid at a high 3CaO·P2O5 portion. The minimum liquidus temperature is 1394°C, which is located at the composition of 70% C3P and 30% M2S. The system 3CaO·P2O5–MgO–2MgO·SiO2 was considered to be complex owing to the presence of nagelschmidtite, but the eutectic among their three components is located at the composition of 70% 3CaO·P2O5, 21% MgO, and 9% SiO2, and 1362±5°C.

From the results described above and from those of the author’s previous reports, the preliminary phase diagram of the system 3CaO·P2O5–MgO–SiO2 was constructed. In this diagram the problem that nagelschmidtite is formed in the composition range which is rich in 3CaO·P2O5 was not mentioned in detail. In addition to this, it was found by X-ray examination that β-tricalcium phosphate may be apparently stabilized at a higher temperature than β-α transition point, and has the appearance of dissolving magnesia component.
Kinetic Studies on Solvolysis. VII. On the Kinetic Resolution at the First Stage of the SNl-type Solvolysis of α-Phenethyl Chloride in Optically Active Carboxylic Acid Solvents
Authors: Okamoto Kunio , Takeuchi Ken-ichi , Shingu Haruo
Published: July 2006

1) In SN2 displacement reactions of (±)-α-phenethyl chloride with triethylammonium (+)-α-methyl camphorate and with triethylammonium (−)-pinonate in dioxane, α-phenethyl chloride of 0.08% of optical purity (l-configuration) and of 0.15% of optical purity (l-configuration) were recovered at the stage of about 5% conversion, respectively.

2) In SN1-type solvolysis of (±)-α-phenethyl chloride with anilinium (+)-α-methyl camphorate and (−)-pinonate in acetonitrile, the recovered α-phenethyl chlorides showed no perceptible optical activity on the half way for each of the reactions. From this, the possibility of the induced resolution caused at the first stage by kinetic resolution at the second stage of the SN1-type solvolysis was eliminated.

3) In SN1-type solvolysis of (±)-α-phenethyl chloride in (+)-α-methyl hydrogen camphorate and in (−)-pinonate, about half of the chloride was converted to the ester at the similar reaction conditions (temperature and time) to the SN2 displacement reactions carried out in dioxane. The recovered chloride in the reaction in hydrogen camphorate showed optical purity of 0.54∼0.58% (l-configuration). In pinonic acids with various optical activities the recovered chlorides possessed optical purity of 0.13∼0.27% (d-configuration).

4) In comparing the configurations and optical purities in SN1- and SN2-conditions, it is concluded that optically active solvent molecules, like (+)-α-methyl hydrogen camphorate and (−)-pinonic acid, can cause kinetic resolution in the first ionization stage of the SN1 type solvolysis and therefore they obviously play a rôle as a kind of reactant molecule which controls the steric course of the solvation reaction in the first stage of this solvolysis.

5) In the SN1-type solvolysis of optically active α-phenethyl chloride in presence of triethylamine in (+)-α-methyl hydrogen camphorate, optically active β-(α-phenethyl)-α-methyl camphorate gave optically active α-phenethyl alcohol of 37% inversion, 63% racemization of configuration. From this it was concluded that SN2-like spatial orientation predominates at the second stage of this solvolysis.

6) For each of the resolution results of α-phenethyl chloride under SN1- and SN2-conditions, the relationship between the configuration of the resolved alcohol and the resolution controlling stage was predicted on the basis of the observed inversion at the second stage of the solvolysis. The configurations observed for the α-phenethyl alcohols were found to be consistent with the predictions.
Abnormal Acceleration of the Rate of Bulk Polymerization of Styrene
Authors: Nishimura Norio
Published: July 2006

The bulk polymerization of styrene initiated by 2,2′-azobisisobutyronitrile was carried out up to high conversion at 60°C. The comparison of the experimental conversions∼time data with calculated ones showed that there was a considerable deviation between them. The rate of the polymerization became explosively great toward the last.

Assuming the combination termination, the cumulative degree of polymerization was calculated and the values were compared with those obtained experimentally. The deviation at high conversion might be owing to the decrease in the catalyst efficiency as suggested by Robertson. However, the assumption that the polymer molecules have been produced only by combination is very doubtful.

The study of the molecular weight distribution suggested that the abnormal increase in the rate and the degree of polymerization seemed to be owing to the burying of the growing polymer radicals in themselves in the highly viscous solution.
Interactions of Surface Active Agents with Congo Red
Authors: Hayashi Makoto
Published: July 2006

The spectral changes of Congo Red solution with the addition of Tween 80 and cetyl pyridinium chloride were measured at various pH.

The wavelength of the absorption peak of the interaction product between Congo Red and Tween 80 is 510 mμ in the acidic medium as well as those in the neutral and the basic ones, from which it is considered that they produce a molecular compound of a definite constitution irrespective of the medium pH. However, since the amount of Tween 80 required to show the same effect in spectra increases with lowering pH, it is considered that only a base form of Congo Red is probably active and binds with Tween 80 at the amino groups.

