bluuebunny/crossref_metadata_2025 huggingface dataset:
Ion-Exchange Separation of Cerium and Thorium with Lead-EDTA Complex as Eluting Agent
Authors: Taketatsu Tomitsugu
Published: July 2006

The separation of cerium and thorium ions was studied with a lead-EDTA complex solution as eluant. The optimum conditions were determined as the following: the concentration of the lead-EDTA solution was 0.015 mole, pH 3.0 and the flow rate 1.0∼1.5ml./min. Thorium ions were completely eluted with 200 ml. of the eluant at the optimum conditions, while no cerium ions were detected in the effluent with 1000 ml. of the eluant. Thus the use of a lead-EDTA complex solution as eluant was concluded to be effective for separation of cerium and thorium ions.
Penetration of Liquids into Filter Paper Used in Paper Chromatography
Authors: Nakagaki Masayuki , Osagawa Kyoko
Published: July 2006

The penetration of liquid into a piece of filter paper hung vertically above a liquid is studied theoretically and experimentally. The height of the ascent of the liquid is proportional to the square root of the time at the initial stage of the penetration, but the proportionality does not hold in a wide range of time. The equation which describes this relationship between the height and time has been derived. The values of the parameters in the equation have been determined for acetone, benzene, water, carbon tetrachloride and ethanol. It is concluded that the capillary gap in the filter paper is about 6 μ in the half distance and the length of the gap is about 3 times larger than the length of the filter paper, if the gap is assumed to be two dimensional.
Effects of Dry Grinding on Talc
Authors: Takahashi Hiroshi
Published: July 2006

The several-hundred-hour mechanicalmortar dry grinding on talc was examined by X-ray diffraction method, differential thermal analysis, electron microscopy and density measurements, and they were compared with those of kaolin minerals. In the dry grinding on talc, some characteristics in the structural changes by dry grinding were found. As the grinding progresses, the original crystals cleave and fracture and then split into fine crystals. Disordering in structure of these fine crystals is observable before the talc structure disintegrates completely. In talc, a new substance is produced by dry grinding, which is somewhat related to but different from the original talc structure. The appearance of this new phase is most remarkable in the stage of grinding where the crystalline pattern of talc entirely disappears in the X-ray diagram. This new phase has a non-crystalline structure, but the strurcture is not completely amorphous. It crystallizes into a new crystal at about 800°C. As the grinding progresses, the structure of this new phase gradually disintegrates to a completely amorphous structure similar to that of a silica-magnesia mixed gel. The formation of a zeolitic structure is not so remarkable; also, even if this structure is formed, the period of its stage is very short. It is an important characteristic that talc wholly changes into a new non-crystalline substance by dry grinding. It is generally supposed that talc does not easily suffer the effects of dry grinding because the structure is stronger than that of kaolin minerals.
Studies on the Interaction of Surface Films with Solute in Solution. V Deposition of Monolayers of Several Amphipathic Compounds from Surfaces of Aqueous Solutions of Congo Red and Crystal Violet
Authors: Muramatsu Mitsuo
Published: July 2006

Attempts were made to obtain the builtup films of stearic acid, cholesterol, cetyl alcohol, ethyl n-hexadecyl ether, ethyl stearate and octadecylamine, by transferring each monolayer from the surfaces of water and aqueous solutions of Congo red and Crystal violet. Deposition of the monolayers of cetyl alcohol, ethyl n-hexadecyl ether and ethyl stearate was unsuccessful, irrespective of whether the substrate contained dye or not. On the other hand, the monolayers of the remaining compounds could easily be deposited onto the solid phase from the surfaces of water and dye solution.

The effect of added dye upon the apparent spacing of the film thus obtained seems to show an attachment of dye to the film substance, though the spacing varied from one case to another. This variation could be explained taking account of the balance of two contributing factors mutually opposite to the apparent spacing: one, increase of the film thickness due to the attachment of dye, and the other, decrease of the refractive index of the film due to the wide separation of n-hydrocarbon chain. Such a consideration was supported by the data on the wettability toward benzene. All these phenomena are in agreement with the data on the effect of dissolved dye upon the limiting area of the monolayer spread on it.
Purification of Silicontetraiodide by Zone-refining Process
Authors: Baba Hideo , Nozaki Tadashi , Araki Hidemaro
Published: July 2006

The behavior of phosphorus and boron as impurity elements in silicon tetraiodide was studied during the normal segregation and zone melting processes. Both of them can be removed efficiently by this process, and it is considered that the colloidal hydrolyzed product suspended in silicon tetraiodide plays a predominant role for segregation because of its high adsorptivity to these elements. The distribution curve of radioactive phosphorus seems to show the influence of this material.
On the Mechanism of Oxidation by Cuprous Chloride, Pyridine and Air. II. The Mechanism of Formation of Azobenzene from Aniline
Authors: Kinoshita Keiz\={o}
Published: July 2006

(1) Attempted aerial oxidation of aniline, catalyzed by cuprous acetate pyridine complex, is unsuccessful even at 80°C.

(2) By the aerial oxidation of equimolar mixture of aniline and p-anisidine, catalyzed by a small amount of cuprous chloride, 4,4′azoanisol is selectively obtained in the early stage of this reaction.

(3) By the aerial oxidation catalyzed by cuprous chloride in a pyridine solution, the yields of the azo compounds, which are produced from p-toluidine and p-anisidine, are almost quantitative. On the other hand, the yields of the azo compounds, which are produced from o-toluidine and o-anisidine, are very poor.

(4) In this reaction, it is postulated that an intermediate [Cu(II)–NHC6H5] is initially formed, and that hydrazobenzene and cuprous complex are produced by the bimolecular reaction of this intermediate.

