bluuebunny/crossref_metadata_2025 huggingface dataset:
Carbon Monoxide Chemisorption on Zinc Oxide
Authors: Kubokawa Yutaka
Published: July 2006

The rates of adsorption and desorption, and the adsorption equilibrium for carbon monoxide chemisorption on zinc oxide were measured over a wide range of temperatures as in the previous study of hydrogen chemisorption on zinc oxide. The behavior of desorption indicated the existence of two types of chemisorption; the non-activated type and the activated type. For the former type the heat of adsorption was estimated as 10∼12 kcal./mol. from the adsorption isotherms, in agreement with the activation energy of desorption. The considerable fraction of the latter type was reversible, i.e. desorbed as such. For this type, the activation energy of adsorption increased with the adsorbed amount from 5 to 16kcal./mol., and the rate was proportional to P0.8∼0.9. Moreover, the heat of adsorption obtained from the adsorption isotherms ranged from 25 to 38 kcal./mol., in fair agreement with those estimated from the activation energy of adsorption and desorption. The behavior of desorption suggested the predominance of surface heterogeneity, the nature of which was such that the activation energy of adsorption and the heat of adsorption varied conversely to each other.
The Aconite Alkaloids, XXXIII. On Lucidusculine. III
Authors: Amiya Takashi
Published: July 2006

The alkaloid lucidusculine was oxidized by hydrogen peroxide and also by perbenzoic acid to lucidusculine N-oxide. The N-oxide could be converted back into the original base by reduction. Oxidation of the alkaloid with N-bromosuccinimide afforded dehydrolucidusculine which was also produced by transformation of lucidusculine N-oxide. Dehydrolucidusculine seems to be a cyclic carbinolamine internal ether. The action of bromine on the alkaloid was noticeable and gave bromoanhydrolucidusculine hydrobromide which was probably obtained from the intermediate dibromide with loss of one mole each of water and hydrogen bromide. Chromium trioxide-pyridine complex oxidized lucidusculine to an amino acid which, on methylation with diazomethane, gave a methyl ester. From these experimental results, the previously proposed partial formula of lucidusculine was further extended.
Ternary Liquid Equilibria in System n-Heptane-Thiophene-Liquid Ammonia. New Tie Line Correlation
Authors: Ishida Kiyoharu
Published: July 2006

Phase equilibria for the system n-heptane-thiophene-liquid ammonia has been determined at temperatures of 0 and 20°C. A new method has been proposed which correlates tie line data in such a manner that a straight line is obtained for most systems including solutropic systems.
Polymerization of Methyl Methacrylate Initiated by a Combined Action of p-Tolylsulfonylacetic Acid and Dimethylaniline
Authors: Uehara Ryoichi
Published: July 2006

It has been found that the polymerization of methyl methacrylate is initiated by the system of p-tolylsulfonylacetic acid and dimethylaniline.
An Interpretation of the Elovich Equation for the Rate of Chemisorption on the Basis of Surface Heterogeneity
Authors: Kubokawa Yutaka
Published: July 2006

For the heterogeneous surface where the distribution function was variable and/or desorption could not be neglected, the rate of adsorption was derived and the physical meaning of constant b in the Elovich equation was given. It was shown that in complicated case the Elovich equation is expected to apply only approximately in a limited range of coverage. The variation in constant b with pressure or temperature was qualitatively explained in terms of the concept that on changing pressure or temperature, different sets of sites are covered and/or the contribution of desorption in adsorption rate measurements, is altered. The chemisorption of hydrogen on zinc oxide and on chromic oxide gel was discussed on the basis of the present interpretation of the Elovich equation. Finally, it was shown that, on the basis of surface heterogeneity, the constant b obtained from the integrated form of the Elovich equation can not be given any physical meaning when the constant t0 of an appreciable magnitude is required.
A Rapid Method for Determining Fission Products Contained in Waters Using an Ion Exchanger
Authors: Tsubota Hiroyuki , Kitano Yasushi
Published: July 2006

The essential point of this method is the use of the formate buffer solution. This method would be used for the analysis of fission products in natural waters and for the preparation of pure and carrier-free radioactive elements from mixed fission products.
A Rapid Method for Determining Alkali and Alkaline Earth Elements Using an Ion Exchanger
Authors: Tsubota Hiroyuki , Kitano Yasushi
Published: July 2006

Alkali and alkaline earth elements, including their rare elements, can be separately eluted easily, rapidly and completely by the elutriants here described. This procedure and its modified procedures can be applied to routine analysis of natural waters.
Pyrolysis of Organic Compounds. II. Pyrolysis of Toluene-3-d and Toluene-4-d
Authors: Takahasi Makoto
Published: July 2006

In order to elucidate the mechanism of the pyrolysis of toluene, pyrolysis of toluene-3-d and -4-d was carried out by the flow method in the temperature range 830∼955°C, and the mole ratios D2: HD : H2 and CH3D : CH4 were determined by mass spectrometry. The involvement of the reaction of ring-hydrogen in the pyrolysis has been confirmed from the formation of HD and CH3D. As there was not any distinct difference in the mole ratios between the reactions of toluene-3-d nor -4-d, it is concluded that the reactivities of m- and p-hydrogens of toluene are of the same order. Considering these results, the possible elementary processes involving ring-hydrogen are discussed.
Studies on Dehydroalanine Derivatives. II. Synthesis of Polydehydroalanine
Authors: Sakakibara Shumpei
Published: July 2006