The solutions of Congo Red containing sufficient cetyl pyridinium chloride have an absorption peak at 460 mμ. The product is completely precipitated as the ratio of Congo Red to cetyl pyridinium chloride is 1/2 and dispersed in both sides of this ratio, which depends little on the medium pH. This is considered to show that cetyl pyridinium chloride binds with Congo Red at the sulfonate groups, the product becomes most hydrophobic as two sulfonates in a molecule are blocked and hydrophilic with an excess of the detergent.
Studies on Polymerization and Depolymerization of ε-Caprolactam Polymer. IX. Reformation Reaction of ε-Caprolactam from Poly-ε-capramide
Authors: Ogata Naoya
Published: July 2006

The reformation reaction of ε-caprolactam from poly-ε-capramide having modified end-groups has been studied. It was found that no ε-caprolactam was reformed at 230°C from the polymer of which all of the end-groups were –COONa or –NHAc groups, while ε-caprolactam was reformed slowly at 257°C. The rate of the reformation of ε-caprolactam from the polymer having –COONa or –NHAc end-groups is about 1/10 of that from the polymer having normal end-groups at 257°C and it is independent of the polymerization degree of the polymer.

The polymerization and the depolymerization reactions of ε-caprolactam polymer occur predominantly on the end-groups and the interchange reaction between two adjacent amide groups in the polymer chain occurs slowly.
Studies on Organophosphorus Compounds. III. On Phosphite Copper Cyanide Complex Compounds
Authors: Nishizawa Yoshihiko
Published: July 2006

Trialky phosphite reacts with copper cyanide to give phosphite or bis-phosphite copper cyanides according to the mole ratio of phosphite to copper cyanide.

It is made clear from their molecular weights that these products form polymer in various organic solvents. Moreover, these products have strong fungicidal action but this will be reported in another paper.
Mass Spectra at Low Ionizing Voltage and Bond Dissociation Energies of Molecular Ions from Hydrocarbons
Authors: Omura Itiro
Published: July 2006

Relative yields of parent and principal fragment ions from four paraffins and olefins by electron impact are measured for the first time. The characteristic features of the ion yields can be classified into four types related with the ionizing voltages. The decomposition processes for some fragment ions can be explained under some assumptions, and those for forbidden ions C2H5+ from isobutane and cis-2-butene under the assumption of hydrogen rerrangement.
Natural Fur an Derivatives. V. The Number of Double Bonds in Obacunone
Authors: Tokoroyama Takashi , Kamikawa Tadao , Kubota Takashi
Published: July 2006

Obacunone has only three double bonds in total, two in its furan ring and one in its α,β-unsaturated lactone group and, therefore, it possesses a bicarbocyclic ring.
Studies on the Composition and Properties of Less Familiar Metal Cyano Complexes. II. Composition of Copper Octacyano Molybdate and the Existence of the Redox System Cu++Mo(CN)83−\ightleftarrows Cu2++Mo(CN)84−
Authors: Malik Wahid U , Ali S Iftikhar
Published: July 2006

The reaction between copper sulfate and potassium molybdocyanide was studied using conductometric, potentiometric and amperometric methods. The stoichiometric ratio of 2 : 1 for Cu2+ to Mo(CN)84− correspond to the formation of Cu2Mo(CN)8. The interaction of cuprous chloride and potassium molybdicyanide resulted in the formation of K2CuIIMoIV(CN)8. Evidence for the existence of a redox potential in the system Cu++ Mo(CN)83−\ightleftarrows Cu2++Mo(CN)84− could be obtained for the latter reaction on the basis of potentiometric titrations.
Molecular Rotations of Terpenes in Relation to their Structures. I. The Internal Conformation of Isopropyl Group in Menthol-like Substance
Authors: Yamana Shukichi
Published: July 2006

From the standpoint of the fact that a menthol-like substance is a kind of hydroxycyclohexane, the molecular rotations of menthol-like substances are calculated by using the PM-method. A comparison of the calculated values with the corresponding observed values seems to make it possibe to presume the type of the internal conformation of (iso-C3H7)4α.
Structure of Enteromycin. I. Derivatives and Products in Various Reactions of Enteromycin
Authors: Mizuno K\={o}mei
Published: July 2006

In order to know its functional groups and the combining state of the groups, enteromycin was subjected to such reactions as methylation, amidation, degradation, and catalytic reduction, and the properties of the products were investigated.
Photochemical Processes due to n-π* and π-π* Transitions of 3-Picoline N-Oxide in the Vapor Phase
Authors: Hata Norisuke
Published: July 2006

Gaseous photolysis of 3-picoline N-oxide was attempted by irradiation with the 3261Å (Cd 3P1) or 2537Å (Hg 3P1 resonance line corresponding to an n-π* or a π-π* absorption region, respectively, of this substance. In either case, the photolytic products were mainly 3-picoline, and we observed a remarkable temperature-dependence for the quantum yield of 3-picoline in the case of 3261Å irradiation but not in the case of 2537Å irradiation. This observation suggests that an activation energy would be required for the production of 3-picoline at 3261Å only. The activation energy estimated from the relation between the quantum yield of produced 3-picoline and the temperature at 3261Å irradiation was about 11.5 kcal. mol−1, which is almost about the same value as that of pyridine N-oxide. The reactions succeeding to an n-π* or a π-π* transition of 3-picoline N-oxide were considered to be similar to the case of pyridine N-oxide.
Studies on the Surface Structure of Porous Materials
Authors: Tsuruizumi Akie
Published: July 2006

1. The adsorption characteristics of ths sugar carbon prepared by carbonization or activation and silica gel were studied in detail by the adsorption of water, benzene and fatty acid vapors, and mercury porosimetry.

The pore distribution of the active carbon was tri-disperse. The effects of the partial filling of the pores were examined. The missing link in the distribution curve between the micro-pore and transitional pore in the previous reports was replenished.

2. The narrow-neck or ink-bottle structure of the pores of sugar carbon complicated the adsorption characteristics. The pores of the silica gel were cylindrical with a uniform section.

