bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies on the Gas-Liquid Interface by Surface Potential Measurements III. The Surface Aging of the Solutions of the Long-chain Dibasic Acids
Authors: Hotta Hiroshri , Isemura Toshizo
Published: July 2006

The surface aging of the solutions of some ω,ω′-dicarboxylic acids was investigated by measuring the surface tension and surface potential, in a function of time. Only the slow adsorption process was studied in the present experiment. Adipic, suberic, and azelaic acid reached readily an equilibrium. Sebacic acid showed considerable surface aging. The mechanism of adsorption was assumed in the light of kinetic molecular theory, and the free energy of activation for adsorption was calculated. We obtained the free activation energy, 17.5-17.9 Kcal. for suberic acid, 18.0-18.5 Kcal. for azelaic acid and 13.8 Kcal. or more than this for sebacic acid. Free energy of activation for adsorption was increased to some extent with the surface concentration of already adsorbed solute molecules and consequently, for a certain solution, with the surface age.
The Spatial Configurations and the Ultraviolet Absorption Spectra of the Stilbene Derivatives
Authors: Suzuki Hiroshi
Published: July 2006

(1) With certain simple assumptions, calculations based on the molecular orbital method have been performed to assess the quantitative relations between the degree of the deviation from the coplanarity of the molecular configuration and the ultraviolet absorption spectrum as well as the resonance energy for the stilbene derivatives.

(2) New measurements of the spectra of the several stilbene derivatives have been carried out.

(3) By these calculations and the measurements of the spectra, it has been clarified that the absorption maximum is shifted progressively toward shorter wave lengths with the increasing angle of twist of the phenyl groups out of the plane of the ethylenic linkage.

(4) Further, from the results of these calculations and the observed position of the absorption maximum, it is possible to deduce the adequate values of the angle of twist and the resonance energy for any stilbene derivative.

(5) It has been shown that the absorption spectra for the trans isomers and those for the cis isomers of the stilbene derivatives from two groups quite distinct from each other in hat the former shows a larger moleculart extinction coefficient than the latter. On the basis of this fact, the assignements of the geometrical configurations have been determined for some stilbene derivatives.

(6) The experiments on the geometrical isomerization of α, α’-dimethylstilbene by heat have been carried out and the results have been carried out and the results have been interpreted, based on a consideration of the spatial configurations of the two isomers.
Dichroisms of Benzene Rings. III. The Dichroism of m-Nitronitrosobenzene Monomer
Authors: Nakamoto Kazuo
Published: July 2006

Absorption spectra of m-nitronitrosobenzene monomer in crystalline state as well as in solution have been measured quantitatively in the visible and the ultraviolet regions. In its π-band of the ultraviolet region, the general rule about the π-band of the benzene ring was found to hold also for the present case. In regard to the nitroso band of the visible region, the absorption by linearly polarized light with the electric vector vibrating perpendicular to the C–N–O bond was hyperchromic to the absorption by the light with those vibrating parallel to it. This result suggests that the green colour of m-nitronitrosobenzene is due to the electronic transition polarized perpendicularly to the C–N–O bond.
Researches on the Polarographic Diffusion Current. III. Higher Order Approximation of the Ilkovi\u{c} Equation
Authors: Kambara Tomihito , Tachi Isamu
Published: July 2006

Starting from the integral equation for the thickness of diffusion layer at the spherical electrode, a new equation for the polarographic diffusion current is derived and discussed.
Physicochemical Properties of the Surface of Aqueous Solutions. III. Mechanical Behavior of Surface of Micellar and Macromolecular Solution
Authors: Sasaki Tunetaka , Kimizuka Hideo
Published: July 2006

1. A torsion ring method using a suspension wire of low torsion constant was employed for the measurement of a surface viscosity and rigidity of aqueous solutions.

2. The mechanical behaviours of the surfaces of the solutions of saponin, polyvinyl alcohol, crystal violet and horse serum albumin aged for one hour were analysed and expressed using mechanical models. The corresponding rigidity and viscosity were estimated.

