bluuebunny/crossref_metadata_2025 huggingface dataset:
Ultraviolet Spectrophotometric Determination of Vanadium in Silicate Rocks
Authors: Yoshimura Jun , Murakami Yoshio
Published: July 2006

1) The absorption spectra of vanadium(V) in the media of various concentrations of hydrochloric acid were studied.

2) A 1 n hydrochloric acid concentration was recommended as the working medium for the spectrophotometric determination of vanadium(V), because the change in the intensity of the absorbance with the change in the reagent concentration is slight.

3) Beer’s law was obeyed up to 25 p. p. m. of the metal, measuring the absorbance at 222 mμ.

4) The analysis of the silicate rocks by this method was studied, and good results were obtained.
Radiation-induced Polymerization of α-Methylstyrene. II. Reply to the Criticism of Bates et al.
Authors: Hirota Kozo , Takemura Fukuo
Published: July 2006

Gamma-ray-induced polymerization of α-methylstyrene occurs mostly according to the radical mehanism, as had been concluded by one of the present authors, but simultaneously it occurs to some extent according to the cationic mechanism, as had been asserted by Bates et al.
Chain Transfer to Telomer. II. In the Case of Catalyzed β-Polymerization
Authors: Okamura Seizo , Katagiri Keizo
Published: July 2006

Catalyzed styrene polymerization in the presence of azobisisobutyronitrile and telomer has been carried out to investigate the effects of the conversion of monomer and of the addition of catalyst on the degree of polymerization of polymer under the same conditions as in the previous report.

The apparent degree of polymerization of polymer was obtained as a rather larger value than expected. This situation is qualitatively explained by the reactions of a catalyst fragment radical with telomer and with polymer freshly produced.
Dehydration Reactions of Benzaldoxime by Means of Compounds Having a Nitrogen-Carbon Double Bond
Authors: Mukaiyama Teruaki , Fujisawa Tamotsu , Mitsunobu Ohyo
Published: July 2006

The dehydration reactions of benzaldoxime with such nitrogen-carbon double bond compounds having halogen and alkoxyl groups as phenylimidophosgen, ethyl N-phenyliminochlo-roformate and ethyl N-phenylformidate were studied.

One mole of phenyl imidophosgene, when reacted with 1 mol. of benzaldoxime, gave phenyl isocyanate and benzonitrile as main products. On the other hand, with 2 mol. of the aldoxime, aniline hydrochloride and benzonitrile were obtained in good yields. The aldoxime was also dehydrated effectively by ethyl N-phenyliminochloroformate to give, among other byproducts, the nitrile and ethyl N-phenylcarbamate. The nitrile and formanilide were obtained by the reaction of the aldoxime with ethyl N-phenylformidate.
Rotational Isomers of Vinyl Ethers. Studies of the Vibrational Spectra and Dipole Moments of cis- and trans-β-Chlorovinyl Methyl Ethers
Authors: Mikawa Yukio , Morita Shiro , Tsunakawa Sukenari
Published: July 2006

Raman and infrared spectra of cis- and trans-β-chlorovinyl methyl ethers (ClCHCHOCH3) were measured in the vapor and liquid states, and the infrared spectra in the solid state were also measured for the trans compound. The dipole moments were measured for both of the compounds in a benzene solution. From the observed value of the dipole moments, it was decided that the compound having the lower boiling point had a trans configuration and the other, a cis configuration.

On the basis of these configuration, interpretation of the vibrational spectra of both compounds was undertaken. As for the trans compound, the existence of the rotational isomers arising from the internal rotation around the C–O axis was verified by the fact that some of the infrared bands disappeared on solidification of the samples. The spectra in the liquid and vapor states were interpreted as a mixture of those of two rotational isomers, and tentative assignments were given for one of the isomers by reference to the spectra of methyl vinyl ether. The most probable form of the molecule was supposed as the planar zigzag form.

On the contrary, it was established that there existed no rotational isomer in the cis compound in any state. The spectra of the cis compound did not resemble those of the trans compound or the methyl vinyl ether and were interpreted as a superposition of group frequencies of the ether linkage and of the –CH=CH- group. Consequently, a non-planar model was proposed, and the angle of internal rotation was determined to be about 90° from the observed value of the dipole moment. In order to explain the difference in the spacial configuration between the cis and the trans compounds, the electrostatic effect, in addition to the resonance effect and the steric repulsion, was considered. From the results of the calculation of the dipole-dipole interaction, it was shown that this electrostatic force played a very significant role in the internal rotation.
The Radiation-Induced Oxidation of Stannous Chloride in Aqueous Hydrochloric Acid
Authors: Sugimoto Ken’ichi , Oae Shigeru
Published: July 2006

The radiation-induced oxidation of stannous to stannic ion in aqueous hydrochloric acid has been studied and that this system is proposed as a chemical dosimeter for higher doses.

The amount of oxidation is proportional to the energy absorbed and the yield of stannic ion is independent of dose rate and initial stannous chloride concentration over a wide range studied, but increases when stannic con-concentration is high or oxygen is present. Mechanism for this oxidation based on G-values is discussed in terms of the primary decomposition products of water radiolysis. The results can be interpreted to mean that the stannic ion is oxidized only by OH radical. This system could be used for a chemical dosimeter having 8% reproducibility.
Viscosities of O/W Emulsions Stabilized by Nonionic Surfactants. I. Characteristics of Nonionic Surfactants in Emulsion Viscosities
Authors: Ohba Noriaki
Published: July 2006

O/W emulsions of mineral oil were prepared, using several types of nonionic surfactants, and their relative viscosities were measured with a rotating-cup viscometer, together with microscopic and visual observation of the emulsions.