The polymerization rate of N-carboxy dehydroalanine anhydride (I) was compared with that of N-carboxy Dl-alanine anhydride, and it was found, that the former was much slower than the latter at 30°C. Polydehydroalanine (IV) was obtained by heating the substance I in dry pyridine at 100°C, or by adding a small amount of triethylamine into the boiling toluene solution of I. The substance IV was water-soluble brown powder, the actual structure of which was supposed to be a pyrolidone-type polypeptide VI containing about 10% of dehydroalanyl residues.
Rotatory Dispersion of Metallic Co-ordination Compounds. II. Absorption Spectra and Rotatory Dispersion of Cobalt(III) Complexes of EDTA
Authors: Hidaka Jinsai , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

The rotatory dispersion measurements have been made for d-Na2[Co(edta)NO2]·3H2O, d-K[Co(edta)]·3H2O, d-K2[Co(edta)Cl]·3H2O and d-cis-[Co en2(NO2)2] I. On the basis of these measurements, the relation of the splitting of the first absorption band with the so-called anomalous rotatory dispersion has been discussed. In the anomalous rotatory dispersion of d-[Co(edta)NO2]2−, there appear two inver-sive dispersions due to the component absorption, Ia and Ib, of the split first absorption band. Similarly considered, it has been shown that the first absorption band of [Co(edta)]− or [Co(edta)Cl]2− may have two component absorptions in accordance with the behavior of its rotatory dispersion curve.
Magnetic Susceptibilities of Sulfur, Selenium and Tellurium from Room Temperature to 1100°C
Authors: Tobisawa Sh\={o}tar\={o}
Published: July 2006

(1) The susceptibility of sulfur showed the first change at about 157°C, showing no changes at the melting point and its neighborhood.The change is attributed to the radical chains owing to the scission of eight-membered sulfur rings.

(2) On fusion the susceptibility-temperature curve for glassy selenium deflected toward sides opposite to that for hexagonal selenium. It is considered that the decrease in susceptibility of glassy selenium can be ascribed to free radicals produced by the scission of selenium rings. On cooling, liquid selenium turned to glassy selenium, showing the increase in susceptibility at about 125°C. It can be considered that this change is related to the reclosing of chains into rings.

(3) The susceptibility of hexagonal tellurium decreased abruptly on fusion. It may be considered that this change is due to a paramagnetic contribution from unpaired spins produced by incomplete ionization of the valence shell.

(4) The susceptibility-temperature curves for sulfur and selenium were deflected toward paramagnetic sides above 353° and 690°C, respectively. The paramagnetism increased reversibly with temperature, while the susceptibility of tellurium was independent of temperature to 1100°C. On sulfur and selenium, the ratios of the weight of the diatomic molecule to the total weight at every temperature were obtained from the weight of the diatomic molecule estimated by comparing the experimental value of paramagnetic susceptibility with the value calculated from Van Vleck’s equation.
π-Electronic Structure of Diphenoquinone
Authors: Kuboyama Akira
Published: July 2006

The electronic structure of diphenoquinone was studied with the simple MO method using the similar integral values as adopted in our previous work on p-quinones. The obtained result was discussed in comparison with the previously obtained one for p-benzoquinone. As for energy levels, the lowest unfilled orbital (b2g) of diphenoquinone is far lower than the other unfilled orbitals as was obtained with the p-quinones The highest filled orbital (b1u) of diphenoquinone is considerably higher than the ones of the p-quinones. From the calculated result the intense absorption band near 390 mμ was unambiguously assigned to the A1g→B3u transition.
Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. I. Synthesis of Ser-Tyr-Ser-Met Sequence
Authors: Inouye Ken , Otsuka Hideo
Published: July 2006

1. Carbobenzoxy-O-benzylseryltyrosyl-O-benzylserylmethionine methyl ester, which has the N-terminal tetrapeptide sequence of corticotropin and α-MSH, has been synthesized.

2. It has been shown that the O-benzylseryl peptide bond is very stable to an alkali treatment.

3. Syntheses of the relating serine peptide derivatives have been described.
Aggregation of Ion-exchange Resin Particles
Authors: Sen\={o} Manabu , Yamabe Takeo
Published: July 2006

Some observations are presented on the aggregation behavior of the ion-exchange resin particles. On mixing the hydrogen-form cation-exchange resin particles with the hydro-xyl-form anion-exchange resin particles, remarkable aggregation takes place. It seems that this aggregation is due to the electrostatic attraction force exerted between resin particles. This is supported by the results that the aggregation is destroyed by addition of salts and that the agglomerates are not formed in non-polar medium in the complete absence of water. Moreover, it was demonstrated that the variation of the size ratio of particles influences markedly the aggregation behavior. A simple explanation is given for such a coagulation phenomena.
Ion-exchange Behavior of Acidic and Basic Amino Acids
Authors: Sen\={o} Manabu , Yamabe Takeo
Published: July 2006

The ion-exchange behavior of the acidic and the basic amino acids was described and discussed. The maximum uptake of amino acids takes place in the pH range close to the iso-electric points and the pH effect is more remarkable and more characteristic, in comparison with the case of neutral amino acids. Theoretical treatment on ion-exchange equilibria, which takes account of the dissociation equilibria of amino acids, explains well the experimental results and the selectivity coefficients were estimated herefrom.
Studies on the Silk-platinum Catalyst. I. Its Preparation and Activity
Authors: Akamatsu Akira , Izumi Yoshiharu , Akabori Shiro
Published: July 2006

1. A silk-platinum chelate, which had the highest platinum content, involving both the total platinum content and the coordinated platinum, was obtained when 400 mg. of silk-fibroin was boiled with 20 ml. of a 0.75% aqueous solution of potassium tetrachloroplatinate for 14 to 20 min.

2. The most active silk-platinum catalyst was obtained when reduction of the chelate was pepeated twice in 1% acetic acid with 90 kg./cm2 of hydrogen at 160°C. The activity was much influenced by the solvent, temperature and time used for its activation.