(5) Hydrazobenzene is converted into azobenzene almost quantitatively under the same condition as aniline is oxidized.
Studies on the Sapogenins of Dioscorea tokoro Mdkino. II The Structure of Tokorogenin
Authors: Morita Katsura
Published: July 2006

(1) The correlation of tokorogenin (I) with the known steroid, 25D-5β-spirostan (IX), was established: Tokorogenin formed an acetonide (IIa), which could be tosylated and then hydrolyzed to give tokorogenin monotosylate (IVb). On treatment with alkali, IVb was led to anhydrotokorogenin (Va), which on oxidation with Py.—CrO3 and subsequent reduction with CrCl2 gave rise to an α,β-unsaturated ketone (VII). Catalytic hydrogenation of VII followed by the Huang-Minion reaction furnished 25D-5β-spirostan (IX).

(2) In order to determine the configuration of the hydroxyl group at C3, IIa was oxidized with Py.—CrO3 and the product was reduced with LiAlH4 to give a mixture of IIa and XIII. Careful chromatography of the mixture revealed that the substance eluted first was XIII, while the second which eluted from the column was IIa, thus leaving only the structural possibility of 25D-5β-spirostan-1β,2β,3α-triol (I) to tokorogenin.
High Resolution Nuclear Magnetic Resonance Spectra of Ring Protons in Substituted Benzenes
Authors: Yamaguchi Ichiro , Hayakawa Naohiro
Published: July 2006

High resolution proton magnetic resonance spectra of a variety of mono- and di-substituted benzenes were observed at 56.4 Mc. The spectra of molecules with higher symmetry were analyzed, and the values of chemical shifts among the ring protons and those referred to benzene were obtained as well as spin coupling constants. The spectra were discussed with correlation to the substituents.
Electrode Processes of Nickel(II) Ions at the Mercury Electrode in Concentrated Calcium Chloride Solutions
Authors: Tanaka Nobuyuki , Tamamushi Reita , Kodama Mutsuo
Published: July 2006

A typical reduction wave with a half wave potential of −0.462 V. vs. S. C. E. was obtained with nickel(II) ions in 6 m calcium chloride solution. The a. c. and the Kalousek’s polarograms revealed that the electrode reaction is a quasi-reversible one. From the coulometric measurement carried out at the constant potential, the overall electrode reaction proved to be a two-electron reduction. Nearly the total amount of nickel reduced by the controlled potential electrolysis with the mercury electrode was recovered from the mercury, indicating that the nickel (II) ions are reduced to nickel metal to form probably nickel amalgam. From these experimental results the electrode reaction of nickel (II) ions in 6 m calcium chloride at the mercury electrode was concluded to proceed quasireversibly according to the equation

Nicl_4^2-+2e+Hg\ightleftarrowsNi(Hg)+4Cl^-
Long-chain Phosphates. I. Reactions of Solid Potassium Kurrol Salt with Solutions of Various Metal Salts
Authors: Ohashi Shigeru , Yamagishi Kazuo
Published: July 2006

Pure crystalline potassium Kurrol salt was prepared and its X-ray pattern was compared with that obtained by Klement et al. The solubility of the potassium Kurrol salt in water was 0.007∼0.009 per cent at room temperature. Qualitative observation was made for the reactions of the potassium Kurrol salt with various metal ions. Therefore was an optimum concentration of sodium chloride to dissolve the potassium Kurrol salt. The investigation of reactions of the potassium Kurrol salt in a solid state with solutions of nickel sulfate indicated that the reaction is a cation-exchange reaction between potassium and nickel ions. It was also found that the reaction is reverssible. The nickel-substituted product is green-colored and gummy. Some properties of the substances obtained by heating the above green product were studied. Exchange reactions of potassium Kurrol salt with various metal ions were investigated. Percentages of exchange for magnesium, calcium, manganese(II), iron(II), cobalt(II), nickel(II), copper(II) and zinc were all in the range 82 to 94 under the conditions used in the present work.
Self-consistent Field Molecular Orbital Treatment of Benzenium Ion for a Simplified Model of Hyperconjugation
Authors: Morita Toshifumi
Published: July 2006

Semi-empirical SCF LCAO MO calculations of benzenium ion was undertaken for the model of localization as well as hyperconjugation of the H2–C bond constructed at the position of proton attack. A simplified model of hyperconjugation in the semi-empirical SCF MO method was extended. Calculated results for the hyperconjugation model agreed satisfactorily with the experimental electronic spectra.

Superiority of the SCF MO method to the Hückel MO or ASMO method was indicated in connection with the ordinarily accepted spectral shift through hyperconjugation. Further, some modifications were tried, for the bond localization model, which would have to be taken in the Hückel MO as well as ASMO calculations.

The proton magnetic resonance signals due to methyl substituents in the carbonium ions of methylbenzenes were discussed from charge densities of benzenium ion.
Estimation of the Energy of Hydrogen Bonds Formed in Crystals. II. Phenols
Authors: Aihara Ariyuki
Published: July 2006

The energies of hydrogen bonds formed in the crystalline state of twelve phenols have been estimated by a procedure proposed in a previous paper. The values of energy range from zero to 7 kcal./mol. depending upon the difference of molecular structures: the phenols with bulky substituents in the vicinity of OH groups are non- or weakly-hydrogen-bonded, while those with carbonyl or methoxy groups at para positions are strongly bonded presumably by head-to-tail association. The other phenols fall between the two extremes. Incidentally it is interesting that the highest values of OH···O bond are rather close to the energies of association of carboxylic acids in the gaseous state.