3. In order to specify the physical selective adsorption, the new term “ sieving coefficient” was defined from the relation between the pore radii and cross sections of the adsorbates.
Non-empirical Study of the π-Electronic Structure of Vinyl Chloride Molecule by Valence Bond Method
Authors: Takekiyo Shozaburo
Published: July 2006

π-electronic energy levels, probabilities of the resonance structures, π-electron densities, and the bond orders of the vinyl chloride molecule have been calculated non-empirically by the standard valence bond method, based on a complete set of the π-type resonance structures. Slater 2pπ- and 3pπ-orbitals have been assumed for the carbon and chlorine atoms and all the multiple exchange integrals have been considered. The calculated transition energy between the ground state and the first excited state is 11.41 eV., the ionic character is 31.54%, and the positive charge on the chlorine atom is 0.0849 (experimental value is 0.06.).
Thermodynamical Studies on Binary Systems Consisting of Polar and Non-polar Liquids. IV. Estimation of the Electrostatic Part of the Excess Enthalpy from the Observed Values aud Comparison with the Calculated Values
Authors: Amaya Kazuo
Published: July 2006

The electrostatic part of the van Laar coefficients were derived from the observed value of heats of mixing and some regularity was found between these values and the dielectric constant of polar components if non-polar components are non-aromatic (group I). However, no regularity exists between them if non-polar components are aromatic (group II). These values were also compared with the calculated values. For group I, qualitative agreements were obtained and this confirms the fact that the variation of α with concentration is due to dipolar interaction of the polar components. The agreement is poor for systems containing a polar component with large dipole moments or for one containing a non-polar component with quadrupole moment. For group II, no qualitative agreement was obtained.
Infrared and Raman Spectra of Dialkoxymethanes in Various Phases and the Assignment of Spectra of Methoxyethoxymethane
Authors: Nukada Kenkichi
Published: July 2006

The rotational isomerism of dialkoxymethanes (CH3OCH2OCH3, CH3OCH2OC2H5, C2H5OCH2OC2H5 and (CH3)2CHOCH2OCH·(CH3)2) is discussed from the spectroscopical point of view. The experimental results are as follows.

1) The appearance of infrared spectra is appreciably different among the vapor, liquid and solid phases. Of these, the solid spectrum gives the most complicated figure.

2) No solvent effect is obtained in acetonitrile solution.

3) No change is observed in the vapor infrared spectrum between room temperature and 100°C.

It is concluded from these results and data of dipole moment that dimethoxymethane exists as one configuration in the liquid and vapor phases, the terminal methyl groups of which are rotating about 120° anticlockwise sense from the central OCO plane.

The configuration of other dialkoxymethanes are assumed to be of one form by the analogy of experimental results.

Finally, the assignment of vibrational spectra of methoxyethoxymethane is presented.
Studies on Tritium Labeled Compounds. II. Preparation of Tritium Labeled Stearic Acid
Authors: Sato Yoshishige , Meshi Teruhiko , Takahashi Tadao
Published: July 2006

Chemical reduction method, exchange method, electric discharge method and recoil tritium labeling method were applied for preparing tritium labeled stearic acid. As the result of the recoil tritium labeling, the irradiated stearic acid was found to contain high destruction products which are mainly composed of esters of fatty acid.
Statistical Thermodynamics of Solutions of Optically Active Substances. I. Excess Free Energy of Binary Solution of d- and l-Isomers
Authors: Amaya Kazuo
Published: July 2006

A statistical mechanical theory of solutions consisting of d- and l-optical isomers is developed based on a new model of optically active molecules, and the excess free energy of the system is also derived and the order of magnitude of this quantity is examined.
Spectroscopic Studies on Molecular Configurations of Some Aliphatic Dinitriles. II. Infrared Spectra of Glutaronitrile and Bis(glutaronitrilo)copper(I) Nitrate
Authors: Matsubara Ikuo
Published: July 2006

The infrared spectra of glutaronitrile and bis(glutaronitrile)copper(I) nitrate, [Cu{NC–(CH2)3–CN}2]NO3, have been studied. the spectrum of the complex has been analysed on the basis of the result of X-ray analysis which disclosed that the ligand glutaronitrile takes the GG configuration in the crystals of this compound. This complex reacts with alkali halides such as free glutaronitrile. Considering the frequency shifts of the nitrate vibrations the reaction of the complex with potassium bromide should be ascribed largely to an ion interchange between the two phases. The increase of 29 cm−1 in the C≡N streching frequency by complex formation may be understood from the linear structure of the Cu-N-C-CH2 group which suggests that the carbon-nitrogen bond is essentially of a triple-bond character, the contributions of polar resonance structures such as –C+=N− being decreased. Glutaro-nitrile can form two different crystaline solid phases, depending on the mode of crystallization. From comparison of the two solid-state spectra with that of the complex and from consideration of the vibrational selection rules it has been concluded that glutaronitrile takes the GG configuration in one crystalline solid state and the TG in the other, and that it exists as a mixture of three isomers, GG, TG and TT in the liquid state. Calculation of the skeletal defornation frequencies for each isomeric form has given the results which support this conclusion. Vibrational assignment of glutaronitrile in various states has been made satisfactorily on the basis of the above results.
Studies on Dehydroalanine Derivatives. V. Radical Polymerization of N-Carboxy-dehydroalanine Anhydride and of N-Phthaloyl-dehydroalanine. Synthesis of a New Amphoteric Polymer
Authors: Sakakibara Shumpei
Published: July 2006