3. The catalyst could be stored for a long period in the dry state and even showed some increase in activity during storage.

4. The most active catalyst had about two hundred and fifty times as much activity as that of a platinic oxide catalyst in the hydro-genation of nitrobenzene to aniline.

5. The characteristic structure of the carrier seems to exert some steric hindrance on the hydrogenation of highly branched aromatic nitro compounds.
Fischer-Tropsch Synthesis with Tubular Reactor of 18.1 1. Catalyst Bed. II. Reactor with Temperature Gradient along Out-side Wall
Authors: Kuraishi Michio , Kurita Minoru , Hosoya Tadasuke , Ichinokawa Hideo , Ogawa Kiyoshi , Uchida Hiroshi
Published: July 2006

The present experiments on the Fischer-Tropsch synthesis have been made with the reactor which was placed in a bath of oil boiling under a reduced nitrogen pressure. The heat transfer efficiency referred to the out-side wall of the reactor has been improved considerably, and, as a consequence, the magnitude of the bed over-temperature remains comparatively small, in spite of the high yield of the product attaining 24∼26 kg./day. The axial and the radial temperature profiles have been separately calculated on the basis of the concentration gradient determined along the heights of the reactor: first the calculation of the former profile under the assumption of uniform temperature across the bed, and secondly that of the latter profile at a cross section in the neighborhood of which the axial temperature is approximately constant. By the convenient choice of 600 kcal./m2 hr. °C for the tube wall coefficient of heat transfer referred to the out-side wall of the present reactor, the calculated axial temperature profile is in good agreement with the experimental profile except for a small intermediate range.
Mercury Photosensitized Decomposition of Carbon Dioxide by 1849 Å (Hg*61P1)
Authors: Mori Yuji
Published: July 2006

The photosensitized decomposition of carbon dioxide by Hg*(61P1) and the direct photolysis by 1849 Å was investigated by the static method. The product in photosensitization was carbon monoxide and no oxygen was detected. The deficiency of oxygen in the product may be due to the formation of an oxide of mercury which was deposited on the front window of the reaction cell.

In photolysis of carbon dioxide, carbon monoxide and oxygen were produced in the ratio around 5:1. The deficiency of oxygen may be due to the wall effect and partly due to the formation of ozone.

The apparent quenching cross section was obtained by assuming a simple mechanism. The large value of the apparent quanching cross section of Hg*(61P1) is discussed from the point of view of intermolecular interaction between the excited mercury atom and carbon dioxide in the ground state.
Kinetic Studies on Solvolysis. VI. Kinetic Evidence of the Distinct Rôle of the Hydrogen Atom of Hydroxylic Solvent Molecules as an Attacking Center at the First Ionization Stage
Authors: Okamoto Kunio , Shingu Haruo
Published: July 2006

The catalytic constants of phenols, alcohols, and several polar and non-polar molecules in acetolysis of tert-butyl bromide were measured in acetic acid-carbon tetrachloride (1:3 by vol., at 25.0°C) in the presence of sodium acetate at 70.0°C. Ortho substituted (NO2, Cl, CH3, OH) phenols gave smaller constants than those of corresponding para derivatives, and among them o-nitrophenol gave the smallest one which was comparable to that of nitrobenzene. Dihydroxylic compounds, like 1,2-cyclohexanediols, ethylene glycol, catechol and water, gave constants greater than twice those of the corresponding monohydroxylic compounds, like cyclohexanol, ethanol, phenol and methanol, respectively. It was concluded that, in view of the lack of catalytic action of intramolecularly hydrogen-bridged hydroxylic compounds, the hydrogen atom of those hydroxylic molecules was distinctly the center of attack in the first ionization stage of the solvolysis and that two adjacent hydroxyl groups in dihydric compounds sterically co-operated in this stage. On these bases, similar accelerating action of various species of associated phenol molecules was suggested and illustrated by the analysis of the data of solvolysis rates of tert-butyl bromide in phenol-carbon tetrachloride mixtures at 20.0°C. It was shown that phenol polymer species with higher association degree exhibited more effective acceleration.
Studies on Long Chain Alkyl Amides of Water-soluble Poly-α-amino Acids. I. Amphipathic Properties of Poly-Dl-alanine Dodecylamide
Authors: Isemura Toshizo , Ikeda Shoichi , Tokiwa Fumikatsu , Noguchi Junzo
Published: July 2006

Poly-Dl-alanine alkyl amide has been synthesized by the polymerization of N-carboxy-Dl-alanine anhydride initiated with alkyl amine at different anhydride-initiator ratios ([A]/[I]). The amphipathic properties of poly-Dl-alanine dodecylamide (PADA) with [A]/[I] = 5 to 20 have been investigated in comparison with poly-Dl-alanine.

The degree of polymerization of poly-Dl-alanine part can be easily controlled by the initial [A]/[I] ratio. The number average degree of polymerization (x) is found to be approximately equal to [A]/[I].

The solubility of PADA in water is higher as x increases, and PADA with x>17 is transparently soluble. PADA with any x value is soluble in aqueous acid solutions, the pH of which is lower than 5.5. The titration curve with an aqueous acid solution shows a break at this pH.

The infrared spectra of PADA in the solid state indicate that PADA with higher x is almost in the random conformation and the portion of the β-conformation increases as x becomes lower.

Surface tension of PADA in aqueous acid solution exhibits typical characteristics of amphipathic substances. The degree of surface tension lowering at low concentration region is the largest for PADA of x=10.