With 1- and 2-naphthols, a parallel relation between the transitions of the above substances and the melting of phenol has been pointed out.
Primary Processes in the Photobleaching of Eosin as Revealed by the Flash Technique
Authors: Kato Shunji , Watanabe Teiko , Nagaki Shigeo , Koizumi Masao
Published: July 2006

Reductive photobleaching of eosin and uranin in ethanol solutions was studied by the flash technique. Transient spectra of semiquinone with a lifetime of millisecond order was established. In addition, another transient spectra with a life of the same order was observed in the case of eosin. This was interpreted to be due to a certain complex intermediate between ethanol and eosin, formed prior to semiquinone. The aerated alcoholic solution and the evacuated aqueous solution, when illuminated by a flash, showed no transient spectra in the wavelength region of the above two intermediates. The fluorescence of the aerated ethanol solution produced by the flash had about twenty times as large intensity as that of the evacuated solution induced under otherwise similar condition. A scheme for the primary processes of the reductive photobleaching involving the above complex can interpret all these results satisfactorily.
Absorption Spectra of Metallic Complexes with Aromatic Molecules
Authors: Yamada Shoichiro , Yamazaki Hiroshi , Nishikawa Hiroaki , Tsuchida Ryutaro
Published: July 2006

Ultraviolet absorption spectra of Cr(CO)6, Cr(C6H6)(CO)3, [Cr(C6H6)2]I and [Cr(C6H5CH3)2]I have been determined in various solvents. Dichroism in the visible and ultraviolet region of Cr(C6H6)(CO)3 has been determined at room temperature by Tsuchida and Kobayashi’s microscopic method with a single crystal of the compound.

The absorption spectrum of Cr(C6H6)(CO)3 shows main features similar to those of the spectrum of the [Cr(C6H6)2]+ ion.

These compounds all show a weak absorption band to the long wavelength side of the intense absorption bands.

The results of the measurements have been discussed in relation to the bonding involved in these compounds. Discussion also has been undertaken about Hein’s polyphenyl-compounds of chromium(I) on the basis of the present measurements. Absorption spectra of Hein’s compounds of chromium(I) seem to be in agreement with the assumption of the sandwich structure.
Benzylideneaniline. I. Structure and Ultraviolet Absorption Spectrum of Benzylideneaniline
Authors: Ebara Nozomu
Published: July 2006

The ultraviolet absorption spectra of benzylideneanilines, as well as of their conjugate acids, have been measured.

These spectra can not be explained with the ever believed stilbene-type planar structures of these molecules.

An alternative structure is proposed for benzylideneaniline with the benzene ring of aniline part nearly perpendicular to the rest of the molecule.

This structure also adequately explains many experimental evidences, which have been investigated previously but are not accounted for by the planar structure.
Effect of Hydrogen and Carbon Monoxide on the Electrical Conductivity of Zinc Oxide
Authors: Kubokawa Yutaka
Published: July 2006

The rate of increase in conductivity of zinc oxide caused by hydrogen was found to be proportional to p0.85 and to have an activation energy of 21 kcal./mol. For this system the activation energy of the increase of donors was shown to be almost the same as that of the conductivity increase. The activation energy of the decrease of donors by evacuation was 31 kcal./mol. A similar conductivity increase was observed with carbon monoxide. On the basis of these results together with those of adsorption measurements reported previously, it was concluded that the conductivity increase was scarcely related at all to the hydrogen chemisorption, indicating that it is untenable to postulate two such types of hydrogen chemisorption as was believed in the previous work, i.e., one responsible for the conductivity increase and the other without such effect. As for the cause of the conductivity increase, the surface reduction of zinc oxide was suggested.
The Transition Polymerization of Acrylamide. I. On the Polymerization Condition and the Property of Polymer
Authors: Ogata Naoya
Published: July 2006

The polymerization condition for the transition polymerization of acrylamide to poly-β-alanine has been investigated in the presence of alkali catalyst. The catalytic effect of alkali catalysts is largest for tertiary alkoxide and that of alkali metals is in the order as K>N>Li. The yield of polymer is larger in the solvents of lower dielectric constant and in aromatic solvents than in aliphatic solvents. The polymerization seldom occurs in the solvents with active hydrogen. The property of the polymer has also been investigated.
Photoreduction of Methylene Blue by Visible Light in the Aqueous Solution Containing Certain Kinds of Inorganic Salts. I. General Features of the Reaction
Authors: Usui Yoshiharu , Obata Hiroshi , Koizumi Masao
Published: July 2006

It was discovered that the irradiation of the aqueous solution of methylene blue containing various kinds of salts, produces the leuco form of dye; accompanied with this reaction, irreversible photodecomposition of dye and demethylation occurs to some extent. Hydroxide, phosphate and borate were found to be most effective in promoting this photoreduction. Careful studies were performed to counteract the possible effect of impurity. Since the present reaction was considered most certainly to be due to the ultimate fission of water, the analysis for Oxygen and hydrogen peroxide was undertaken. The former was not detected by means of a mass-spectrograph in case of phosphate, but the latter was chemically detected in case of borate buffer. The connection between the quantity of demethylation and that of the formation of leuco dye was investigated and clarified to some extent.
Thermodynamical Studies on Binary Systems Consisting of Polar and Non-polar Liquids. II. The Measurement of the Heats of Mixing for Binary Systems of Polar and Non-polar Liquids
Authors: Amaya Kazuo
Published: July 2006

The heats of mixing were measured for 22 binary systems of polar and non-polar liquids where the pairs of liquids have similar molecular sizes.