It was found that there are two maxima in the curve of the relative viscosity vs. the ratio of the two surfactants in the mixed emulsifier employed. From these figures, the relative effects of the nonionic surfactants on the emulsion viscosities were discussed.

It was confirmed that the emulsion viscosity at the optimum composition decreases in the following order:

for sorbitan fatty acid esters,

SMS>SMP>SML>SMO>SSO>STS

for polyoxyethylene sorbitan fatty acid esters,

E–SMS–20>E–SMP–20>E–SMO–20>E–SML–20

for glyceryl monostearates,

GMS–IV>GMS–III>>GMS–V>GMS–II>GMS–I

For the other types the order of the series was not distinct. In the former two series, the orders of the arrangements are parallel with those of the decreasing carbon atom numbers in the molecule in the case of saturated fatty acid derivatives.

The soap effect is considered to appear in the case of glyceryl monostearates, the so-called self-emulsifying types of the emulsifier.

Using the scale of viscosity vs. virtual HLB value, we can determine by means of emulsification the most probable HLB value of the nonionic surfactants.

Good agreements are seen between the HLB values determined by viscosity minimum and those determined by the emulsification test reported on in the preceding paper.
Viscosities of O/W Emulsions Stabilized by Nonionic Surfactants. II. Effects of Oil Mixtures on the Emulsion Viscosities
Authors: Ohba Noriaki
Published: July 2006

To study the effects on the viscosities of O/W emulsions of the addition of several materials to the oil phase, oil mixtures were emulsified and the viscosities of the emulsions so obtained were measured with a rotating-cup viscometer,

The effects of these additives in increasing emulsion viscosity are in the following order, with respect both to the amounts required to give a specified increase in viscosity and to the minimum amount required for a sudden increase in viscosity:

C-Alc, AGMS-IV>S-Ac, AGMS-III>La-Alc>AGMS-I, L-Ac, L-Alc>B-W>AGMO-II,AGMO-I, C-W, La

It was confirmed that in order to be effective as an additive in increasing emulsion viscosity, the iodine value should be small, while an ineffective additive always shows a low Δ as well as a low hydroxyl value. The melting point of an additive has, on the whole, no correlation with the power of increasing the emulsion viscosity. The acid value also shows no correlation with the viscosity of the emulsion formed.

A sudden increase in emulsion viscosity was observed beyond a certain amount characteristic of each additive.
Proton Magnetic Resonance in Cupric Formate Tetrahydrate, Cu(HCO2)2·4H2O
Authors: Kiriyama (née Ibamoto) Hideko
Published: July 2006

The proton magnetic resonance spectra of Cu(HCO2)2·4H2O have been investigated over the range 110° to 315°K, using both single crystal and powdered samples. The water molecules are effectively rigid below the phase transition temperature, 237°K, and the most probable positions of the protons of the two non-equivalent water molecules are postulated on the basis of Pake’s method.

The narrowing of the absorption line occurs above 237°K; this implies the gradual onset of a certain motion of both kinds of water molecules. The absorption spectra in the higher temperature range of 300∼315°K indicate that the reorientation of the water molecules takes place almost exclusively about one axis.
On Glumamycin, a New Antibiotic. II. Isolation and Identification of Amino Acids Constituting Glumamycin
Authors: Inoue Michitaka
Published: July 2006

Isoation of the amino acids constituting glumamycin, a new antibiotic, was effected. As a result, α(l), β-methylaspartic acid, besides l-aspartic acid was obtained as an acidic amino acid. In addition to l-valine, glycine, and l-proline, d-pipecolic acid was yielded as a neutral amino acid. Further, α, β-diaminobutyric acid was obtained as a basic amino acid and its structure was established to be α, β-diamino-n-butyric acid. For positive confirmation of the structure the acid was synthesized, and it was found that the N, N-dibenzoyl ethyl ester of the synthetic product and that of the basic amino acid derived from glumamycin were in complete agreement.
Temperature Dependences of the Nuclear Quadrupole Resonance Frequencies in 1,4-Dihalogenocyclohexanes
Authors: Tokuhiro Tadashi
Published: July 2006

The temperature dependences of the 79Br and 127I nuclear quadrupole resonance frequencies in 1,4-dihalogenocyclohexanes were investigated. According to Bayer’s theory (Eq. 8), the torsional frequencies were calculated by the use of the calculated moments of inertia and the experimental values of the temperature coefficients of the resonance frequencies at various temperatures. From a comparison of the torsional frequencies, the line of higher frequency at 77°K in cis-1,4-dibromocyclohexane may be assigned to the equatorial bromine nucleus. All the calculated torsional frequencies decrease with the increasing temperature. Such variation in the frequencies agrees with the variation obtained by Raman studies of various molecules in crystals. The resonance lines in the trans-compounds fade out at temperatures considerably below their melting points.
Studies of the Cross-linking and Glass Transition of Fatty Acid-Modified Alkyd Resins
Authors: Kumanotani J\={u} , Chen L W , Kuwata Tsutomu
Published: July 2006

a) The degree of cross-linking observed in films of fatty acid modified alkyd resins increases with the content of unsaturated acids. Moreover, cross-linking is not so effective in raising the Tg as the benzene ring, which has a larger cohesive energy.

b) Both the Tg and the degree of cross-linking increase with the increase in the molecular weight of the prepolymer.