The surface film of PADA is of condensed type and the limiting area is larger as x increases. PADA with higher x becomes more spread as surface film, more Dl-alanyl residues being on the aqueous surface.
Physicochemical Properties of Dilute Aqueous Solutions of Amylose. Optical Rotatory, Viscometric and Osmometric Studies
Authors: Kuge Takashi , Ono Sôzaburo
Published: July 2006

Optical rotatory power, viscosity and osmotic pressure of dilute aqueous solutions of amylose have been studied. Optical rotatory dispersions of amylose and β -limit dextrin in 0.2 m potassium chloride and 0.5 m potassium hydroxide are normal and can be well expressed by a single term Drude equation. All of the λc obtained from the analysis of the dispersion curves are close to 140 mμ which may be considered as a characteristic value of glucopyranose residue. This seems to indicate that there is no well-oriented helix of amylose in the solutions. With increasing temperature, the optical rotations of amylose and β-limit dextrin decrease. Amylose, especially in a neutral aqueous solution, has an unusually great temperature coefficient of specific rotation amounting to −1.4°/°C a the largest value. Parallel with this change, the viscosities of the amylose solutions decrease with increasing temperature. These results seem to be well explained by assuming that the flexibility of amylose molecules is considerably influenced by temperature through the change of the degree of hydrogen bonding between segments of the molecules. Osmotic measurements have given evidence to prove the occurrance of the association of amylose molecules in the solution examined. The degree of the association has been found to decrease with increasing temperature. These facts indicate that hydrogen bonding plays a significant role in the properties of the dilute aqueous solution.

The molecular configuration of amylose in aqueous solutions has been discussed. It seems to be most probable that amylose molecules in the solutions take the configuration of deformed helix, and associate highly with each other. No linear extended configuration is possible. The figure of the supposed configuration is drawn.
Thermodynamical Studies on Binary Systems Consisting of Polar and Non-polar Liquids. I. Construction of a Semi-automatic Microcalorimeter Suitable for the Rapid Measurement of Heats of Mixing of Binary Solutions
Authors: Amaya Kazuo
Published: July 2006

A semi-automatic microcalorimeter is constructed which is convenient for a large number of the measurements of heats of mixing of two kinds of liquid.

The calorimeter is equipped with a removable mixing vessel, its holder, and a container, by which the efficiency of the measurement is much increased. Automatic registering of the time intervals during which the electrical current is supplied to the calorimeter, as well as automatic thermal compensation for endo-thermic systems, are performed. It is another feature of the apparatus to require only less than 1 cc. of each component for each measurement. The elimination of the vapor phase of the liquids in the mixing vessel makes the results certain. The heat sensitivity is 10−3 joule.
Studies on the Silk-platinum Catalyst. II. General Properties
Authors: Akamatsu Akira , Izumi Yoshiharu , Akabori Shiro
Published: July 2006

1. The silk-platinum catalyst showed quite different behaviors with various compounds from that of other platinum catalysts. The difference is probably due to the characteristic spacing of the active centers on the silk-platinum catalyst, due to the structure of the carrier silk-fibroin protein.

2. The catalyst was found to catalize the hydrogenation of some aldehydes, unconjugated aliphatic ketones and C=C double bonds, aliphatic nitro groups and oxime, more weakly, than that of the aromatic nitro groups.

3. Carbon monoxide, benzyl mercaptan and cupric ion poisoned the catalyst, and the activity of the catalyst inhibited by cupric ion, was not recovered by treatment with ethylene-diamine tetra-acetic acid.

4. Ferric ion scarcely inhibited the catalyst and acetylation of the catalyst scarcely decreased its activity, unlike that of the silk-palladium catalyst.
Thermodynamical Studies on Binary Systems Consisting of Polar and Non-polar Liquids. III. Caculation of the Electrostatic Part of the Thermodynamic Excess Functions due only to the Dipole of the Polar Molecule for the Binary System Composed of Polar and Non-polar Liquids according to Onsager’s Model
Authors: Amaya Kazuo
Published: July 2006

The electrostatic part of the excess functions for 21 binary systems consisting of polar and non-polar liquids were calculated according to Onsager’s model. The electrostatic part of the excess free energy and excess enthalpy are positive over all the concentrations for all of these systems and these quantities are unsymmetric with regard to the mole fractions x against the value at the point x = 0.5.

The concentrations xmax where these quantities have maximum values, shift to a lower concentration of polar component. The larger the dipole moment of the polar components, the larger the maximum values and the shifts are. The electrostatic part of excess entropies have positive values over the whole concentration for systems consisting of a polar component of small dipole moment, but for those consisting of one with a larger dipole moment, these quantities take negative values for a high concentration of polar component, but take positive values for a low concentration range. The electrostatic part of van Laar coefficients is also calculated and these values increase with the decrease of concentration of polar component.
Structure of Enteromycin. II. Derivatives and Products in Various Reactions of Dimethoxyenteromycin
Authors: Mizuno K\={o}mei
Published: July 2006

The structure of dehydroxytetrahydrodemethoxyenteromycin was established to be glycyl-β-alanine. Demethoxyenteromycin yielded O-acetyldemethoxyenteromycin by acetylation, N-methyl- and O-methyldemethoxyenteromycins by methylation, and demethoxyenteromycin amide by amidation. Catalytic reduction of demethoxyenteromycin gave first dehydroxydihydrodemethoxyenteromycin and then glycyl-β-alanine. Acid decomposition products of demethoxyenteromycin were the same those of enteromycin, except methyliodide.
Refractometric Study of Some Cyano and Oxalato Complex Anions
Authors: Matsunaga Yoshio
Published: July 2006