Homopolymers of N-carboxy-dehydroalanine anhydride (I) and of N-phthaloyl-dehydroalanine (II), and copolymers of II with vinyl acetate were synthesized. Hydrolysis or hydrazinolysis was carried out to obtain polymers containing α-amino acid structures. Actual structures of these polymers were discussed.
Thermodynamic Studies on Cobalt Complexes. IX. Chemical Equilibrium between Diaquotetramminecobalt(III) Complex and Oxalate Ion
Authors: Mori Motoshichi , Tsuchiya Ryokichi , Matsuda Eisei
Published: July 2006

The equilibrium of the reaction, [Co(NH3)4·(OH2)2]3++C2O42−=[Co(NH3)4C2O4]++2H2O (1), was measured spectrophotometrically and the free energy of formation of oxalatotetramminecobalt(III) ion was calculated. The large increase of the entropy for the above reaction was interpreted by the chelate effect of oxalate ion.

When the mixture of oxalic acid and potassium oxalate reacts with diaquotetramminecobalt(III) complex, oxalate ion is coordinated as a bidentate ligand, whereas it is coordinated as an unidentate ligand when ammonium oxalate reacts with the same diaquo-complex.
Visible Absorption Spectra of 1,3,5-Trinitrobenzene and its Derivatives in Aqueous Alkaline Acetone
Authors: Abe Takehiro
Published: July 2006

The visible absorption spectra of the colored solutions produced by adding aqueous sodium hydroxide solution or ammonia water to the acetone solutions of 1,3,5-trinitrobenzene and its derivatives (2,4,6-trinitrotoluene, tetryl and picryl chloride) were measured at room temperature in order to investigate the difference of the chemical actions between stong-alkaline sodium hydroxide and weak-alkaline ammonia water.

These trinitro compounds in acetone containing sodium hydroxide show spectra similar to that of the aqueous sodium hydroxide solution of tetryl. The spectrum of this aqueous colored solution is considered to be due to an intermediate of the Meisenheimer type in the process of the substitution reaction of tetryl to picric acid. Consequently, all the spectra of the colored solutions from the trinitro componds are also probably due to the intermediates ot the Meisenheimer type.

Each colored solution of the trinitro compounds in acetone containing ammonia water initially shows the same spectrum as that with sodium hydroxide, except for the case of trinitrotoluene, and changes to the other colored solution having an intense and stable band entirely different from the initial spectrum. The initially formed colored solutions of these trinitro compounds, except the solution from trinitrotoluene, may also be due to the Meisenheimer intermediates.
Statistical Thermodynamics of Solutions of Optically Active Substances. II. Solubility of d- and l-Isomers in Optically Active Solvents
Authors: Amaya Kazuo
Published: July 2006

The statistical mechanical expression relating the solubilities of d- and l-optical isomers in optically active solvent is derived.

It is shown that there exists a difference between these two solubilities.

The possibility of optical resolution is also discussed.
Adsorbabilities of Diacidotetrammine Type Cobalt (III) Complex Ions on a Cation Exchanger
Authors: Mori Motoshichi , Shibata Muraji , Hori Kuniko
Published: July 2006

Additional elution experiments for confirming the fact that the trans ions of the diacidotetrammine-type complexes are always eluted faster than the corresponding cis ions have been performed by using several diacido-type complexes which are relatively unstable. By comparing the elution maxima for the whole complex ions which have been used to date, the relative adsorbabilities of the isomeric ions on a cation exchanger have been predicted as follows:

For the trans ions,

[Co en2(NCS)2]+<[Co en2(NO2)2]+\simeq

[Co en2Br2]+<[Co en2Cl2]+\simeq

[Co en2NO2Cl]+<[Co(NH3)4(NO2)2]+<

[Co en(NH3)2Cl2]+

For the cis ions,

[Co en2Cl2]+<[Co en2(NCS)2]+<

[Co en(NH3)2Cl2]+\simeq[Co en2NO2Cl]+<

[Co en2(NO2)2]+<[Co(NH3)4(NO2)2]+

A part of the present work was supported by a grant-in-aid from the Ministry of Education.
Visco-elastic Behaviors of Aluminum Soap-Hydrocarbon Systems. I. Aluminum Stearate in Nujol
Authors: Shiba Sukekuni
Published: July 2006

Dynamic visco-elastic behaviors of the aluminum stearate nujol system were studied, using a concentric cylinder type forced oscillation rheometer. The system behaves always as a typical visco-elastic body in a wide range of concentrations and temperatures, and manifests conspicuous amplitude and frequency dependence, which indicates non-linear visco-elastic properties. Wedge type relaxation spectra of the system were obtained, and it was found that the system is thermo-rheologically simple in a confined region of temperatures. The time effect of the specimen and temperature dependence of dynamic properties were examined, and the rheological structures in the system under various conditions were discussed.
Studies on Mass Spectra and Appearance Potentials of Acetic Acid and Deuteroacetic Acid CD3COOH
Authors: Hirota Kozo , Nagoshi Kazuo , Hatada Motoyoshi
Published: July 2006

In order to obtain information on the decomposition process of acetic acid in radiation chemistry, not only mass spectra of both acetic acid and deuteroacetic acid but also appearance potentials of parent and main fragment ions of both acids have been measured.

By studying the effects of ion source temperature and of electron accelerating voltage on the spectra, and by comparing the mass spectra of both acids, it has been possible to identify the chemical species produced by electron impact without ambiguity and also to estimate the process of their production to some extent.