For the systems in which the non-polar components are non-aromatic, the van Laar coefficients α are positive and increase smoothly as the concentration of polar liquids decrease. This variation of α with concentration is attributed to the effect of dipole of the polar component.

However, for the systems where the nonpolar components are aromatic, the values of α are smaller than that of the corresponding non-aromatic system and are even negative for most of the cases and decrease with concentration of polar component in most concentration ranges.

The sharp difference between two groups of the binary systems, was attributed to the structural difference of aromatic and non-aromatic non-polar components.

The effect presumably due to the quadrupole of the non-polar components was noticed.
Photochemical Processes due to n-π* and π-π* Transitions of 2-Picoline N-Oxide in the Vapor Phase
Authors: Hata Norisuke
Published: July 2006

The gaseous photolysis of 2-picoline N-oxide was carried out by irradiation with the 3261Å (Cd 3P1) or 2537Å (Hg 3P1) resonance lines corresponding to an n-π* or a π-π* absorption of this substance, respectively.

In the case of 3261Å irradiation, the major product was 2-pyridinemethanol, whose quantum yield showed a marked temperature-dependence. The activation energy necessary for the production of 2-pyridinemethanol was estimated to be about 3.4 kcal. mol−1.

On the other hand, the photolytic products at 2537 Å irradiation were 2-picoline and other decomposition products and polymers. The quantum yield of 2-picoline showed a marked temperature-dependence, which may be attributed to the interaction between the 2-methyl group and the N→O group. The activation energy necessary for the production of 2-picoline was estimated to be about 1.1 kcal. mol−1.
Dehydrogenation of Secondary Alcohols with Reduced Copper. III. Catalytic Dehydrogenation of Isopropyl Alcohol (Part 1)
Authors: Kawamoto Kazuaki
Published: July 2006

In order to determine whether the dehydrogenating activity of reduced copper is affected by the species of precipitants in the preparation, the dehydrogenation of isopropyl alcohol to acetone was studied by using five different precipitants, i. e. sodium hydroxide, potassium hydroxide, potassium carbonate, sodium bicarbonate and potassium bicarbonate. The dehydrogenation was the highest with no side reaction at 305∼325°C, especially when potassium bicarbonate was used as precipitant.

When the copper catalysts, prepared with sodium hydroxide, potassium hydroxide and potassium carbonate, were used, condensation together with dehydrogenation occurred. The formation of higher ketones is explained by the assumption of intermolecular dehydration between acetone and original isopropyl alcohol.
Syntheses and Ultraviolet Spectra of Aromatic Azo Compounds. I. Bromo-methylazobenzenes
Authors: Nomura Yujiro
Published: July 2006

1) Twelve bromo-methylazobenzenes have been synthesized by the reactions of Grignard reagents with zinc chloride double salts of diazonium compounds. Ten of them are new compounds.

2) The ultraviolet absorption spectra of bromo-methylazobenzenes have been measured and some regularities of the absorption maxima have been observed in them.
Acid-Base Property and Metal Chelate Formation of 4-(2-Pyridylazo)-resorcinol
Authors: Iwamoto Toschitake
Published: July 2006

Acid dissociation stages of analytical reagent 4-(2-pyridylazo)-resorcinol (PAR) and metal chelate formation of PAR were investigated by absorption measurements and pH-titrations. The first acid dissociation constant was determined as 1.48×10−6 (pka1=5.83) and the second as 3.2×10−13 (pka2=12.5) at 25°C. PAR forms 1 : 2 chelate with Fe(III), Co(II) and Ni(II), and forms 1:1 chelate with Cu(II), Zn(II), Cd(II), Hg(II) and Pb(II). The stability constant of copper(II)-PAR chelate was determined as 5×1011 at 25°C. Some analytical aspects of PAR were also discussed.
Nuclear Magnetic Resonance Study of the Steric Effect in Dimethylphenols
Authors: Yamaguchi Ichiro
Published: July 2006

The nuclear magnetic resonance in dimethylphenols were observed. The dependences of the chemical shifts for the methyl, hydroxyl and ring protons on solvent and concentration were measured and several clear differences were observed among the spectra of the isomers. The phenols with one or two ortho methyl groups showed peculiar behaviors which may be ascribed to the interaction between the hydroxyl group and the ortho proton or ortho methyl protons. The evidience of the steric hindrance of the ortho methyl group to form an intermolecular hydrogen bond is also shown in the present measurements.
Dehydrogenation of Secondary Alcohols with Reduced Copper. V. Catalytic Dehydrogenation of sec-Butyl Alcohol
Authors: Kawamoto Kazuaki
Published: July 2006

It was confirmed that ethyl methyl ketone and 5-methyl-3-heptanone are produced from sec-butyl alcohol with reduced copper alone. Two distinct types of reduced copper were prepared by precipitation with sodium hydroxide and with potassium carbonate. They differ somewhat in their ability to promote dehydrogenation of sec-butyl alcohol and differ greatly in their power to bring about condensation. The copper catalyst prepared with potassium carbonate acts to dehydrogenate sec-butyl alcohol at all the temperatures examined (185∼325°C), giving ethyl methyl ketone, but the catalyst prepared with sodium hydroxide acts to dehydrogenate and to condense simultaneously at a certain temperature (220°C), giving 5-methyl-3-heptanone along with ethyl methyl ketone, and this affords a new synthetic method for 5-methyl-3-heptanone. sec-Butyl alcohol was converted into ethyl methyl ketone in 94∼96% yield with no side reaction by passing it over these catalysts at 325°C.
Investigation on Mixed Complexes. VI. General Discussion on the Formation of Mixed Complexes
Authors: Kida Sigeo
Published: July 2006

The stability of a mixed complex, [MAiBj], was discussed and compared with the complexes, [MAn] and [MBn], (where A, B and M represent ligands and central ion, respectively, and i+j=n).