The molar refractions of ten cyano and two oxalato complex salts were measured in the dissolved state using the NaD line. The molar refractions of complex anions were assumed to be given by the sum of (1) the molar refractions of the ligands and the central metal ion in the gaseous state, (2) the polarization of the ligands due to the field of the central metal ion, and (3) the delocalization of electrons by the metal-ligand π-bonding. The estimation of each term was attempted on the assumption that the chief difference between isoelectronic anions, for example Cu(CN)43− and Zn(CN)42−, is that of the valency of the central metal ions and the contribution of delocalization is roughly the same in such a pair. The polarization of a cyanide ion was found to be about 1.6 cc. per unit charge of metal ion for tetrahedral anions and about 0.9 cc. for octahedral ones. The contribution of π-bonding was estimated to be around 3 cc. per metal-ligand bond for both of the above-mentioned cyano complex anions. The small polarization and delocalization effects were observed in the case of oxalato complex anions.
Studies on Dehydroalanine Derivatives. IV. Synthesis of N-PhthaloylDehydroalanine by Thermal Decomposition of Cysteine and Serine in the Presence of Phthalic Anhydride
Authors: Sakakibara Shumpei
Published: July 2006

N-Phthaloyl dehydroalanine (I) was synthesized by heating cysteine or serine in the presence of phthalic anhydride. Yellow mercuric oxide greatly accelerated the desulfhydration reaction. The yield of I from serine was inferior to that from cysteine. N-Phthaloyl-Dl-alanine and lanthionine were derived from I.
Synthesis and Physical Properties of Normal Higher Primary Alcohols. IV. Thermal and X-Ray Studies on the Polymorphism of the Alcohols of Even Carbon Numbers from Dodecanol to Tetratriacontanol
Authors: Watanabe Akira
Published: July 2006

1. Determination of the melting points and transition points of the even carbon numbered alcohols from C12 to C34 was made by thermal analysis. The transition points of the alcohols above C18, except C22, have never been reported.

2. The reversible transition sets in at C14 and terminates at C26. The transition of C28 and C32 is irreversible, appearing only on cooling and both transitions disappear at C34. Probably the pure sample of dodecanol may indicate no transition in any methods of measurements.

3. Properties of the a forms gradually change with increasing chain lengths.

4. The β to γ and α to γ transformations were examined by X-ray pattern measurements and the results were discussed.

5. Transition points and X-ray spacings may be reliable criteria of purity of higher alcohols, and probably of some other long chain compounds.
Chemical Studies on Radioactive Indicators. XXIV. Separation of Rhenium from Technetium by the Distillation Method
Authors: Koyama Mutsuo
Published: July 2006

The separation of rhenium from technetium was investigated. Pertechnetate is reduced to non-volatile species by the use of hydroxylamine, but perrhenate is not reduced by such an agent. Rhenium is distilled out with steam from sulfuric acid medium and technetium remains in the solution containing hydroxylamine. Rhenium from carrier-free amounts up to 10 mg. can be separated quantitatively from technetium by this method.
A Study on Anion Exchange aud Amine Extraction of Rare Earth Elements in Nitric Acid
Authors: Ichikawa Fujio
Published: July 2006

The amine extraction of rare earth elements in nitric acid is compared with anion exchange and TBP extraction with respect to the increase or decrease in Kd value with increasing atomic number of rare earth elements.

Concerning the relationship between distribution coefficient and atomic number of rare earth element, a similar trend is observed in anion exchange and amine extraction. The distribution coefficient decreases with increase in the atomic number. In TBP extraction, however, the corresponding value increases with increasing atomic number. It seems that the mechanism of amine extraction for rare earth element is similar to that of anion exchange.
Studies on Metal Complex Species Using an Anion Exchange Resin. II. On the Adsorption of Silver from Nitrate Solution
Authors: Waki Hirohiko
Published: July 2006

1) It was found that silver was to some extent adsorbed on a strong base anion exchange resin from nitrate solutions. Its behavior was significantly different from that of alkali metals.

2) The equations derived in the previous paper were applied to a study of silver-nitrate complex. Starting from the same equation, two methods using either NaNO3 + NaClO4 mixed media or the loading of the complex were employed, and the two results were in good agreement.

3) It was presumed that most silver in the resin exists as Ag(NO3)2− in neutral nitrate media where the external nitrate concentrations were about 2∼3 m, although such anionic species may not be considered to exist in an ordinary nitrate solution.
Vinyl Polymerization. XLVIII. Polymerization of Methylstyrenes and the Effect of Dimethylaniline on their Polymerization
Authors: Imoto Minoru , Takemoto Kiichi , Iikubo Yuichi
Published: July 2006

1. Solution polymerizations of styrene, p-methyl-, p-ethyl-, p-tert-butyl-, m-methyl-, 2,4-dimethyl-, 2,5-dimethyl- and 3,4-dimethylstyrene were carried out at 50 and 70°C by ABIN in benzene, and the rates of polymerization and [η]’s of the polymers were determined. For 3,4-dimethylstyrene, the same equation as for styrene was obtained:

R 0=k[M] [ABIN]1⁄2

2. Rate constants of initiation of the polymerizations of styrene and p-methylstyrene were determined, according to the FeCl3-method as follows:

k i=0.67×10−5 (sec−1) (for p-methylstyrene)

k i=0.76×10−5 (sec−1) (for styrene)

3. Polymerizations of styrene and p-methylstyrene were carried out at 70°C by the Bz2O2-DMA system, and the same equation as styrene was derived for p-methylstyrene as follows:

R 0=k′[Bz2O2]1⁄2[DMA]1⁄2

4. Polymerizations of styrene, p-methyl-, and dimethylstyrenes were carried out at 50 and 70°C by ABIN-DMA system, and the results for the rate of polymerization and the value of [η] were discussed. A correction was made for the results previously obtained.