c) The excess of glycerol employed in fatty acid-modified alkyd resin is effective in raising the Tg and encouraging the progress of the cross-linking.

d) Generally, the cross-linking is not soon completed; as time elapses, the Tg rises, and the cross-linking progresses. No change in the Gh with the elevation of the Tg (baked film with the addition of a drier) is considered to be caused by the formation of polar groups by air-oxidation.

e) In the early period of drying, a sub-glass transition caused by the unrestrained chain of the acyl groups is observed.
The Kinetics of the Transition of Titanium Dioxide
Authors: Suzuki Akira , Kotera Yoshihide
Published: July 2006

The kinetics of the transition of anatase to rutile have been studied in the temperature range 750∼800°C by means of dielectric constant measurements. The kinetic data can be fitted reasonably well by the first order equation. The transition rate is significantly affected by the heating atmosphere and the flux, and the values of the activation energy show a significantly large difference in these cases. In an air or oxygen atmosphere the value of the activation energy in the transition of pure titanium dioxide is 110 or 116 kcal./mol. and 90 kcal./mol. respectively. When 1% of lithium chloride is added to the titanium dioxide, the value of the activation energy of the transition is 150 kcal./mol.
Relations between the Degree of Orientation and the Conditions of the Deposition of Pyrolytic Graphite
Authors: Noda Tokichi , Iinagaki Michio , Kato Hajime
Published: July 2006

Pyrolytic graphites were deposited on carbon rods by the thermal decomposition of a commercial propane gas at various temperatures and at various rates of gas flow. The orientation functions of the graphite crystallites in the deposited graphites were measured by means of the X-ray diffraction method. It was shown that the degree of orientation in the deposited graphites increased with the increase in the temperature of deposition and decreased with the increase in the rate of gas flow. The graphites deposited at temperatures above 2000°C were composed of two layers; the inner layers had a larger degree of orientation and a higher graphitizability than the outer layers. Almost all the (0 0 l) diffraction profiles of the deposited graphites were found to be asymmetrical and to the apparently composed of two kinds of profiles, whose c0 values were 6.72 and 6.86Å.
Studies on Tritium-labeled Compounds. VI. The Platinum-catalyzed Exposure Technique
Authors: Meshi Teruhiko , Takahashi Tadao
Published: July 2006

To increase the efficiency of labeling according to the Wilzbach procedure by absorbing the β-ray energy of tritium in the system, three typical hydrogenation catalysts were applied to the salicylic acid-T2 system.

The platinum catalyst was found to be most effective in promoting the labeling. The results obtained in labeling six compounds by the platinum-catalyzed-exposure technique showed that by this procedure higher specific activities in the range of 3∼1880 fold were obtained.

The increase in labeling changed considerably with different compounds, and the relative amount of labeling for aromatics was higher than for aliphatics.
Electronic States of p-Benzoquinone. VII. Intensity of the Symmetry-forbidden Electronic Absorption Bands of p-Benzoquinone
Authors: Sadô Akira
Published: July 2006

The intensity of the symmetry-forbidden electronic absorption band of p-benzoquinone, whose excited states belong to 1B2g, 1Au and 1B1g, has been calculated by the perturbation method. It has been concluded that the absorption band around 2900Å corresponds to the 1B2u←1Ag transition, which is allowed through vibronic interaction with the allowed 1B1g←1Ag transition. The interaction is contributed to almost entirely by b3u C=O bending vibration, whose frequency is 370 cm−1 in the ground state.
On the Structures of p-tert-Butylphenol Resin and α-Naphthol Resin. III. Infrared Absorption Spectra of Resins of p-tert-Butylphenol and α-Naphthol
Authors: Soda Reisuke
Published: July 2006

Polymers of p-tert-butylphenol with formaldehyde and α-naphthol with formaldehyde have been synthesized, and infrared spectra have been observed in solid and in solutions. The following conclusions have been obtained concerning band assignments and the polymer structures.

(1) p-tert-Butylphenol polymer is a linear chain polymer connected with the methylene bridge, and O–H bonds restrict each other by a strong intramolecular hydrogen bonding. This hydrogen bonding is partly loosened in a benzene and carbon tetrachloride solution, but not in an acetone solution.

(2) With p-tert-butylphenol polymer the bands at 1425 and 1205 cm−1 are assigned to the deformation vibration of the O–H bond coupled with the C–O stretching vibration. Out-of-plane O–H bending is considered to give rise to the bands in the 550 to 500 cm−1 region, and the bands at 548 and 520 cm−1 are assumed to be concerned with those vibrations.

(3) The O–H bond in α-naphthol polymer is bound by an intramolecular hydrogen bonding in solid, but in solution almost all the O–H bonds are liberated from the H–bonding. The polymer is considered to be a linear chain molecule whose O–H bonds can only with difficulty interact with each other to make an intramolecular hydrogen bonding.