It has been found that, although the appearance potentials of the parent ion of both acids coincide fairly well, those of CH3+ and COOH+ from CH3COOH are higher than those of corresponding ions from deuterated acid. The breaks of ionization-efficiency curves have been observed in CH3+ and CD3+ ions at about 6 volts higher than the appearance potentials suggesting a possibility of the presence of an excited state of the product ions.
The Resonance Effect of Amide Group on the Polymerizability of Lactam Derivatives. I. The Infrared Spectrum of N-Methyl Lactams
Authors: Ogata Naoya
Published: July 2006

The infrared spectra of several N-methyl lactams and acid amides have been measured in chloroform solution in order to investigate the correlation between the polymerizability of lactams and the frequencies of the carbonyl absorption of the amide group. The observed frequency lowering of the amide I band by N-methyl substitution can be related to the increasing contribution of the ionic structure to the resonance in the amide group, and to the low polymerizability. The infrared spectra of N-methyl lactams exhibit doublets or triplets in the carbonyl stretching region.
Vinyl Polymerization XLVII. Polymerization of Acenaphthylene with Ziegler-Type Catalysts
Authors: Imoto Minoru , Soematsu Isamu
Published: July 2006

Polymerization of acenaphthylene was studied kinetically in heptane or toluene in the presence of titanium butanate-aluminum triethyl or titanium butanate-lithium aluminum hydride at 40∼95°C. Activation energy was computed as 14.3 and about 13kcal./mol.

Molecular weight of the polymer obtained was 125000, while [η]Benzene30° was only 0.035 (c=g./ 100ml.).
Studies on the Mucilage of the Root of “Tororo-aoi” (Abelmoschus manihot, MEDIC). III. On the Mechanism of the Characteristic Colloidal Nature of the Mucilage
Authors: Inokawa Saburo
Published: July 2006

1) The colloidal characteristics of the mucilage from “Tororo-aoi” such as the elasticity, spinnability, and so on are caused by the network built by interlocking between short branched chains of the mucin molecules, fibrous glucosans and proteins.

2) The remarkable change of the colloidal nature by heating is caused by breaking down the interlocking by oxidation.
The Effect of Alcohols on the Solubilization of Oleic Acid in the Aqueous Solution of Sodium Dodecyl Sulfate
Authors: Matuura Ryohei , Furudate Kazuo , Tsutsumi Hidetoshi , Miida Seido
Published: July 2006

The solubilization of oleic acid in the aqueous solution of sodium dodecyl sulfate was studied in the presence of various kinds of alcohols in various concentrations. When the concentration of alcohols in the detergent solution is not so great, the solubility of oleic acid decreases as the amount of alcohols increases. This is explained by the solution of oleic acid and alcohols in the same place in the micelle, i. e., in the palisade layer. When the water soluble alcohols are used the solubilization of oleic acid turns out to increase at a certain concentration of the alcohols in the detergent solution. This is explained by the solution of oleic acid in the solvent liquid as well as in the detergent micelles.
The Effects of Various Spinning Processes on the Fine Structure of Viscose Rayon Staples (Distribution of Chain Length of Oxidizing-hydrolyzed Residue)
Authors: K\={o}shiro Taketoshi , Fujimura Toshikazu
Published: July 2006

The fractionation of oxidizing-hydrolyzed residue was applied to study the fine structure of various types of rayons.

It was assured that tirecord, high-tenacity rayon spun in high zinc percent Muller’s bath, Toramomen and ordinary rayon have one sharp peak in each crystalline size distribution curve and smaller crystallites than Lilienfeldt-type rayon which shows two peaks in the crystalline size distribution curve.

The alkali-treatment of Lilienfeldt-type rayon increases not only its crystallinity but also the crystalline size, probably owing to the fusion of two adjacent crystallities.

There can be a correlation between the crystalline size distribution by oxidizing-hydrolysis and the lateral-order distribution; namely, the higher lateral-order portion may consist of the longer crystallite.

The carboxyl group in the oxidizing-hydrolyzed residue increases rapidly in the initial stage of hydrolysis and then decreases to an equilibrium value. The apparently lower accessibility by iodine sorption may be due to the negative carboxyl group remaining.
On the Reaction of Aromatic Dinitriles and Formaldehyde
Authors: Tachikawa Toshihisa
Published: July 2006

1. Like aliphatic dinitriles, polyamide having benzene nucleus and -CONH- linkages was synthesized by condensation polymerization reaction of aromatic dinitriles and formaldehyde in concentrated sulfuric acid.

2. The condensation polymer obtained from terephthalonitrile had the greatest intrinsic viscosity among ortho-, iso-, tere-phthalonitrile and p-xylylene cyanide. A product of the highest condensation polymerization degree was obtained, by adding the 1.025: 1 molar mixture of paraformaldehyde and terephthalonitrile in small portions into ten molar amounts of 95% sulfuric acid at 0°C and then stirring for ten hours at the same temperature.

3. These condensation polymers were insoluble in almost all organic solvents and had no melting and softening point. They decomposed above 300°C.
Polarographic Investigations of Vitamin C. III. Reduction Waves of the Condensation Products of Dehydro-l-ascorbic Acid and its Related Compounds with o-Phenylenediamine. Application to the Simultaneous Determination of l-Ascorbic Acid, Dehydro-l-ascorbic Acid and their Related Compounds
Authors: Wasa Tamotsu , Takagi Masanosuke , Ono Sôzaburo
Published: July 2006

The polarographic behavior of dehydro-l-ascorbic acid (DAA), dehydroreductic acid (DRA), alloxan, mesoxalaldehyde (MOA) and 2,3-diketogulonic acid (DGA) in acid buffer solutions containing o-phenylenediamine(OPD), has been investigated.