5. The effect of DMA on the induction period for the polymerization of p-methylstyrene was studied at 60°C. In the case of polymerization with FeCl3 in DMF, no effect of DMA on the induction period was observed, while in the case of that with p-benzoquinone in benzene, the induction period was decreased with the amount of DMA.
Mass-spectrometric Study on Ionization and Dissociation of Formaldehyde, Acetaldehyde, Acetone and Ethyl Methyl Ketone by Electron Impact
Authors: Kanomata Ichiro
Published: July 2006

A study of the ionization and dissociation of formaldehyde, acetaldehyde, acetone and ethyl methyl ketone, all of which have an oxygen atom, was carried out through the appearance potential method. As appearance potentials were obtained by the retarding potential difference method, break points, which correspond to successively occurring ionization, appeared in the ionization efficiency curves of molecules and fragments. By considering the relation of energy, it is concluded that the ionization of the molecule takes place at first by the removal of one of the lone pair electrons of oxygen atom in the molecule, and that, in the formation of a fragment ion including an oxygen atom, dissociation takes place to create a triple bond, satisfying the trivalency of O+ in the fragment ions.

The total bond energy of O+ in CH3C≡O+ and C2H5C≡O+ are calculated as about 200 kcal./mol., while in HC≡O+ it is 170∼180 kcal./mol. as in the case of diethyl ether reported previously. This fact may be explained by the number of resonance structures related.

The second and the third ionization potentials are thought to correspond to the removal of the π-electron and σ-electron in C–O bond respectively. The heat of formation of CHO+, CH3CO+ and C2H5CO+ are obtained from various reactions.
The Beckmann Rearrangement of the Geometrical Isomers of Cyclohexyl Phenyl Ketoxime in Liquid Sulfur Dioxide
Authors: Tada Ritsuro , Masubuchi Yoichi , Tokura Niichiro
Published: July 2006

The Beckmann rearrangement of the isomeric cylcohexyl phenyl ketoximes was carried out in liquid sulfur dioxide at low temperature (–70°C) with thionyl chloride, benzenesulfonyl chloride, bromine and hydrogen halides. In liquid sulfur dioxide, the β-oxime was unstable and isomerized slowly to the α-oxime with no reagent. The α-oxime yielded N-cyclohexyl benzamide and the β-oxime yielded cyclohexanecarboxyanilide, respectively, by the Beckmann rearrangement in liquid sulfur dioxide. The geometrical structure of the isomers and isomerization between them were discussed. As for the β-oxime, the rate of the rearrangement by far surpassed the rate of the isomerization. The principle of the trans migration in the Beckmann rearrangement has been confirmed within the range of this experiment. The deoximation of the oxime to the parent ketone, cyclohexyl phenyl ketone was observed in the reaction of β-oxime with hydrogen chloride and bromide.
On the Reactivity of Various Silicate Minerals toward Acids
Authors: Mase Hanzo
Published: July 2006

In this paper, the author proposed a classified table of metals contained in silicate minerals, and the qualitative and conventional rules in which it appeared possible to predict the reactivity of all the known silicate minerals toward ordinary mineral acids. In the classification and rules, ionic potential, Goldschmidt’s polarizing power, and field strength of the metals in the silicate minerals play important roles.

The rules are summarized as follows: 1) the silicate minerals—especially, the neso- and sorosilicate ones composed of the comparative simple ionic crystal lattices—containing the less electropositive metals (e.g., Ti, Be, Al, Cr, V(III), Fe(III), Mn(III), Zr, etc.) are generally unattacked by acids; 2) in the ino-, phyllo-, and tecto-silicate minerals, which contain various polymerized and giant silicate ions, their structures exert a favorable influence upon their reactivity toward acids. Thus, in these minerals, it is necessary for us to take their structural effects into consideration, besides the above rule 1) ; and 3) the bonding energies of silicate minerals are closely related to their reactivity. In general, the neso-, soro-, ino-, and phyllo-silicate minerals of which bonding energies are less than about 30500 kcal. and the tectosilicate ones of which the energies are less than about 33500 kcal. seem to be decomposed by acids.
Studies on Antibiotics and Related Substances. XII. Syntheses of 10-Oxo-11-dodecenoic Acid and 11-Oxo-12-tridecenoic Acid, Antitumor Substances
Authors: Kinoshita Mitsuhiro , Umezawa Sumio
Published: July 2006

1) 11-Oxo-12-tridecenoic acid (IXa) has been prepared from ethyl 9-bromononanoate (II) via 11-oxododecanoic acid (IVa) and the corresponding Mannich base Va.

2) 10-Oxo-11-dodecenoic acid (IXb) has been prepared from 10-oxoundecanoic acid (IVb) via the corresponding Mannich base Vb.

3) It has been found that IXa and IXb possess antitumor and antifugal activities.
Dielectric Investigation on Coals. V. Microwave Dielectric Constant
Authors: Chitoku Kazuo , Higasi Keniti
Published: July 2006

1. Using the transmission method, resonance method and bridge method, dielectric constants and losses are measured on paraffin-wax mixtures of twelve specimens of coal ranging from C Rough 65 to 92%.

2. Dielectric constants of coals are estimated for these coals by means of Böttcher’s equation

3. The relation between dielectric constant and oxygen content is discussed and it is shown that polar groups contribute to dielectric constant.