(4) In-plane O–H deformation vibration coupled with C–O stretching vibration of α-naphthol polymer gives rise to the bands at 1385 or 1357 and 1176 cm−1. The bands at 560 cm−1 may be concerned in out-of-plane O–H bending vibration.
Equilibria in the PdS–H2–Pd4S–H2S and Pd4S–H2–Pd–H2S Systems
Authors: Niwa Kichizo , Yokokawa Toshio , Isoya Toshiro
Published: July 2006

Equilibrium measurements were carried out by a streaming method on the systems of palladium sulfides and of hydrogen-hydrogen sulfide gaseous mixtures. From the results, the dissociation pressures of PdS and Pd4S were calculated, and the free energies of the formation of PdS2, PdS and Pd4S from palladium metal and sulfur diatomic gas were obtained.
Polarography of Pyridine N-Oxide and its Alkyl Derivatives
Authors: Kubota Tanekazu , Miyazaki Hiroshi
Published: July 2006

The polarographic behavior of pyridine, 4-methylpyridine and 4-ethylpyridine N-oxides has been investigated. The reduction wave of these N-oxides decreases rapidly with the increasing pH value in pH values above 5 and disappears in alkali. It was clearly shown by the polarographic and spectroscopic investigations that the main reason for this phenomenon is the kinetic current. Quantitative treatment of the pH-dependence of the limiting current was also carried out.
On Glumamycin, a New Antibiotic. IV. The Amino Acid Moiety
Authors: Inoue Michitaka
Published: July 2006

Separatory determination was conducted on the seven amino acids contained in glumamycin. By the Moore-Stein method and by paper chromatography of the DNP-derivatives of the amino acids, 4 mol. of aspartic acid (including α(l, β-methylaspartic acid), 2 mol. each of glycine and α, β-diaminobutyric acid, and 1 mol. each of valine, pipecolic acid and proline were detected. Also, investigation was made into the free amino group of this antibiotic.

The hydrolysate of DNP-glumamycin showed one yellow spot at Rf 0.68, which spot turned purple with ninhydrin.

Compared these results with paper chromatogram of partially dinitrophenylated α, β-diaminobutyric acid, it was assumed that the β-amino group of one of the acids, is free, that the α-amino group participates in the peptide linkage in glumamycin, and that both amino groups of another α, β-diaminobutyric acid take part in the peptide linkage.
Adsorption Characteristics of 60Co-ions towards Polystyrene Treated with Sulfuric Acid Relative to Radioactive Decontamination
Authors: Seimiya Tsutomu , Sasaki Tsunetaka
Published: July 2006

The adsorption of cobalt ions by polystyrene treated with sulfuric acid was measured using the radiotracer technique. We also studied the type of adsorption of the cobalt ions by polystyrene, with or without sulfuric acid treatment, by observing the rate of desorption by the use of several rinsing liquids. It was confirmed that, although cobalt ion adsorption on an untreated surface is much less than that on a treated surface, the former is rather harder to remove by rinsing than the latter, regardless of the nature of the rinsing liquid.
Dissolution and Anion Exchange Behavior of the Rare Earth Elements in Potassium and Ammonium Carbonate Solutions
Authors: Taketatsu Tomitsugu
Published: July 2006

The amounts of rare earth elements dissolved in potassium and ammonium carbonate solutions of various concentrations have been determined. These amounts increase with the increase in the concentration of the carbonate and also with the increase in atomic number, except for cerium, yttrium and scandium. When the precipitates of the rare earth elements were completely dissolved in carbonate solutions more concentrated than a certain known concentration, the distribution coefficients, Kd, of the rare earth carbonate ions between an anion exchange resin of a carbonate form and potassium or ammonium carbonate solutions of various concentrations were determined. The values of Kd increased both with the decrease in the concentration of carbonate ions and with the increasing atomic number of the rare earth elements. Since the slopes of the curve log Kd vs. log(CO32−) in a potassium carbonate solution are found to be almost the same value for all the rare earth elements investigated, it has been concluded that the soluble complex of rare earth elements possesses an identical negative charge.
Electronic Interactions between Molecules and Atoms (Radicals) Involving Excited States
Authors: Mori Yuji
Published: July 2006

In the first section, the chemical reactivity of conjugated molecules toward a radical attack has been explained. The index of chemical reactivity for a radical attack can be represented in terms of polarizability (πrrS, πrrT) and of γr, which is similar to the superdelocalizability for a radical attack. The role of the lowest triplet states of molecules in a radical reaction has been discussed.

Secondly, the quenching of excited (2P) sodium was discussed. It has been concluded that the quenching cross-section is determined by the symmetry character of the lowest electron-transfer state and by the electron affinity of the molecule.
Changes of the Lattice Constants and Crystallite Sizes of Various Types of Carbons with Heat Treatment
Authors: Inagaki Michio , Noda Tokiti
Published: July 2006

Two kinds of cokes, six kinds of carbon black and a charcoal were heat-treated at temperatures between 1500 and 3400°C in a resistance furnace under atmospheric pressure. The lattice constants and crystallite sizes of these carbons were measured by means of the X-ray diffraction method, using extra-pure silicon as an inner standard.

The co values of the graphitizing carbons, such as the petroleum coke and the pitch coke, were not less than 6.718Å, even when these carbons were heat-treated at 3400°C. It was concluded that the graphitizability of carbon was affected by its original texture even at such a high temperature as 3400°C.

The co value of carbon black became smaller and the value of Lc, larger with the increase in the particle size of carbon black. It has been said that the particle size is the main limiting factor for the growth of graphite crystallite in carbon black, but the experimental results suggest that such other properties as micropores may also be limiting factors.

The discrepancy between the Lc values calculated from the (002) and (004) diffractions was accounted for by the heterogeneity of the interlayer spacing in crystallite.