It was verified by calculation that the electrostatic effect exerts an influence so as to promote the formation of a mixed complex. The effect of σ-covalency of the coordination bond can be considered analogously to the electrostatic one, and is expected to have a similar influence upon mixed-complex formation. The above discussion is supported by experimental data, showing that the mixed complex is formed, in general, more often than can be expected statistically.

However, there are some exceptions to the above-mentioned rule, for instance, in the cases of cyano platinum(II) complexes or dipyridyl complexes. They are attributed to π-bonding between the ligands and the central ion. Discussion has been made concerning the reason why π-bonds depress the formation of mixed complexes.
Catalytic Asymmetric Cyanohydrin Synthesis with Synthetic Optically Active Polymer. I. Synthesis of Benzaldehyde Cyanohydrin
Authors: Tsuboyama Sei
Published: July 2006

Poly-s-isobutyl-ethylenimine was synthesized and with it asymmetric synthesis of benzaldehyde cyanohydrin was carried out with good results: P% is 20%.

This is ascribable to (1) the steric effect of the isobutyl group adjacent to the amino group in the polymer, (2) the stereo-regularity of the polymer, and presence of an asymmetric center and functional group in the main chain of the polymer, and (3) the spiral structure, if it exists, of the polymer enhancing its stereoregularity effect.
The Reaction of Tropoids and Quinone Derivatives. III. Reaction of Several Tropolones and o-Benzoquinone Dibenzimide
Authors: Seto Shuichi , Nishiyama Yukio
Published: July 2006

Reaction of tropolone and o-benzoquinone dibenzimide was carried out and the structure of its product was determined by deriving it to a 2-phenylbenzimidazole derivative. This revealed that the product is N-(tropolone-5-yl)-N,N′-dibenzoly-o-phennylenediamine. 3-Bromotropolone and 3, 7-dibromotropolone also underwent the same reaction to afford the corresponding bromo derivatives. For the sake of identification, 1-(4′-methoxycarbonylphenyl)-2-phenylbenzimidazole was synthesized from 2-amino-4′-methyldiphenylamine.
Krypton-85 in the Atmosphere
Authors: Kigoshi Kunihiko
Published: July 2006

The activities of atmospheric krypton-85 were measured on the samples of krypton collected in Tokyo. The observed activities show a remarkable increase after May, 1960, which can not be explained by the production of krypton-85 by nuclear tests. The slow increase before May, 1960, does not contradict an assumed parallelism between the behavior of the man-made carbon-14 in the atmosphere and that of the krypton-85 produced by nuclear tests.
Gas Absorption by Cobalt Soaps
Authors: Funakoshi Hideo
Published: July 2006

The gas absorption by cobalt oleate and stearate has been studied. It was found that cobalt oleate absorbs oxygen very remarkably, but nitrogen and hydrogen, very little. Cobalt stearate absorbs oxygen negligibly, but in the presence of oleic acid the absorption becomes considerable. From the studies of ultraviolet and infrared spectra and X-ray analysis of the oxygen absorption by cobalt oleate, it was found that oxygen is coordinated by the cobalt atom and destroys the double bond structure. The probable mechanism of the catalytic action of cobalt soaps has also been presented.
Infrared Absorption Spectra of Water of Crystallization in Sodium Sulfate Decahydrate Crystals
Authors: Gamo Itaru
Published: July 2006

The observed spectra of water of crystallization were interpreted on the basis of the effect of hydrogen bonding. It was proposed that at least two kinds of water molecules exist in the unit cell of the crystal. The corresponding two O–H…O distances were roughly estimated to be 3.01 and 2.58 Å respectively by the use of Glemser’s relationship between the stretching frequency and the hydrogen bond distance.
Studies of the Structure and Properties of Aromatic Polyamide. I. Physical Properties of Poly(m-xylyleneadipamide)
Authors: Yoda Naoya
Published: July 2006

Poly(m-xylyleneadipamide) was synthesized by the polycondensation of m-xylylenediamine and adipic acid, and the resulting polymer was melt-spun to afford a mono-filament. The physical properties of the undrawn filament, the stretched filament, and the stretched and annealed filament were investigated. It was found that the dynamic mechanical behavior and the chemical property of the aromatic polyamide are intermediate between poly-s-capramide and polyethylene terephthalate.
On the Association of Condensed Polycyclic Aromatic Compounds in Concentrated Sulfuric Acid
Authors: Handa Takashi
Published: July 2006

The effect of the concentration on the absorption spectra of condensed polycyclic aromatic hydrocarbons and their related carbonyl derivatives in concentrated surfuric acid was studied in the concentration range from 10−6to 10−3 mol. per liter. The free energies and heats of formation of these associates were also measured.

In the case of the dibenzopyrene molecule in 96 per cent sulfuric acid, it is observed that various kinds of association, such as 8, 16 etc., were obtained in successive steps with the increase in the concentration of the solute, while in the case of carbonyl derivatives, only one kind of associate was observed, the number of degree of association of which was observed to be 2, 4 and 16.

In the case of dibenzopyrene in 96 per cent sulfuric acid, where it is believed to be doubly protonated, the cause of association might be explained by the dispersion effect, while the blue-shift of the absorption peak of the monomer is clearly observed in successive steps succession with the increase in the concentration of the solute.

However in the case of carbonyl derivatives and dibenzopyrene in 86 per cent sulfuric acid, where they are singly protonated, it is observed that they do not show any blue-shift of their absorption peaks but a lowering of the extinction coefficient.