DAA shows three diffusion controlled reduction waves, whose half-wave potentials(E1⁄2) at pH 3.60 are −0.26, −0.44 and −0.67 V. (vs. N. C. E.), respectively. The limiting currents of the three waves depend on the time after the addition of OPD into the electrolytic solution, the concentration of OPD. pH and the temperature. When the electrolytic solution contains both AA and DAA, the oxidation wave of l-ascorbic acid (AA) can be obtained independently of the three waves for DAA in one polarogram.

DGA shows two reduction waves whose E1⁄2 at pH 3.44 are −0.27 and −0.40 V., respectively. The E1⁄2 of the first wave is very close to that of the first wave for DAA and the second wave seems to be identical with the second wave for DAA, but the velocities of the condensation reactions of DGA with OPD are much slower than those of DAA with OPD.

Alloxan and DRA show single well defined reduction waves, whose E1⁄2 at pH 3.60 are −0.32 and −0.19 V., respectively. The oxidation wave of reductic acid (RA) can be obtained with the reduction wave for DRA in one polarogram, while the oxidation wave of dialuric acid decreases very fast when alloxan and OPD are added into the electrolytic solution even after the careful removal of the atmospheric oxygen.

MOA shows a somewhat complicated behavior. In acid pH, the waves are not well defined and are considerably smaller than those of the above substances of the same concentration.

Discussions are made on the structures of the condensation products corresponding to their reduction waves.

Since the linear relationship between the limiting current and the concentration has been obtained, for DAA (the 3rd wave), DRA and alloxan, these polarographic phenomena have been applied to the simultaneous determination of AA and DAA, and to that of RA and DRA and further to that of AA and RA. The method is also applicable to the determination of alloxan, but not to those of MOA (or TR) and DGA, none of which, however, seriously interfere with the determination of DAA (or AA) by means of this polarographic OPD method.
Simultaneous Polarographic Determination of a System of o-Nitroanisole, o-Chloronitrobenzene and o-Nitrophenol
Authors: Honda Kenichi , Kikuchi Shin-ichi
Published: July 2006

1) The solution of o-nitroanisole, o-chloronitrobenzene and o-nitrophenol is investigated polarographically with the intention of their simultaneous determination.

2) The most suitable supporting electrolyte solution for the above object is the mixture of 4 parts of 1 n sodium hydroxide and 1 part of methanol.

3) Although this solution is not buffered, the variation of concentration of one component does not exert appreciable influence upon the wave-heights and the relative positions of the waves of other two components.

4) o-Nitrophenol can be determined directly from the ordinary polarogram. The accuracy of determination is under ±10%.

5) The residual current compensation gives aid to the determination of o-nitroanisole and o-chloronitrobenzene. By passing the compensating current very excessively, their reduction waves become better defined. The accuracy of determination is +8∼−17% for o-nitroanisole and −24∼−9% for o-chloronitrobenzene.

6) The half-wave potentials of three compounds, 5×10−4  m/l. in 1 n sodium hydroxidemethanol (4:1) solution are as follows;

(Remark: Graphics omitted.)

These values would give some indications for the estimation of the separation of waves.
Secondary Electron Emission from Copper-Beryllium (4%) Surface by Bombardment of Various Positive Ions
Authors: Sugiura Toshio , Hayakawa Teruo
Published: July 2006

The secondary electron emission from the non-activated and activated surfaces of copperberyllium (4%) by the impacts of various noble gas and hydrocarbon ions was studied together with the determination of the surface structure by the electron diffraction analysis. The main results obtained are as follows.

(1) The considerably thick layer of beryllium oxide is formed in the neighborhood of the target surface activated by oxygen at the temperature range of 350 to 480°C.

(2) The oxide films of copper are formed on the target surface by electropolishing, but these oxides easily undergo reduction by the prolonged ion bombardments.

(3) The optimum temperature of activation for the electron yield seems to be about 420°C, and the electron yield for the activated target surface treated at 350 or 420°C is only slightly dependent upon the ion kinetic energy.

(4) No measurable decrease in the electron yield for the activated surface treated at 420°C was obtained by the prolonged bombardments of various positive ions for ten hours, while the electron yield for the non-activated surface decrease about 20 per cent by the prolonged bombardments of ions for five hours.

(5) Under the present experimental conditions, the mechanism of the electron ejection process seems to be considerably complicated and it is difficult to deduce any definite conclusion for the electron ejection process.
Mineral Content of Mixed Fertilizer
Authors: Ando Jumpei , Matsuno Seiichi
Published: July 2006

The mineral content of mixed fertilizer produced with calcium superphosphate, ammonium sulfate and potassium chloride and also the reactions during the production process were investigated by X-ray diffraction.

It was observed that remarkable reactions took place between monocalcium phosphate, calcium sulfate, ammonium sulfate and potassium chloride by the addition of water for granulation. At the beginning of drying of the wet granules these minerals almost disappeared to form ammonium chloride and crystalline solutions of ammonium and potassium syngenite and those of monoammonium and monopotassium phosphate.