3. The mechanical models observed were the Newtonian flow, non-Newtonian flow, Maxwell model with Newtonian or non-Newtonian flow, Voigt model, and three para-meter model consisting of a series combination of a spring and a Voigt element.
The Crystal Structure of Trans-dichloro-diethylenediamine-cobalt. (III). Chloride Hydrochloride Dihydrate, [Coen2Cl2]Cl·HCl·2H2O
Authors: Nakahara Akitsugu , Saito Yoshihiko , Kuroya Hisao
Published: July 2006

The crystal structure of trans-dichlorodiethylenediamine-cobalt (III) chloride hydrochloride has been determined using the rotation method (Fe Kαλ=1.937 a.). The substance crystallizes in a monoclinic lattice with two formula units in the unit cell, the dimensions of which are a= 10.68 a., b=7.89 a., c=9.09 a. with β=110°26.

The determined structure seems most easily described as consisting of layers of [Coen2Cl2]+ ions parallel to the plane (100) and those of Cl−, H2O and H+. Two chlorine atoms are co-ordinated to a cobalt atom in trans-positions. The line joining them is perpendicular to the plane in which four nitrogen atoms are found to lie. The dimensions of a complex ion are given. The water molecules probably form a group [H2O···H···H2O]+ together with a proton, O···O distance being 2.66 a. These groups are located between them. The dichroism of the crystal is, discussed on the basis of the determined structure.
Notes on The Polymer-Mixed Solvents System. I The refinement of the free energy expression
Authors: Kawai Toru
Published: July 2006

The free energy expression derived by Scott for the polymer-mixed solvents system are refined and amplified, removing the assumptions which are not always applicable to the actual cases, although it was introduced by him for the sake of simplicity.

Owing to scantiness of the available data and to difficulties of exact, calculation, the phase diagrams of the system using the results obtained are not given here. Determination of plait points and the problems in the osmotic pressure measurement in mixed solvents will be discuss d elsewhere. Here, we confined ourselves to formulate the free energy expression for various systems also involving the systems in which one or two of the constituents are associated liquids as a special case where the assumption (b) is far from true. Application of the result obtained to some problems-in viscosity, osmotic pressure, and swelling phenomena will be presented in the following-articles.

This paper was presented at the Annual Meeting of the Tokyo Institute of Technology, where the treatment of associated liquids was discussed with particular reference to the applicability of the above methods to the thermodynamic problems of association.

In the writer’s opinion, the generality of the thermodynamic function derived here in the application to equilibria involving transformation between various “polymeric” species of the associated liquid may be accessible when the volume effect of the associated liquid on the entropy term in these systems must be encountered. Obviously the Flory-Tobolsk y-Bratz treatment is applicable only to the linear “polymer” such as alcohol, and we may go too far to say that our treatment is also-applicable to the three dimentional “polymer”-Our treatment is supposed, however, to be not far from true even in such a case, since the entropy of mixing in the above systems containing associated liquids as one or two components was formulated on the assumption that the submolecules of the “polymer” are distributed at random, i. e., this corresponds to the Bragg-Williams approximation.
On the Vapor Pressure of Liquid Mixture
Authors: Kurata Michio
Published: July 2006

(1) The kinetic method was applied to the vapor pressure of regular solution; the result being in agreement with that of the statistical method.

(2) New semi-empirical equations having simple form were derived for the vapor pressures of binary and ternary mixtures of liquids and satisfactory agreements of these equations with the experimental data were illustrated in regard to about 20 examples.
On the Thermal Dissociation of Organic Compounds. III. The Dissociation of Ester Linkage in Phenylcarbaminic acid phenylester in Butyric acid.
Authors: Hoshino Toshio , Mukaiyama Teruaki , Hoshino Hiroko
Published: July 2006

(1) The rate constant and the activation energy of thermal dissociation of phenylcarbaminic acid phenylester in butyric acid are determined.