4. From the comparison with optical dielectric constant, the motion of dipoles in coals in the electric field can be discussed. Rough estimates of dipole moments are also given.
Syntheses of Peptides Related to the N-Terminal Structure of Corticotropin. II. Synthesis of Gly-Lys-Pro-Val Sequence
Authors: Inouye Ken , Otsuka Hideo
Published: July 2006

Formylglycyl-ε-carbobenzoxylysylprolylvaline benzyl ester, which has a sequence occurring in corticotropin and α-MSH, has been synthesized.
Studies on Extraction of Polonium(IV) by Hexone from Acid Solution
Authors: Matsuura Niro , Ouchi Akira , Kojima Masuo
Published: July 2006

The ionic state of polonium(IV) in hydrochloric and sulfuric acid solution was studied by the solvent extraction with hexone (methyl isobutyl ketone).

1) The polonium solution stored in 0.4 n nitric acid is strongly hydrolysed by aging. The low extraction coefficient caused by hydrolysis became higher by heating the polonium solution in stronger nitric acid. On the other hand, the polonium stored in 6 n nitric acid can be extracted with constant extraction coefficient, about 80%, through the entire acidity range from 1 to 6 n., if the extraction was carried out without any aging.

2) The aging effect of polonium(IV) in hydrochloric acid is rather complicated. A minimum extraction appeared in the acidity range near 2 n hydrochloric acid. By applying mass action law the probable form of polonium(IV) in that range was Po(OH)2Cl42− or PoO2+, assuming that PoCl62− was the stable form of polonium(IV) in 6 n hydrochloric acid which is readily soluble in hexone.

3) Almost no polonium(IV) was extracted by hexone from sulfuric acid solution. Here, the polonium(IV) in sulfuric acid exists probably as PoO2+ rather than as PoO32−.
The Composition and the Solubility Product Constant of Lead(II) Ethylenediaminetetraacetatoplumbate(II)
Authors: Tanaka Nobuyuki , Kamada Minoru , Satô Gen
Published: July 2006

The slightly soluble white crystals which form when lead (II) nitrate is added to the lead (II) ethylenediaminetetraacetate complexes in acetate buffer solution have been investigated. From the chemical analysis, it was found that the crystals have the composition of lead (II) ethylenediaminetetraacetatoplumbate(II) monohydrate. The solubility product constant,

K sp=[Pb2+][PbY2−]

where Y4 means an ethylenediaminetetraacetate anion was determined at ionic strength 0.2 as 3.54×10−6(mol./1.)2 at 15°C, 4.34×10−6(mol./1.)2 at 25°C and 5.72×10−6 (mol./1.)2 at 35°C.
Kinetics of the Reduction of Selenious Acid by Sulfur Dioxide. I. Reduction in Acidic Solution with Hydrochloric Acid
Authors: Hamada Keinosuke
Published: July 2006

(1) The reduction of selenious acid in hydrochloric acid by sulfur dioxide is a typical second order reaction with respect to selenious acid, while the reaction is of zero order with respect to sulfur dioxide because of the continuous passage of sulfur dioxide through a solution.

(2) The results obtained at 70, 60, 55 and 50°C (a=0.0184 mol./l., [H+]=0.49g. ion/l.) give a good Arrhenius plot, leading to the value of 24.5 kcal. mol−1 for the energy of activation.

(3) The rate constant of this reaction under a certain condition can be evaluated by the general equation,

k 1=2.054×1015×[H+]2exp(−E⁄RT)

where [H+] is hydrogen ion concentration, E, the energy of activation and T absolute temperature.

(4) The reduction of selenious acid in sulfuric acid, which will be published in a subsequent paper, is a reversible reaction. The above equation for the rate constant is utilized as a basic equation, in order to determine the rate constant in the forward direction of the reversible reaction.
Studies on Antibiotics and Related Substances. XI. Methylated Amino-sugar Moieties from Methylated Kanamycin
Authors: Umezawa Sumio , It\={o} Yukio
Published: July 2006

1) 3-Acetamido-3-deoxy-2,4,6-tri-O-methyl-d-glucose (I) and N-2,4-dinitrophenyl) derivative (II) of 6-amino-6-deoxy-2,3,4-tri-O-methyl-d-glucose have been isolated from the hydrolyzate of exhaustively methylated N-acetyl kanamycin.

2) II has been synthesized from 6-amino-6-deoxy-3,5-benzylidene -1,2-isopropylidene-d-glucose.
Determination of Lanthanum, Samarium and Europium in Manganese Nodules by Neutron Activation
Authors: Kawashima Toshi , Osawa Masumi , Mochizuki Yoko , Hamaguchi Hiroshi
Published: July 2006

The gamma spectrometric method has been developed for simultaneous determination of microgram amounts of lanthanum, samarium and europium without chemical separation of each other. The method was based on the chemical separation of rare earth mixtures from neutron irradiated samples and subsequent γ-ray scintillation counting of the isolated rare earth fractions. The sample was irradiated for 2∼3 days, 5 hr. each day, in the nuclear reactor JRR-1 at a flux of the order of 1011n/cm2/sec. The rare earth mixture purified by lanthanum fluoride cycles was used for γ-ray counting at a given pulse height peak. The activity of each component could be evaluated by resolving the decay curves obtained, and the amount calculated by comparing the activity with that of each monitor.
On the Electrical Conductivity of the Organic Thin Films: Perylene, Coronene and Violanthrene
Authors: Inokuchi Hiroo , Kuroda Haruo , Akamatu Hideo
Published: July 2006