The syngenite thus formed decomposed partly by further drying and again formed while the product was placed in a storage pile. It seems that the caking of the product which often occurs in a storage pile is caused mainly by the crystallization of syngenite which decreases the amount of free water in the product and makes other salts crystallize at the same time.
Application of RADME to the Chelatometric Determination of Metals Employing the Alternating Current Polarographic Method
Authors: Kodama Mutsuo
Published: July 2006

RADME was applied to the chelatometric determination of copper, cadmium and lead with NTA by employing the A.C. polarographic method. At RADME practically no kinetic effects due to the dissociation of metal-nitrilotriacetate complex were observed and the concentration of metal ions could be determined accurately in the concentration range from 1×10−3m to 1×10−5m.
Synthesis of α-Maltosides. I
Authors: Matsubara Shoji
Published: July 2006

Substituted phenyl-, α-naphthyl-, and cyclohexyl-α-maltosides were prepared from octaacetyl-β-maltose and the corresponding phenols. p-Nitrophenyl-α-maltoside was also prepared by another method from the nitration of heptaacetylphenyl-α-maltoside. Alkyl-α-maltoside were prepared from maltose and corresponding alcohol.
Spectrophotometric Determination of Beryllium, Copper and Iron with Sodium-2″,6″-dichloro-4′-hydroxy-3,3′-dimethylfuchsone-5,5′-dicarboxylate
Authors: Katsube Yukiteru , Uesugi Katsuya , Yoe John H
Published: July 2006

Procedures have been developed for the spectrophotometric determination of trace amounts of beryllium, copper and iron(III) with sodium-2″,6″-dichloro-4′-hydroxy-3,3′-dimethylfuchsone-5,5′-dicarboxylate. Certain ions that interfere with the beryllium determination are removed by an oxine precipitation. Ions that interfere with the analysis of copper and iron(III) are removed with an anion exchange resin column.

Accuracy and precision are good. Beer’s law is obeyed up to about 0.3 p.p.m. of beryllium, about 4 p.p.m. of copper and about 3 p.p.m. of iron.
Infrared Spectra of Water of Crystallization in Some Inorganic Chlorides and Sulfates
Authors: Gamo Itaru
Published: July 2006

The characteristic bands of water of crystallization in various chlorides and sulfates were determined in the rock salt region. The results were classified and explained inclusively by the effects of coördination and hydrogen bonding.
Dehydrogenation of Secondary Alcohols with Reduced Copper. IV. Catalytic Dehydrogenation of Isopropyl Alcohol (Part 2)
Authors: Kawamoto Kazuaki
Published: July 2006

The present work is to determine whether the yields of acetone and of the oily products (isobutyl methyl ketone and diisobutyl ketone) to be obtained from isopropyl alcohol by the catalytic action of reduced copper are affected by the precipitation temperature in the preparation of the catalysts, and to find a catalyst efficient for the production of oily products. Isopropyl alcohol was changed to acetone in 91∼95% yield with no side reaction, by being passed over various copper catalysts at 325°C. The maximum yield of the oily products was obtained with the catalyst prepared with sodium hydroxide as a precipitant and at 22°C as the precipitation temperature, and at the reaction temperature of 220°C, amounting to 39.28% based on isopropyl alcohol used.
Differential Thermal Analysis of Aluminum Soaps
Authors: Shiba Sukekuni
Published: July 2006

Differential thermal analysis of two series of aluminum soaps–aluminum stearates of different compositions, and aluminum soaps from various parent fatty acids–are carried out, and transition temperatures and the heats of transition are obtained. Each transition point is assigned to a certain change in the structure of the soap or to the soap composition. The structure of the the soaps and the mechanism of soap formation are also discussed, based on the differential thermal analysis and infrared data.
Spectrophotometric Determination of Uranium with Sodium 2″,6″-dichloro-4′-hydroxy-3,3′-dimethylfuchsone-5,5′-dicarboxylate
Authors: Katsube Yukiteru , Uesugi Katsuya , Yoe John H
Published: July 2006

A procedure has been developed for the spectrophotometric determination of small amounts of uranium with sodium 2″,6″-dichloro-4′-hydroxy-3,3′-dimethylfuchsone-5,5′-dicarboxylate. Beer’s law is obeyed up to about 9 γ of uranium per milliliter. The accuracy and precision are satisfactory. Interference of foreign ions is eliminated by using an anion exchange resin.
Iodine-catalyzed Thermal cis-trans Isomerization of Azobenzene
Authors: Yamashita Shigeru
Published: July 2006

The equilibrium of 1 : 1 molecular complex formation between cis-azobenzene and iodine in n-hexane has been studied spectrophotometrically in the temperature range 10∼25°C. The heat of formation of the complex has been found to be −ΔH=7.5 kcal./mol. The rate of iodine-catalyzed isomerization of cis-azobenzene determined spectrophotometrically in n-hexane solution has been found to be proportional to the concentration of cis-azobenzene as well as to that of iodine, with an activation energy of 6.3 kcal./mol. over the temperature range 30∼50°C. The most probable interpretation of the rate measurements is that the complex of cis-azobenzene with iodine isomerizes with an activation energy of 13.8 kcal./mol. under the experimental conditions of the present work.
Infrared Spectra of Troponoid Compounds. II. Absorption Band of O–H Stretching Vibration in Some Tropolones
Authors: Ikegami Yusaku
Published: July 2006

Infrared spectra of tropolone, 4-isopropyltropolone and 3-bromotropolone in the solid, liquid and solution in carbon tetrachloride were measured with a calcium fluoride prism in the region of 3600∼2600 cm−1. The absorptions of O-H stretching vibration in these compounds in dilute solution are strongest at around 3120 cm−1 with numerous branches, and these bands shift gradually to the higher wave number side with 100∼88 cm−1, as the concentration increases and the compound transits to the liquid or solid state. This character was explained by the assumption that the tropolone skeleton has a stable chelate system and that the intermolecular action increases with the increase of concentration. In the solid state, a distinct band corresponding to the O–H group of Ib type was also observed at around 3540 cm−1.
Chemical Studies on Wood Hemicelluloses. III. On the Hemicellulose of Ganpi Bast Fibers. II
Authors: Machida Seishi , Nishikori Sadanori
Published: July 2006

The hemicellulose of Ganpi bast fibers (Wickstroemia sikokiana Franch. et Sav.) gave upon hydrolysis a mixture of an aldobiouronic acid, 4-O-methyl-d-glucuronic acid and d-xylose together with small amounts of d-galacturonic acid, d-mannose, d-galactose, l-arabinose and l-rhamnose.