(2) It has been made clear on the basis of reaction mechanism that dissociation of ester linkage requires larger activation energy than that of urea linkage.
Dipole Moments of Methyltropolones and their Bromoderivatives
Authors: Kurita Yukio , Mizuno Toshikuni , Mukai Toshio , Kubo Masaji
Published: July 2006

The dipole moments of three methyltro-polones and their bromoderivatives were measured in benzene solution at 25° or 30°. The values obtained were compared with the theoretical data for the moments of these compounds with substituents at various presumed positions. The final decision of the position of substitu-ents were made as shown in Table 3.
Studies on Pyrethrins The Synthesis of Some β-Keto Esters
Authors: Matsui Masanao , Yamaguchi Tokuji , Kato Takeaki , Funazo Giichi
Published: July 2006

A new procedure for preparing β-keto esters from methyl ketones, sodamide and diethyl carbonate using these reagents in the molar ratio of 1:3:3 is reported. The yields of β-keto esters approach to those of the preparation using sodium hydride as condensing agent. Furthermore, some cyclopentenolones were prepared from the β-keto esters synthesized by this-procedure.
Magnetic Susceptibilities of Reduced and Oxygenated Hemerythrins
Authors: Kubo Masaji
Published: July 2006

The magnetic susceptibilities of reduced and oxygenated hemerythrin solutions of the same concentration were measured by a Gouy magnetic balance at 25°. The susceptibility of the reduced solution was found to be higher than that of the oxygenated one, indicating a paramagnetic contribution of iron atoms in the reduced molecule. With the assumptions that the four groups acting as oxygen combining centers in the molecule are equivalent to one another and that they are magnetostatically independent, the number of unpaired electrons in the group was calculated to be twelve in the reduced state and zero in the oxygenated preparation. In the reduced state the bonds of the iron atoms are ionic or ion-dipole type in nature. A profound change in the electronic structure takes place when oxygen molecules are combined with the hemerythrin molecule. An oxygen molecule not only loses its own paramagnetism, but also affects all three iron atoms in the group in such a way that the bond type is essentially covalent. These iron atoms are supposed to be coupled with each other in a polynuclear complex so as to be able to transmit the effect of the change of electronic state directly to the others.
Electron Diffraction Investigation on Tropolone
Authors: Kimura Masao , Kubo Masaji
Published: July 2006

The molecular structure of tropolone was studied by the electron diffraction method. The most plausible model was found to be a plane regular heptagon form with C-C distance 1.39 A. long and C-H distance 1.10 A., having two slightly different C-O distances, i.e., C-O =1.34 A. and C=O=1.26A.
Determination of Small Quantity of Pentosan in Cellulosic Materials
Authors: Abe Toru , Matsuzaki Kei , Hatano Akira , Sobue Hiroshi
Published: July 2006

1. For the estimation of a small quantity of pentosan in cellulosic materials, an improvement of phloroglucin method and colorimetry with aniline were investigated on mixtures of glucose and xylose, and the results were compared with brornate, the usual phloroglucin and barbituric acid methods.

2. Treatment of the undried phloroglucide with alcohol remarkably removes the influence of hexosan on pentosan determination but it is not complete. As the solubility of the furfural-phloroglucide increases with phloroglucin added, it is desirable to increase the amount of the latter to twice the theoretical.

3. Colorimetry with aniline is superior to other methods. The color reaction is stable at low temperatures.

4. Pentosan contents of some cellulosic materials, such as rayons, pulps and cellulose acetates, are tabulated.
Polarographic Behavior of Cinnamic-, Styrylacetic-and Crotonic- Acids
Authors: Ono Shin-ichi , Hayashi Tadao
Published: July 2006

1) In neutral solution, both styrylacetic acid and crotonic acid gave a single wave (ca. −1.6–−1.7v.), on the other hand cinnamic acid gave a well-defined two-step polarographic wave (ca. −1.5v. and ca. −2.0v.) corresponding to the reduction of carbon-carbon double bond. The half-wave potentials of cinnamic acid were shifted by the presence of divalent cations.

2) Ethyl cinnamate gave a single wave (ca. −1.7v.) in neutral solution, but in alkaline solution it gave two waves (ca. −1.7v. and ca. −2.0v.). The first wave was observed to diminish by the hydrolysis in alkaline solution.
Dipole Moments of Tropone, 2-Phenyltropone, Tropolone Methyl Ether and their Derivatives
Authors: Kurita Yukio , Seto Shuichi , Nozoe Tetsuo , Kubo Masaji
Published: July 2006