As is illustrated in Table I, their experimental heat of association may possibly not be explained by the dispersion effect alone. It may be necessary to take into consideration some kind of hydrogen-bonding between the carbonyl oxygen atoms and the proton.
The Formation and Crystalline Nature of Boron Nitride in the Reaction of Boron Oxide with Sodium Amide
Authors: Tagawa Hiroaki , Itouji Otokichi
Published: July 2006

The reaction of boron oxide with sodium amide has been investigated using differential thermal analysis and thermogravimetry. The reaction occurs at 210°C, the melting point of sodium amide, while in the presence of a large amount of sodium hydroxide, the reaction temperature is lowered to 165°C. It has been shown from the results of the differential thermal analysis that the reaction of boron oxide with sodium amide commences as soon as the sodium amide melts.

The boron nitride formed completes the skeletal structure of B–N hexagonal layers even at 200°C. The fundamental infrared absorption spectra of boron nitride is very little influenced by the fabrication temperature. The crystal-linity of boron nitride as shown by the inter layer spacing and the crystallite size increases with the reaction temperature.
The Solution Behavior of Polystyrene Derivatives: Poly-p-chlorostyrene
Authors: Saito Takahide
Published: July 2006

The polar group in the para position of the benzene ring of poly-p-chlorostyrene has a remarkable influence on the solution behavior and that, especially, the chain in the polar solvent is particularly extensive because of the interaction between the C–Cl group in the para position and the polar solvent.
The Structural Assignments for the Geometrical Isomers of α,α′ -Dimethylstilbene
Authors: Nagai Yoichiro , Simamura Osamu , Ehara Leo
Published: July 2006

cis- and trans-4, 4′-Dinitro-α, α′ -dimethylstilbene were prepared by oxidation of p-nitroacetophenone hydrazone with lead dioxide in benzene, followed by treatment with sulphur dioxide. Catalytic reduction of the trans-dinitro compound gave at least 64% of trans-4,4′-diamino-α, α′-dimethylstilbene, m. p. 157.6°C, and a similar reduction of the cis-dinitro compound afforded a mixture of the cis- and trans-diamino compound which was shown to contain at least 61% of the cis-isomer. On de-amination, the trans-diamino compound yielded α, α′-dimethylstilbene melting at 107°C, and the above mixture of the cis- and trans-isomer, a mixture of the isomeric α, α′-dimethylstil-benes in which the lower melting form predominated (at least 70%). These findings establish that α, α′-dimethylstilbene, m.p. 107°C, has the trans- and the isomer, m. p. 67 °C, the cis-configuration.
Physicochemical Studies on Cobalt Salts of Higher Fatty Acids. VII. Effects of Solvents on Cobalt Soaps. Solubilities and Color Changes of Cobalt Soaps in Solvents, and Adsorption of Water Vapor on Cobalt Soaps
Authors: Kambe Hirotaro
Published: July 2006

The effects of various solvents on cobalt soaps were investigated. The solubility of cobalt soap was low in general. In pyridine and bromoform, it showed a considerable value. In a hot state, several solvents dissolved cobalt soaps fairly well. In some solvents, jellies were obtained on cooling. In other solvents, the color changed to a dirty yellow. Absorption spectra showed that the absorption maxima in these solutions were displaced for a shorter wavelength. This means that a change of the electronic configuration occurred.

Adsorption of water vapor on cobalt soaps was measured. Red dihydrate seemed to adsorb much more water vapor than blue anhydrate.
Periodic Acid Oxidation on N-Arylamino Alcohols
Authors: Hattori Kiyoshi , Harada Hirokiti , Hirata Yoshimasa
Published: July 2006

The authors have examined the cleavage reaction with periodic acid of the N-aryl-α-amino alcohols. It has been seen that the α-amino alcohols do not react with the oxidant when substituted by the N-2,4-dinitrophenyl or o-nitrophenyl group. When N-aryl-α-amino aldehyde groups were produced during the course of oxidation, the normal cleavage reaction took place even if the substituent was a N-2,4-dinitrophenyl group. An over-oxidation was observed in the periodate oxidation of other N-aryl-α-amino alcohols, and it was proved that the cause of such high consumption of periodic acid was due to the oxidation of the aromatic amine that was produced by the normal cleavage of the N-aryl-α-amino alcohol group.
Electronic Structures of Naphthalenediols. II. β, β′-Naphthalenediols
Authors: Nishimoto Kichisuke , Fujishiro Ryoichi
Published: July 2006

The molecular diagrams and extradelocalization energies of the 2,3-, 2,6- and 2,7-naphthalenediols were calculated by using the LCAO MO method. To elucidate the effect of the 9–10 bond on the molecular properties of naphthalene derivatives, we carried out calculations of the electronic structures of naphthalene hydroxy derivatives based on the perimeter model. These calculations proved that:

1) The 3-position in the naphthalene derivatives in less reative than the other positions.

2) The α-derivatives are more stable than the β-derivatives.

3) The insertion of the 9–10 bond in the perimeter model causes a decrease in the degree of conjugation interactions among the ring and the substituents.

4) In the cases of A, A-derivatives, the substituents have no significant influence on the unsubstituted ring, but produce rather a large effect on the substituted rings.