The acidic components were separated, and by means of chromatography on a column of cellulose, 4-O-methyl-d-glucuronic acid, d-galacturonic acid and 2-O-(4-O-methyl-d-glucopyranosyluronic acid)-d-xylopyranose were isolated and characterized.

A structure was proposed for the hemicellulose which has a straight chain of about 160 1,4-linked-β-d-xylopyranose residues with, on the average, every sixth residue carrying a terminal 4-O-methyl-α-d-glucopyranosyluronic acid residue linked through position 2.

The d-galacturonic acid is believed to originate in pectic substance and not a component of the hemicellulose.

A part of the expense for this work was defrayed by the Grant-in-Aid for Scientific Research from the Ministry of Education. This is gratefully acknowledged.
A Study of Dehydration and Hydration of Sodium Dihydrogen Phosphate and Racemic Acid by Means of the Deuterium Exchange Reaction
Authors: Okazaki Nobukazu , Okumura Akiko
Published: July 2006

In order to examine the generality of the results obtained with oxalic acid, the following questions were studied with sodium dihydrogen phosphate and in part with racemic acid: (1) the relation between the deuterium exchange reaction and the surface area of the anhydrate, and the amorphous character of the anhydrate prepared by dehydration in vacuo at low temperatures, (2) recrystallization of the amorphous anhydrate under the catalytic action of adsorbed water, and (3) deuterium exchange reaction in anhydrate-hydrate mixture.

The results obtained with sodium dihydrogen phosphate and racemic acid are similar to those obtained with oxalic acid. It appears that formation of amorphous anhydrate in the dehydration of crystal hydrate in vacuo at low temperatures and its recrystallization under the catalytic action of adsorbed water are phenomena of general occurrence.

The deuterium exchange reaction of crystalline anhydrate may be used to determine the composition of the hydrate formed on hydrating an anhydrate under a given condition.
Biochemical Studies on Oils and Fats. X. Toxicity of Thermally Denatured Ethyl Linolenate
Authors: Matsuo Noboru
Published: July 2006

When ethyl linolenate is thermally denatured at 250°C for 40 hr. in a carbon dioxide stream, the product is toxic to rats. The origin of the toxicity of thermally denatured ethyl linolenate is a monomeric cyclization product, which is mainly a compound having a cyclohexene ring.
Infrared Absorption Spectra of Water of Crystallization in Aluminum Sulfate Octodecahydrate Crystals
Authors: Gamo Itaru
Published: July 2006

The observed spectra of water of crystallization were compared with those of aluminum chloride hexahydrate and interpreted on the basis of the effects of aluminum-water coördination and hydrogen bonding O–H…O. The wagging and the rocking frequency were both much higher than is usual in water of crystallization. It was proposed that this result, together with other peculiarities, may have some connection with the coördination strength between aluminum and water.
Thermodynamical Studies on Binary Systems Consisting of Polar and Non-polar Liquids. VI. Refined Calculation of the Electrostatic Part of van Laar Coefficients and Comparison with the Experimental Results
Authors: Amaya Kazuo
Published: July 2006

The electrostatic parts of van Laar coefficients for binary systems of polar and non-polar liquids were calculated, assuming that (1) the polar molecule is anisotropic in polarizability, (2) that the polar molecule is an ellipsoid, and (3) that the dipole is a point dipole and its position is not at the center of the molecule.

The results were compared with the experimental results.

The agreement between the experimental values and the calculated values based on the refined model cannot be said to have been improved compared with the previous results, in which the calculations were made based on the much simpler model in which the polar molecule was spherical and isotropic, and the dipole was at the center of the sphere.
Dye-sensitized Photopolymerization of Vinyl Monomers. II. Photo-bleaching of Acridine Yellow in Some Vinyl Monomers
Authors: Takemura Fukuo
Published: July 2006

The photobleaching of acridine yellow has been studied in various vinyl monomers, such as acrylonitrile, vinyl acetate, styrene, α-methylstyrene and methyl methacrylate.

It has been found that (a) the photobleaching is apparently different in featue depending on the type of monomer; (b) the absorption maximum of the dye in the reaction systems shifted rapidly to a shorter wavelength in the cases of both styrene and α-methylstyrene by the irradiation of light, while it did not in the cases of acrylonitrile, vinyl acetate and methyl methacrylate; (c) a new absorption maximum at a shorter wavelength may result from the production of a relatively stable intermediate from the dye and styrene.

Considering also the effects of such quenchers as potassium iodide and hydroqinone on the photobleaching and the polymerization, it has been concluded that the interaction of the triplet state of the dye molecule with the monomers is responsible for both the bleaching and the polymerization.
Factors which Determine Solubility
Authors: Shinoda K\={o}z\={o}
Published: July 2006

The factors which determine solubility in various systems have been analyzed and discussed. The orientation of the molecule, the pseudo-phase dispersion, the liquid state of the solute, solvation and the pseudo-phase inversion are important factors in increasing solubility in various non-regular solutions.