The dipole moments of tropone, 2-phenyltropone, tropolone methyl ether and their derivatives were measured in benzene solution at 25°. The increase of moment of tropone over that of cycloheptanone was adequately explained by mesomeric effect and an additional effect due to the formation of cycloheptatriene ring. The latter effect was supported by the theoretical moment for heptafulvene. The moments of various derivatives were compared with the theoretical data. The agreement between them confirmed the correctness of the position of substituents in these compounds already determined or inferred from the standpoint of organic syntheses. The apparent moment of tropolone methyl ether hydrate indicates that in benzene the hydrate dissociates into three separate molecules.
The Separation of Isotopes by Countercurrent Gaseous Exchange Column. I. Transport Equation and Over-All Separation
Authors: Kigoshi Kunihiko
Published: July 2006

The theoretical treatment of the countercurrent gaseous exchange method for the separation of isotopes isdeveloped here. The equation of transport is derived with the assumption that the equilibrium of the isotopic exchange reaction holds only in the sharply defined region in which temperature is higher than Tb. An appropriate approximation leads the transport equation to one which is formally similar to the transport equation of thermal diffusion column. The mechanism of isotope enrichment by countercurrent gaseous exchange method is discussed using the transport equation. The equilibrium separation factor is also derived from the transport equation.
The Separation of Isotopes by Countercurrent Gaseous Exchange Column. II. Experimental Tests of the Theory
Authors: Kigoshi Kunihiko
Published: July 2006

The separation of carbon isotope C14 by the countercurrent gaseous exchange method has been studied using a hot wire type thermal diffusion column. The isotopic exchange reaction employed for the experiments was a reaction between carbon dioxide and carbon monoxide. The separation column was constructed with a water-jacketed glass tube of 150 cm. long and 12.7 mm. in diameter. An electrically heated platinum wire was placed at the center of the tube, and its temperature was measured by thermal expansion of the wire. The column was filled with carbon dioxide. A converter was put at the bottom of the column in order to reduce carbon dioxide to carbon monoxide. The concentration of C14 at the bottom of the column was measured by a Lauritsen type electrometer. The over-all separations at the equilibrium states were observed for the various filament temperatures between 570 and 1170°C. The dependence of over-all separation on the filament temperature and initial isotopic transports were in reasonable agneement witd theoretical estimates.
Researches by the Chromatography. IV. On the Impurities of Cotton Cellulose and Wood Cellulose
Authors: Hatano Akira , Sobue Hiroshi
Published: July 2006

Egyptian cotton linters, its purified linters, Japanese red pine and beech were hydrolyzed. It has been shown by paper chromatography that the hydrolyzates contain certain monosaccharides, uronic acids and amino acids.

Raw cotton linters have been found to contain, besides glucose, about 1,5% arabinose, and a small amount of glactose, glucuronic acid and galacturonic acid.

The amounts of the various amino acids contained in the hydrolyzates of raw cotton linters, red pine and beech are somewhat different from each other, but the kinds of the amino acids are the same and they are assumed to be cystine, aspartic acid, aspargine, arginine, glutamic acid, alanine and tryptophane.

Glutamic acid changes to pyrrolidoncarboxylic acid in the process of hydrolysis of the materials and shows special colorizations reactions with ninhydrin and bromo-phenol-blue indicator.

Purified cotton linters and sulfate rayon pulps treated by alkali cooking do not contain any amino acid, but sulfite rayon pulps contain cystine, alanine and pyrrolidoncarboxylic acid.
Studies on the Molecular Structures of Gaseous Acetamide and N-methylacetamide by Electron Diffraction
Authors: Kimura Masao , Aoki Michiro
Published: July 2006

1) The molecular structures of acetamide and N-methylacetamide were determined using electron diffraction by gases. The results were compared with the values obtained from X-ray diffraction by crystals.

2) C=O distance is longer in the crystalline state than in the gaseous state, while C–N distance is shorter in the crystalline state than in the gaseous state. This is due to the hydrogen bond which is absent in the gaseous state but exists in the crystalline state.
Wettability of Solid Surface. VI. The Effects of Metallic Cations on Stearic Acid Built-up Film
Authors: Inaba Ayako
Published: July 2006

1. Wettability of mixed built-up film of stearic acid and barium or calcium stearate decreased with the number of layers, the advancing contact angle tending to the value of about 115°. The difference between θa and θr of built-up film was larger than that of solidified surface.