With the charcoal, so-called three-phase graphitization was observed.
Spectrophotometric Determination of Cerium(III) and Some Rare Earths with Xylenol Orange
Authors: Tonosaki Kôichi , Otomo Makoto
Published: July 2006

A method has been described for the spectrophotometric determination of 20 to 100μg. of a rare earth element using xylenol orange. The complexes of cerium(III), lanthanum-(III), neodymium(III) and yttrium(III) with xylenol orange have an absorption maximum at 575 to 578μ vs. the reagent blank. Each of them is a 1 : 1 complex and has a formation constant of approximately 105 under the conditions studied. Anions such as NTA and EDTA inhibit the color development of the complexes.
The Radiation-Induced Exchange Reaction of Oxygen Atoms in Carbon Dioxide
Authors: Hirota Kozo , Terasaki Hideo , Hatada Motoyoshi
Published: July 2006

Oxygen exchange of carbon dioxide induced by β-ray irradiation has been investigated by use of oxygen isotope O*. From the decrease of O* amount, the apparent and total values of the exchange reaction, Gcorr(-CO2*) and Gtotalexc, have been calculated to be 1.72 and 51, respectively. The latter value 51 would be equivalent to the forward reaction, but has been shown to be larger than the corresponding value (8.5) in Harteck’s experiment.
Isomerization of Cyclohexyl Phenyl Ketoxirne in Liquid Sulfur Dioxide
Authors: Tokura Niichiro , Shiina Katsuo
Published: July 2006

1. The syn-anti isomerization of β-cyclohexyl phenyl ketoxime is carried out in liquid sulfur dioxide.

2. The isomerization is accerelated by light and retarded by hydroquinone. The degree of the dehydration of liquid sulfur dioxide has little effect on the rate of isomerization.

3. The kinetic result has shown that the reaction is of the first order with respect to the concentration of the oxime and that the rate constant, k for R=k[β-oxime], may be expressed as:

k=6.3×1011 exp [−19.1⁄RT]

4. A complex between the oxime and sulfur dioxide is assumed as the intermediate step, the isomerization of the complex being the rate-determining step. The dual (radical and ionic) nature of the isomerization in liquid sulfur dioxide may well be elucidated by such an assumption.
Polarographic Study of the Rate of the Dissociation Reaction of the Zinc(II)-Nitrilotriacetate Complex in Ammonia-Ammonium Nitrate Buffer Solutions
Authors: Kodama Mutsuo , Hashimoto Mitsuo
Published: July 2006

The kinetic current due to the dissociation of zinc-nitrilotriacetate complexes has been investigated in buffers with pH values from 8.3 to 9.5 and containing a large excess of calcium ions with respect to the total concentration of nitrilotriacetate. The ionic strength was kept at 0.4.

It was confirmed that the electrode reaction at the surface of the dropping mercury electrode proceeds according to the mechanism:

ZnX−+2NH3\ightleftharpoonsZn(NH3)22++X3− (slow)

Zn(NH3)22++2e+Hg\ightleftharpoonsZn(Hg)+2NH3 (fast)

The rate constants were calculated as 0.850(mol./l.)−2 sec−1 for the dissociation reaction of ZnX−+2NH3=Zn(NH3)22++X3− and 2.42×105(mol./l.)−1 sec−1 for the association reaction at 25°C. in buffer solutions of pH values from 8.3 to 9.5 with an ionic strength of 0.4 and containg 0.1 m calcium nitrate. The heat of activation and the entropy of activation of the dissociation reaction were calculated as 31.1 kcal. and −25.4 e. u. respectively.
The Gelation of Lead Aldose-cysteinate. The Properties of Gel and the Structure of Lead Aldose-cysteinate
Authors: Takahashi Fujio , Mizuguchi Jun
Published: July 2006

When a solution containing HGC or HGaC and lead acetate on nitrate was allowed to stand for sometime, it was found to form a stable gel like agar-agar in the pH range between 3.8 and 11 and with a concentration over 0.3%. The turbidity and rigidity of the gel began to increase rapidly with gelation. A solution containing HMC and lead salt did not form a gel, but precipitated lead cysteinate with the liberation of mannose.

It was found that the lead aldose-cysteinates isolated, which are the essentials materials for gelation, are composed of one atom of lead, one molecule of HSC, and one univalent anion, and that the sulfur atom and one hydroxyl group HGC coordinate with the lead atom, but that the carboxyl group of HGC does not coordinate to the lead atom.
Preparation of Some Tricyclohexylsilyl Derivatives
Authors: Kanazashi Motonori , Takakura Michio
Published: July 2006

Hydrogenations of hexaphenyldisilane, hexaphenyldisiloxane and triphenylsilanol were carried out in the presence of Raney nickel catalyst (W-6), and hexacyclohexyldisilane, hexacyclohexyldisiloxane and tricyclohexylsilanol were obtained (41, 56, 84%, respectively). Infrared spectra of the products and the starting materials were measured.
Study on Unimolecular Decomposition of Excited Olefin Ions
Authors: Omura Itiro
Published: July 2006

The decomposition probabilities, rate constants, and frequency factors for some olefins have been calculated on the basis of mass spectrometric data and the quasi-equilibrium theory.

The rate constant of the parent ion in a homologous series increases with the size of the ion. Fragment ions of the same form but from different parent ions sometimes reveal different rate constants.

The scheme of hydrogen molecule abstraction in the secondary decomposition processes of propane is analogous to that of propylene, and reasonable ionic structures of primary ions can be presumed.