5) α-Substitutions cause an increase in the mobilities of π-electrons in the direction of the short molecular axis, but the β-substitutions lead to an increase in the direction of the long molecular axis.
Infrared Absorption Spectra of Hydrazides. III. Hydrazides of Aliphatic Acids
Authors: Mashima Mitsuo
Published: July 2006

The infrared absorption spectra of the hydrazides of aliphatic acids have been examined in the rock salt region. The N-H stretching frequencies are found near 3200 and 3030 cm−1 in the solid state and near 3320 cm−1 in dilute solution. The amide I band is seen near 1600 cm−1 in the solid state, while in solution there are two bands, near 1720 and 1690 cm−1. In the solid state the amide II band appears near 1490 cm−1. The amide III band is found near the lower limit of the normal range of 1305∼1200 cm−1 for the secondary amides.
Complexing Behavior of Kojic Acid with Metal Ions. I. Mg(II) and Mn(II) Chelates
Authors: Murakami Yukito
Published: July 2006

Chelating tendencies of kojic acid toward divalent magnesium and manganese ions have been investigated in aqueous media at 25.0±0.1°C and 0.10 m of ionic strength. In spite of the difference in their electronic configurations, both metal ions formed similar chelate compounds and indicated an optimum coördination number of four. Both metal ions formed kojate chelates whose stabilities are nearly equal to the corresponding metal chelates of β-diketones of the same acidity.
Effect of Non-hydrogen Bonding Solvents on the Electronic Spectra of Aromatic N-Oxides
Authors: Kubota Tanekazu , Yamakawa Masumi
Published: July 2006

The strong π-π* absorption bands of pyridine N-oxide, 4-nitropyridine N-oxide, acridine N-oxide and N-methylbenzaldoxime were measured in various solvents, and the frequency shifts induced by solvents were quantitatively analyzed by applying the McRae’s theory of the solvent effect. On the other hand, the fluorescence spectra of acridine N-oxide have also been recorded in various solvents, and the solvent effect has been discussed in connection with that of the absorption spectra. The results show that the π-electron transfer from the oxygen atom to the ring is much greater in the excited state than in the ground state.
The Effect of Dissolved Paramagnetic Ion on the ESR Spectra of Diphenyl Nitric Oxide
Authors: Deguchi Yasuo
Published: July 2006

The broadening effect of dissolved oxygen and foreign paramagnetic ions on the ESR spectra of the DPNO solution has been discussed. Using the BPP theory, it is explained that this effect is mainly caused by the magnetic dipole-dipole interaction of an electron with with a proton nuclear spin.
Solvent Extractive Fractionation of Ziegler Polystyrene
Authors: Yamada Akira , Yamamuro Yoshio , Yanagita Masaya
Published: July 2006

The solvent extractive fractional ability has been described, using Ziegler polystyrene as sample. The order in hot extraction is tetra-hydrofuran >dioxane >ethyl methyl ketone ≥ ethyl acetate, while that in cold extraction is benzene >> ethyl methyl ketone≥ethyl acetate=toluene.
The Tubular Structure of Collagen Fibril
Authors: Haisa Masao
Published: July 2006

1. The X-ray scattering has been measured for moist and dry collagens of fowl-neck tendon, untreated or treated with formaldehyde or acetic acid. Some modifications of the collagen fibril were also examined by electron microscope.

2. The wide-angle scattering data are compatible with a structure consisting of crystalline and amorphous parts. The intensity distribution of the small-angle diffraction is interpreted by a helical groove structure. The Fourier transform calculated for this model is shown.

3. The electron micrographs show that collagen fibril has a kind of tubular structure with a circular or flat and coiled cross section.

4. The data are discussed with respect to the assumption that collagen fibril is composed of a woven sheet of polypeptide chains in which the crystalline and amorphous parts occur alternatively.

5. A reasonable assignment of hydration to the helical groove is possible; this gives the fibril an approximately uniform electron density in the moist state.
Rapid Microdetermination of Dysprosium in Terbium Oxide by Neutron Activation and γ-Ray Spectrometry
Authors: Okada Minoru
Published: July 2006

Dysprosium in terbium oxide powder was determined by a simple method involving 1 min. irradiation with pile neutrons of 3×1011neutrons per cm2/sec. and repeated γ-ray spectrometry using a 2 in. thick sodium-iodide crystal attached to a 256-channel pulse-height analyzer. Both interferences and the self-shielding effect were negligible. The coefficient of variation of single analyses was 5.2% for a 24 mg. sample of 48 p. p. m. dysprosium content.
Using Iron Ores of Kalabagh. II. Production of Limonite-Acid Method
Authors: Ali M I
Published: July 2006

A method of limonite production has been developed in this laboratory and it was produced from both “Kalabagh iron ores” and “spent limonite” by using local sulfuric acid (60° Bé). Ammonium sulfate, by-product, was also recovered. The process comprised of (i) digestion of the raw materials with 70.0% sulfuric acid, (ii) ammonia treatment of the resultant ferric sulfate solution to produce ferric hydroxide and (iii) careful drying and blending of ferric hydroxide (and oxide) to the desired consistency. The over-all recovery of spent limonite was found to be 80.0%. A material balance sheet is also presented. For the production of 20.0% make-up limonite “siderite” iron ore is suggested to be of use.
Studies on Micro-paraffin. VI. Properties of the Micro-paraffin
Authors: Negoro Kazuo
Published: July 2006

1) The micro-paraffin has longer mean carbon chains than those of ordinary crystalline paraffins, and the content of side-chain hydrocarbons is less than that in ordinary paraffins; its crystals belong to an orthorhombic system, and the formation of fine crystal grains is a result of secondary causes.

2) If the paraffin is recrystallized in ethyl alcohol in the presence of organic compounds of a similar structure which have benzene rings with hydroxyl groups such as Santopour, picric acid, p-hydroxybiphenyl, etc., the crystal growth is inhibited and the crystallized amount of the paraffin crystals is reduced, which is the cause of the formation of fine crystal grains.