It was found that the various types of conductivity cells of aromatic hydrocarbons possess great discrepancies of their electrical resistivity. The resistivity observed with the sandwich-type cell, perylene; 1018∼19 Ωcm., coronene; 1017∼18 Ωcm., and violanthrene; 1014 Ωcm., is in quite good agreement with that of the bulk specimen. However, a great difference was found between the resistivities of the sandwich-type and the surface-type cells, perylene; 1013 Ωcm., coronene; 1012∼13 Ωcm., and violanthrene ; 109 Ωcm. This discrepancy in resistivity can be assumed to be introduced from the textured structure of the evaporated films and the substantial anisotropy of crystals; the crystals are in alignment with their a·b plane with the film surface. This orientation was found from the X-ray diffraction results, combined with the electron microscopic observation and the electron microdiffraction results.
Diffusion in Glassy Polymers. II. Effects of Polymer-penetrant Interaction ; Diffusion of Ethyl Methyl Ketone in Atactic Polystyrene
Authors: Odani Hisashi , Hayashi Jun , Tamura Mikio
Published: July 2006

The successive differential absorptions for the A–PS-ethyl methyl ketone system change with the initial concentration according to the same scheme as that presented previously as typical systems of amorphous polymer-organic vapor; that is,

sigmoid type →pseudo-Fickian type → two-stage type → pseudo-Fickian type → Fickian type

The last transition, from pseudo-Fickian to Fickian types, for ethyl methyl ketone occurs at lower concentration than that for benzene. The second stage portion of the two-stage process shifts rapidly to the short time regions as the initial concentration of each step increases. The rate of this shift depends upon initial concentration in nearly the same manner as in the A–PS-benzene system. The general features of integral absorptions for the present system are very similar to those for benzene system, irrespective of the difference in the penetrant-polymer interaction between the two systems. The dependence of absorption rate upon ΔC is also similar in general character to that for benzene system.
Infrared Spectra of Troponoid Compounds. III. Tropolone and 2-Deuteroxytropone
Authors: Ikegami Yusaku
Published: July 2006

In order to find infrared absorption of tropolone, especially the absorption that can be assigned to the C–O–H group, the spectrum of 2-deuteroxytropone was measured and there were discussions chiefly on absorptions in the finger-print region. The absorption bands at around 3150, 1490, 1267 and 726 cm−1 were assigned to the vibration of C–O–H group. In this connection, some mention was made on deuterated tropolone and considerations were made on the assignment of vibrational spectra of tropolone, as summarized in Table II.
Distribution of Various Elements between Nitric Acid and Anion Exchange Resin
Authors: Ichikawa Fujio , Uruno Shinobu , Imai Hisashi
Published: July 2006

Distribution coefficient of some metallic elements between nitric acid and anion exchange resin were measured. From the results described above, the fundamental data on the separation of each element in nitric acid were obtained.
Dye-sensitized Photopolymerization of Vinyl Monomers. I. Preliminary Report on the Polymerization of Acrylonitrile by Various Dyes
Authors: Takemura Fukuo
Published: July 2006

Among various dyes, the dyes suitable for the sensitization of the polymerization of acrylonitrile have been determined. Acridine and xanthene dyes have been found to be the most effective.

Using acridine yellow, one of the most effective, the dye-sensitized photopolymerization has been investigated in detail; it has been shown that the reaction has several features characteristic of heterogeneous polymerization, e.g., its order is higher than one-and-a-half on monomer concentration.

Assuming the initiation process to be a direct interaction between excited dye and monomer, and assuming the unimolecular termination by occlusion of the propagating radicals, the kinetic data has been interpreted.
A Selective Phosphorylation by Means of α-Bromocyano acetamides and Trialkyl Phosphites
Authors: Hata Tsujiaki , Mukaiyama Teruaki
Published: July 2006

A method of selective phosphorylation by means of α-bromocyanoacetamides and trialkyl phosphites was devised. In this method, various phosphates, pyrophosphates and phosphoramidate were obtained in excellent yields under mild conditions without isolating the intermediate, enol-phosphate.

The use of dibromocyanoacetamide in place of monobromocyanoacetamide produced the same results, the yields being, however, less.

A new method for the preparation of monobromocyanoacetamide was also described.
Syntheses and Ultraviolet Spectra of Aromatic Azo Compounds. II. Azobenzenecarboxylic Acids, Methylazobenzenecarboxylic Acids and their Ethyl Esters
Authors: Nomura Yujiro , Anzai Hiroyuki
Published: July 2006

1) The zinc chloride double salts of ethoxy-carbonylbenzenediazonium chlorides reacted with aryl Grignard reagents to give ethyl azobenzenecarboxylates. This provides a new method for the preparation of these compounds, as has been demonstrated by the preparation of twelve azo compounds, including ten substances not hitherto known.

2) A group of azobenzenecarboxylic acids was prepared by the hydrolysis of the corresponding ethyl esters obtained above ; seven of them are new compounds.

3) The ultraviolet absorption spectra of these esters and free acids were measured.
Studies of the Drawing of Polyamide Fibers. I. Dependence of Some Physical Properties on the Draw Ratio
Authors: Hattori Hiroshi , Takagi Yasuo , Kawaguchi Tatsuro
Published: July 2006

The relation between the draw ratio and some physical properties of nylon 6 fibers was investigated, using monofilament drawn in hot water to various draw ratios. The tensile strength decreases, passes through a minimum at a draw ratio near 2, and then increases as the draw ratio becomes higher. The decrease in strength at the minimum in the sample drawn immediately after spinning amounts to 60% of the strength of the undrawn sample. The shrinkage in boiling water of the sample drawn immediately after spinning is nearly zero in the range of a low draw ratio, increases in the range of the ratio from ca. 2 to ca. 3.5, and gradually approaches a saturating value, but that of the samples drawn many days after spinning increases most rapidly in the range of the ratio from 1 to ca. 2 and then gradually approaches to a saturating value with the draw ratio. On the first stage of drawing, the rate of increase in birefringence with the draw ratio of the sample drawn immediately after spinning is smaller than that of the sample drawn many days after spinning. On the basis of these results, the authors discussed the mechanism of the drawing of polyamide filaments.