For a more quantitative discussion, however, there remain some indistinct points in the application of the quasi-equilibrium theory. For instance, the time of reaction along with the rate constant is assumed to be 1×10−5 sec. and to be constant for all ions. Further studies should be carried out both in theory and experiments.
The cis-trans Photoisomerization of Azobenzene
Authors: Yamashita Shigeru , Ono Hiroshi , Toyama Osamu
Published: July 2006

The photoisomerization of cis- and trans-azobenzene in an n-hexane solution has been studied in the n-π* and π-π* absorption wave-length regions. The rate of isomerization has always been found to be proportional to the product of the incident light intensity and the concentration of cis- or trans-azobenzene. This simply means that the rate of isomerization is proportional to that of light absorption. Quantum yields of isomerization are independent of the temperature except for the trans→cis conversion caused by n-π* absorption, where the quantum yield is slightly dependent on temperature. The sum of quantum yields for cis→trans and trans→cis conversions caused by n-π* absorption is approximately unity, while the sum obtained with π-π* absorption is much smaller than unity. The mechanism of photoisomerization has been discussed with reference to these results.
Relations between the Electronic Absorption Spectra and the Spatial Configurations of Conjugated Systems. XIII. Phenyl-carbonyl and Vinyl-carbonyl Systems
Authors: Suzuki Hiroshi
Published: July 2006

It has been shown that the characteristic feature of the steric effect on the conjugation band in the case of the phenyl-carbonyl and vinyl-carbonyl systems, i. e., the relatively small hypsochromic shift and the relatively large decrease in the intensity of the band, as compared with that in the case of the conjugated hydrocarbon systems, can be adequately interpreted using the simple MO approach. From theoretical considerations it has especially been concluded that the proportionality of the intensity of the band to the cosine-square of the angle of twist of the formally single bond in these systems, formerly assumed by Braude, may be admitted as a rough approximation in spite of the invalidity of its original reasoning.
Photoreduction of Methylene Blue by Some Derivatives of N-Phenylglycine. Relation between the Structure and the Reactivity of the Electron Donors
Authors: Matsumoto Shiro
Published: July 2006

The photobleaching of methylene blue in the presence of various derivatives of N-phenylglycine has been examined to investigate the relation between the structure and the reactivity of the electron donor and to get information about the nature of the photoreaction. The time course of the photobleaching is well expressed by the superposition of two terms decreasing exponentially with time.

The hydrogen atom on the nitrogen or α-carbon atom of the N-phenylglycine molecule seems to take no part in the photoreduction process, and the first stage is probably the electron transfer between the interacting species.

As judged from the initial quantum yield,Φ, of the photoreductions, the influence of substituents in the ortho- and para-positions of the benzene ring is much larger than that in the meta-position. Both electropositive and electronegative substituents reduce Φ. The small Φ in the former cases is attributed to the ability of such φ·G’s to deactivate the excited dye ions. From spectral data, no sign of complex formation between φ·G’s and unexcited dye molecules can be inferred. The fluorescence of methylene blue is not quenched by φ·G’s in the range of concentrations used in the photochemical reaction. In view of these results, the kinetic data are treated by use of a current kinetic scheme, when a relation akin to Hammett’s rule is found between a certain rate constant and the σ value of the substituent in the benzene ring of the N-phenylglycine.

Kinetic data are also used to estimate the life-time of the metastable excited state of the dye, which is calculated to be about 4.2×10−5sec. or longer. This value is in a range reasonable to be interpreted as that of the lowest triplet state of the dye.
Photosensitized Oxidation of Leuco-uranine. II. Kinetics of an Acridine-sensitized Photoöxidation in the Deaerated Solution
Authors: Uchida Kengo , Koizumi Masao
Published: July 2006

The acridine-sensitized photoöxidation of leuco-uranine in the deareated aqueous solution was studied kinetically. It was established that about 0.24 of the excited acridine molecules goes to the triplet state and then reacts with leuco-uranine. In favorable conditions, the quantum yield is near 0.20, which shows that the genuine reaction rather predominates over the deactivation process of the triplet state.

The pH value dependence of the rate was successfully interpreted from the assumption that each of the different molecular species has a different rate constant.
Anionic Polymerization of Vinylidene Chloride. I. Susceptibilities of Vinyl Monomers to Initiation by Ionic Catalysis
Authors: Konishi Akio
Published: July 2006

The relative reactivities of vinyl monomers under ionic conditions have been discussed using a Q-e or q-ε map. It has been deduced that the larger the value of the polarity factor e (or ε) and the resonance factor Q (or q) of the monomer, the greater the susceptibility of the monomers to ionic catalysis. The possibility of new ionic polymerization reaction and the relative reactivity of monomers in ionic copolymerization have been discussed. As the result of this scheme, it seems that the anionic polymerization of vinylidene chloride is possible.
Molecular Rotations of Glucides in Relation to their Structures. X. On the ζ-Coefficient of the Hydroxyl Group in Pentose and Methylpentose
Authors: Yamana Shukichi
Published: July 2006

As there are four hydroxyl groups in the pentose and methylpentose molecules, the ζOH values in some of them may be nearly equal to that in the polyhydroxycyclohexane which has four hydroxyl groups in the molecule. In order to satisfy this condition, the ζ-coefficient of (H)1,ζ(OH)1 was distinguished from that of the other (OH), ζOH. Next, by using the PM-method, the values of ζ(OH), ζOH and were calculated. Making use of these ζ-coefficient a table of [μ]D obs20 values was made. By using this table, the [M]D20(W) values of some carbohydrates, hitherto unknown, were calculated. The validity of the presumed values was then tested by applying Hudson’s methyl glycoside and a rule new anticipation proposed by the author.
Reaction of Benzoyl Peroxide with Phenols Substituted with Electron-Withdrawing Groups
Authors: Inoue Hakuai , Simamura Osamu , Takamizawa Kanichiro
Published: July 2006

Benzoyl peroxide has been allowed to react with various halogenophenols in boiling carbon tetrachloride and the nature of the products has been examined.