3) The alcohol-extracted fraction, isolated from the micro-paraffin materials, has a fairly long alkyl chain and benzene rings with the hydroxyl groups. The crystalline or n-paraffin is micro-crystallized, the same as the above organic compounds, when a very small amount of the fraction is added to it.

4) The content of n-paraffin in the microparaffin is less than that in ordinary crystalline paraffin, but the former contains more sidechain components. The paraffin forms fine crystal grains in the presence of compounds such as the alcohol-extracted fraction.

5) As a result of the purification by the urea method and chromatography, X-ray diffraction, etc., a considerable amount of the crystalline n-paraffins has clearly been found to be contained in micro-paraffin. Therefore, the micro-paraffin does not consist of sidechain paraffin and is not originally micro-crystallized, as has hitherto been believed.

6) The effects of such additive organic compounds on n-dotriacontane, on crystalline paraffins or on a mixture of various hydrocarbons are not the same. In the case of the latter, the tips of the carbon chain in the crystal lattice are arranged in disorder, with a few side-chains; therefore, the crystal growth of the paraffin is believed to be inhibited and then the formation of fine crystal grains occurs.

7) The additive organic compounds wrap up paraffin molecules in the crystallization of paraffin, and the process from the formation of the crystal lattices to the growth of large crystals is so inhibited that the crystal growth is prevented. Crystallization seems to be partially prevented, and micro-crystallization or needle crystallization of small tabular crystals occurs.
Determination of Uranium in Thorium by X-Ray Fluorescent Spectroscopy. The Organometallic Precipitation Method
Authors: Hirokawa Kichinosuke , Gotô Hidehiro
Published: July 2006

A method for the determination of a small amount of uranium in thorium using the separation method with precipitation, combined with X-ray fluorescent spectroscopy, was investigated. About 100 μg. of uranium in thorium could be determined simply and rapidly by using alizarin blue as the precipitant for uranium and EDTA as the masking reagent for thorium.
Spectrophotometric Studies on the Kinetics of Decomposition of Tetramethylmurexide in Acid Medium
Authors: Chaturvedi R K
Published: July 2006

Kinetics of the decomposition of tetramethylmurexide in acid solutions have been investigated spectrophotometrically by following the absorption at λ=530 mμ. The optical density of tetramethylmurexide at this wavelength has been shown to obey Beer’s law with a value of 1.464×104 for the Beer’s constant. The change in the optical density with time of tetramethylmurexide solutions in presence of hydrochloric acid has been shown to obey a first order law and from these data the rate constants of the reaction have been computed at different temperatures in the range 25∼45°C. These data have been employed to obtain quantities such as energy and entropy of activation etc. and the Arrhenius frequency factor; the comparison of this last has been made with the collision theory. The possible mechanism of the reaction has been discussed.
High-kinetic Energy Fragment Ions from Aliphatic Hydrocarbons under Electron Impact. III. Nine Hydrocarbons Ranging from C2 to C4
Authors: Tsuchiya Toshikazu
Published: July 2006

Fragment ions produced by electron impact with excess kinetic energies from into nine hydrocarbons ranging from C2 to C4 have been investigated. Fragment ions of a higher mass number could not be measured. The decomposition mechanism of propylene has been explained by the mechanisms proposed by Hustrulid and by Mohler et al. To explain, the decomposition of other molecules, reactions producing ions with excess kinetic energy as well as neutral fragments must also be taken into consideration.
The Electronic Spectra of Nitrones and the Solvent Effect on Them
Authors: Kubota Tanekazu , Yamakawa Masumi , Mori Yutaka
Published: July 2006

The ultraviolet spectra of nitrones, the configurations of which were assumed from their dipole moments and chemical reactivities, and their related compounds have been measured in various solvents. The following results have been obtained:

(1) Nitrones show a characteristic strong π-π* band in the 280∼370 mμ region as well as one or two additional bands with a relatively low intensity in the 200∼260 mμ region. The molecular extinction coefficient (ε) of the former is about 20000. The decrease in intensity of the π-π* band is observed in the spectra of the sterically-hindered compounds.

(2) These bands always show a blue shifs with the increasing polarity of the solvent. The general rule of solvent effect on heterocyclic N-oxides applies also to nitrones, the conjugated N-oxide band of which has the same property as that of heterocyclic N-oxides.

(3) It has been confirmed by ultraviolet and infrared spectra that the formation of a hydrogen bond such as N→O…H (solvent) plays an important role in this blue shift phenomenon.
The Synthesis and the Physical Properties of Normal Higher Primary Alcohols. V. Thermal and X-Ray Studies of the Polymorphism of Alcohols of Odd Carbon Numbers from Undecanol to Heptatriacontanol
Authors: Watanabe Akira
Published: July 2006

On the phase transition of n-higher alcohols with odd carbon atoms from undecanol (C11) to heptatriacontanol (C37), thermal analyses and X-ray pattern measurements were made, with the following results:

1. Tridecanol (C13) shows an irreversible transition which appers only on cooling. A reversible transition sets in at pentadecanol (C15) and continues to the end member of the series (C37).

2. X-Ray pattern measurements indicated that, in the alcohols up to nonacosanol (C29), the transtition is β to α, while in the alcohols above C29 the transition is γ2 to α.

3. Presumably, the γ2 to α transition is gradual.

4. The properties of the α forms change gradually with an increase in the chain length.

5. The results of the present study and those of previous studies with the even series have been discussed from the configurations of the β and γ1 forms, as determined by X-ray structure analyses.