2. X-film and Y-film of barium or calcium stearate prepared occasionally at almost the same condition showed the same wettability. Increase of barium or calcium content in the film was considered to result in the wettability decrease.

3. Of the three types of metallic ion classified according to the influence on wettability of stearic acid, the following two were studied precisely.

(a) Ions of the type III, forming relatively simple stoichiometric compound with stearic acid, the stearates being able to overturn themselves easily in the surface, and the wettability changing with the condition. (Ba, Ca)

(b) Ions of the type II, forming a network of a complex structure with stearic acid, which overturn themselves with difficulty in the surface and their wettability does not change with the condition.

II—1. Ions, rapidly forming network and render the surface hydrophilic tempolarily. (Al, Cu)

II—2. Ions, slowly forming network and rendering the surface hydrophobic (Hg).
Studies of Molecular Structures by Electron Diffraction. II. The Structures of o-,p-Fluorochrolobenzene and p-Fluorobromobenzene
Authors: Oosaka Hajime , Akimoto Yûmi
Published: July 2006

The molecular structures of o-,p-fluoro-chlorobenzene and p-fluorobromobenzene have been investigated by the electron diffraction method. The following values have been obtained by the analysis based on coplanar structures; C–F=1.30±0.03Å, C–Cl=1.68±0.02Å for p fluorochlorobenzene; C–F=1.30±0.03Å, C–Br=1.87±0.02Å for p fluorobromobenzene; and C–F=1.30±0.03Å, C–Cl=1.69±0.02Å, and <C1–C2–F=<C2–C1–Cl 121±1° for fluorochlorobenzene. C–C=1.40Å, C–H=1.04Å are assumed throughthe analysis.
An Improved Accurate Film Balance
Authors: Inokuchi Kiyoshi
Published: July 2006

An improved apparatus and technique for measuring low film pressures, have been described. Although the apparatus bears resem-balance to the Marcelin’s balance, the following improvements were achieved in order to enable the low pressure measurement to be generally accessible.

(1) The main construction is laid beside the trough, unlike the usual apparatus whose construction is placed above the surface of water. This design is well suited for minimizing the chance of contamination which more or less occurs on the surface during assembling or operation of the instrument.

(2) Since one of the disadvantages of this type balance lies in the possibility of leakage at the solid-thread connections, especially at the connection between rims of the trough and thread, properly designed metal blocks are used to ensure the perfect connection with simple technique.

(3) An important point in the design of the apparatus is that it should be capable of easy dismantling and reassembling, so that the operation of cleaning can be easily conducted. This requirement is satisfied by the use of a carrier for the float and threads which is easily removable from the main construction of the apparatus.

(4) The float is so designed that the connection between the float and the supporter is an independent bearing, when the float is allowed to be in contact with the water surface. Owing to such construction, the change of water level during run does not matter.

(5) The optical system, which makes the deflection of the floating barrier visible, is equipped with the apparatus. Since the frosted glass, on which the light image is projected, lies just beside the reading scale, observations can be made with no unnecessary delay.

These designs meet well the requirements for measuring low film pressures. Continuous use for eighteen months has shown the apparatus to be very convenient and reliable.
Sterols and Other Unsaponifiable Substances in the Lipids of Shell Fishes, Crustacea and Echinoderms. XII. Occurrence of Δ7-Cholestenol as a Major Component of the Sterol Mixture of Chiton
Authors: Toyama Yoshiyuki , Tanaka Tatsuo
Published: July 2006

Sterol mixture of the chitons caught around Osaki-Shimojima Island in the Inland Sea of Seto contains predominantly Δ7-cholestenol, the acetate of which is easily obtainable in a pure state by several recrystallizations of the acetate of sterol mixture. From sterolfree components of unsaponifiable matter, a saturated fraction, possibly consisting of chimyl and batyl alcohols, was separated.
Surface Chemistry of Synthetic Protein Analogues. III. On the Surface Viscosity of Monolayers of Non-electrolytic Synthetic Polypeptides
Authors: Isemura Toshizo , Hamaguchi Kozo
Published: July 2006