2,4,6-Tribromophenol gave benzoic acid, polydibromophenylene oxide H(OC6H2Br2)nBr, 4-hydroxy-3,5,2′,4′,6′-pentabromodiphenyl ether, carbon dioxide and bromine, whereas in the case of 2,4,6-trichlorophenol the corresponding polymeric material could not be isolated, but p-benzoquinones substituted with chlorine and the 2,4,6-trichlorophenoxy group were formed. The reaction with 2,6-dichloro-and 2,6-dibromophenol gave a small amount of the corresponding 3,5,3′,5′-tetrahalogeno-4,4′-dihydroxybiphenyls, a type of product which were not obtained in the other cases. p-Halogenophenols yielded an appreciable amount of halogenocatechol monobenzoates.

p-Nitrophenol did not react with benzoyl peroxide in boiling carbon tetrachloride, but at 100°C in the absence of any solvent this phenol as well as the ortho isomer underwent reaction with evolution of considerable amount of carbon dioxide. These observations are discussed in terms of mechanisms involving free radicals.
Anionic Polymerization of Vinylidene Chloride. II. Homopolymerization Initiated by n-Butyllithium
Authors: Konishi Akio
Published: July 2006

The polymerization of vinylidene chloride initiated by n-butyllithium in n-hexane has been investigated. It has been found that the initial rate of polymerization is independent of the catalyst concentration above a critical value and is proportional to the square of the monomer concentration. The activation energy of the over-all rate was 10.7kcal./mol. The chlorine content of the polymer decreased inversely with the increase of catalyst concentration. An anionic mechanism is suggested for the polymerization kinetics.
A Study of the Polymorphic Formation of Calcium Carbonate in Thermal Springs with an Emphasis on the Effect of Temperature
Authors: Kitano Yasushi
Published: July 2006

1) When calcium carbonate was formed in the laboratory from the calcium bicarbonate solution through which carbon dioxide gas had not been bubbled during the process of the calcium carbonate formation: a) Only calcite was formed at a temperature below 25°C; aragonite was formed above 25°C, and vaterite was formed above 40°C. Between 40 and 60°C a large amount of vaterite was formed. With a rise in the temperature of the mother solution, the proportion of calcite decreased, b) Vaterite was easily formed from the calcium bicarbonate solution containing sodium chloride at a high temperature. With an increase in the temperature and in sodium chloride concentration, the proportion of vaterite increased, c) With an increase in both temperature and magnesium chloride concentration, the proportion of aragonite increased but that of calcite decreased. The presence of magnesium chloride in the mother solution hindered the formation of vaterite.

2) When calcium carbonate was formed in the laboratory from the calcium bicarbonate solution containing sodium chloride (or magnesium chloride) and bubbled with carbon dioxide gas continuously during the calcium carbonate formation, only calcite was formed despite a high temperature.

3) When calcium carbonate was deposited in thermal spring waters of a high temperature, aragonite was formed. However, from the waters into which carbon dioxide gas was supplied, in other words, from the acidic solution, calcite was formed despite a high temperature, and aragonite was formed from the waters to which carbon dioxide was not supplied, in other words, from the basic waters, despite a low temperature.

4) Up to the present time, vaterite has not been found in the deposits of thermal springs because: a) Calcium carbonate deposits of thermal springs were either formed at a location where carbon dioxide gas was supplied to the mother waters or where the concentration of magnesium ions in the waters was rather high, or b) even if vaterite had been formed, it would have changed to calcite or aragonite very quickly because of its low stability in solution.

5) In spring waters with the same chemical constituents, pH value, and temperature, the proportion of aragonite increased and that of calcite decreased with an increase in the rate of carbon dioxide gas escape from the waters and in the rate of calcium carbonate formation.

6) Aragonite was readily found in calcium carbonate precipitates formed floating on the surface of thermal spring waters, but it was not likely to be found in the precipitates deposited on the wall or bottom in the same waters.

The polymorphic formation of calcium carbonate formed in thermal springs depends mainly on the temperature, the concentrations of sodium ions, magnesium ions and carbon dioxide (pH) in the waters, and on the rate of calcium carbonate formation when calcium carbonate is formed from a similar water.
Synthesis of Dl-Lysine from 1,1,1,5-Tetrachloropentane
Authors: Saotome Kazuo , Kodaira Yasuto
Published: July 2006

Dl-Lysine was synthesized from 1,1,1,5-tetrachloropentane. The process involves seven steps; 1,1,5-trichloropentene-1 (92%), 1,1-dichloro-5-cyanopetene-1 (88%), 1,1-dichloro-6-aminohexene-1 (59%), 1,1-dichloro-6-phthaliminohexene-1 (96%), 2-chloro-6-phthaliminocaproic acid (95%), Dl-lysine monohydrochloride (53%). The over-all yield from 1,1,1,5-tetrachloropentane to Dl-lysine monohydrochloride was 23%.

In the hydrogenation of 1,1-dichloro-5-cyanopentene-1 to 1,1-dichloro-6-aminohexene-1, the Raney cobalt was found to be a favorable catalyst for attacking the nitrile group selectively.
Gouy Magnetic Balance for Use at Low Temperatures
Authors: Shiraiwa Yoshiaki , Kikuchi Katsunari , Kishi Eichi , Nagano Hiroshi , Oshima Keichi
Published: July 2006

This paper has reported on the performance, in the range between room and liquid nitrogen temperatures, of a Gouy-type magnetic balance, which had been constructed for absolute measurements of the magnetic susceptibility of paramagnetic salts. As a magnetic field, we used a highly homogeneous permanent magnet which was easily movable by hand. Therefore, precise measurement of the susceptibily is possible. With this balance, the susceptibility of 10−5c.g.s. units was measurable within a range of error of 5%.
Separation of Uranium from Fission Products using Cellulose
Authors: Oi Noboru
Published: July 2006

The separation of uranium from fission products by using cellulose has been demonstrated. Uranyl nitrate hexahydrate containing fission products was dissolved in an organic solvent that had low solubility of water, and this solution was passed through the column of cellulose. Almost all the fission products were retained on the cellulose, while uranium passed almost unadsorbed. The most labile nuclides were found to be ruthenium and cesium. Free nitric acid must be eliminated to prevent the elution of ruthenium.

The distribution ratios of individual fission products and neptunium between cellulose and an uranyl nitrate solution in n-butyl acetate were determined, and it was found that the adsorption of fission products decreased with the increase in the uranium concentration of the organic solvent. Therefore, the concentration of uranium that passed through the column was limited to below 0.2 m.

It was also found that water was necessary. This indicated partition as one of the mechanisms of this separation.

In this method the mass transfer of uranium between two different phases is not performed, so the contamination of fission products is rather small. Moreover, uranium can be easily recovered and fission products are condensed on a small amount of cellulose.
Energy Distribution of Secondary Electrons from Copper-Beryllium Alloy by Bombardment of Positive Ions of Inert Gases. II. Activated Copper-Beryllium
Authors: Sugiura Toshio
Published: July 2006

The distribution curves of the kinetic energis of secondary electrons from the activated copper-beryllium surface impacted by inert gas ions were together with the yield of the secondary electrons, measured by the retarding potential method. The contact potential difference between the ion target (activated copper-beryllium) and the electron collector (gold) was also measured by the retarding potential method for the thermal electrons from tungsten, and the correction to the kinetic energies of secondary electrons by this contact potential difference was made. For the purpose of obtaining information about the emission characteristics of the increase in the yield ot secondary electrons by target activation, the distribution of ΔN0(Ek), which is the difference in the secondary electrons emitted from activated and from electro-polished copper-beryllium, was plotted by electron energies. The main results obtained are as follows:

(1) The contact potential difference between activated copper-beryllium and gold is 0.25 eV. (gold, negative).

(2) The general features of the distribution curves of the secondary electrons emitted from activated copper-beryllium show a tendency similar to that of the secondary electrons emitted from electro-polished copper-beryllium, and they also show a great similarity to the distribution curves obtained from the not atomically clean semiconductor surface (germanium or silicon) by Hagstrum.

(3) The distribution of ΔN0(Ek) show a remarkable difference from the distribution curves for activated copper-beryllium. Distribution curves of ΔN0(Ek) higher than about 4eV. in electron energies showed a great similarity to the distribution curves of the Auger electron obtained by Hagstrum. Moreover, the distribution of ΔN0(Ek) for singly-charged ions shows clearly a separation in the electron energy scale; this result was explained by the fact that the stopping cross-section of the beryllium oxide is greater than that of the cupric oxide.

(4) From the explanation of the distribution of ΔN0(Ek), it is considered that the increase in the yield of secondary electrons by target activation depends on the stopping cross-section of beryllium oxide and on the Auger process of electron emission.
Differences in the Catalytic Activity of Nickel, Platinum and Palladium as Observed in the Isotopic Exchange Reaction of Paraxylene with Deuterium Oxide
Authors: Hirota Kozo , Ueda Tomiko
Published: July 2006

It has been confirmed that nickel can exchange catalytically only hydrogen atoms of methyl groups of paraxylene with deuterium oxide, irrespective of the method of preparation, while platinum and palladium can exchange hydrogen atoms of both methyl groups and benzene ring under similar experimental conditions.

It has been found that the catalytic activity of nickel becomes similar to that of platinum and palladium if nickel is supported on alumina, but remains unchanged if it is supported on silica or kieselguhr.

It has been shown to be difficult to explain these two findings perfectly.
Studies on Solvent Extraction using Radioactive Isotopes. VIII. Solvent Extraction of Cerium with Acetylacetone
Authors: Suzuki Nobuo , Oki Shohachiro
Published: July 2006

The extraction of cerium with acetylacetone was studied, using 144Ce as a tracer. Cerous cerium can not be extracted without an oxidizing agent. After the mixture of 0.61 m sodium Bromate and 5×10−6m cerium had been left standing for 100min. at pH 5∼6, 95% of the cerium was extracted in benezene.The reaction was accelerated by heating, e.g., at 40°C, or by increasing the concentration of acetylacetone and bromate. Care should be taken not heat too long. this avoiding the decomposition of the chelate by hydrolysis.The presence of phospate, oxalic acid, Citric acid, tartaric acid and EDTA causd interference.
Estimation of Micellar Charge from Conductivity Data of Aqueous Detergent Solutions
Authors: Kimizuka Hideo , Satake Iwao
Published: July 2006

An equation relating the micellar charge to the conductivity data was derived for the ionic detergent solutions. It was found that the calculated values of the micellar charge were approximately the same as the micellar aggregation number observed by means of the light scattering technique. The ratio of the fixed gegen ion to the micelle was also estimated.