The surface viscosity of the spread monolayers of synthetic polypeptides with non-electrolytic side chains was investigated in relation to the surface area and to the surface pressure. If the length of a side chain becomes longer than six carbon atoms, the limiting area becomes larger with the length of the side chain. Polypeptide with no side chains or very short ones such as glycinealanine copolymer might be changed to α-configuration from “extended” β-configuration merely by compression. The ease of transition from one configuration to another corresponds to the discovery by Elliott in bulk solution with poly-alanine. αII→β transformation of poly-γ-methyl-l-glutamate which had been reported in the previous paper, was observed also by the surface viscosity measurements. The difference of the nature of films of optical active and of racemic polypeptide was investigated. The polypeptide consisting of single optical isomeride was able to be more closely packed in the film than that of racemic. Our discovery by surface pressure measurement that the polymer of ε-aminocaproic acid, namely, amilan is not adequate as the model of protein, was again confirmed from the study of surface viscosity.
Studies on the Oxy-acid Phosphors. II. Vanadate Phosphors (Part 1)
Authors: Kotera Yoshihide , Sekine Tadao
Published: July 2006

The preparations and the measurements of the general characteristics of the pyrovanadate phosphors have been carried out. When excited by the ultraviolet, zinc pyrovanadate shows a relatively strong emission. Strontium pyrovanadate emits white color on irradiation by the cathode ray. Magnesium, calcium, barium, and cadmium salts show emission by the various methods of excitation. It has been suggested that pyrovanadate phosphors belong to the unactivated type similar to the tungstate phosphors.
Dipole Moments of Cyclic Siloxanes and Thiosiloxanes
Authors: Kurita Yukio , Kondo Michio
Published: July 2006

The dipole moments of several cyclosiloxanes and cyclothiosiloxanes were measured in benzene solution. The values obtained are: Hexamethyldisiloxane (I), 0.80D; octamethylcyclotetrasiloxane (III), 0.67D; hexamethylcyclotrithiosiloxane (V), 1.03D. The atomic polarizations obtained are: hexamethylcyclotrisiloxane (II), 10.9 cc.; tetramethylcyclodithiosiloxane (IV), 9.0 cc. The unexpectedly small bond moment of Si-O (1.55D) can be explained by the double bond character of the bond. For the configuration of (III) and (V), it is impossible to draw any definite conclusion from the study of the dipole moment alone.
Molecular Structure Investigations by Electron Diffraction Method. I. The Molecular Structures of Isopropyl Alcohol and -Chloride
Authors: Yamaha Mashio
Published: July 2006

The molecular structures of isopropyl alcohol and -chloride have been investigated by the electron diffraction method. The atomic distances, C-O : 1.45±0.03Å, C-C : 1.54±0.02Å and valence angles,<CCC≈<CCO : 110°±2.5° are determined for the former molecule, and distances C-Cl : 1.76±0.02Å, C-C : 1.55±0.02Å and angles <CCC≈<CCCl : 109.5±1.5° for the latter.

The approximate thermal vibration factors have been taken into account for the determination of the best molecular models. The rotational configurations of methyl groups have been considered, but the equilibrium position of two methyl groups cannot be determined conclusively, in spite of the fact that this effect upon the intensity curves are not to be ignored in the case of isopropyl alcohol molecule.
The Studies of Molecular Structures by Electron Diffraction. III. The Structures of m- and p Difluorobenzene
Authors: Oosaka Hajime , Sekine Hiroshi , Saito Takahide
Published: July 2006

The C–F distances of m-difluorobenzene and p-difluorobenzene are investigated to be almost equal, 1.30±0.03 Å.
The Condensations of Furfural with Acetylacetone and Ethyl Propionylacetate
Authors: Midorikawa Hiroshi
Published: July 2006

3-Acetyl-4-(2-furyl)-3-buten-2-one (I) and ethyl α-propionyl-2-furanacrylate (V) were obtained by the condensations of furfural with acetylacetone and ethyl propionylacetate by piperidine, respectively.

3-Acetyl-4-(2-furyl)-3-buten-2-one (I) was oxidised by sodium hypochlorite to furfurylidenemalonic acid (II), and, on refluxing with alcohoric hydrochloric acid and subsequent hydrolysis, gave β-(4-acetyl-5-methyl-2-furyl)-propionic acid (IV).

Ethyl α-propionyl-2-furanacrylate (V) gave γ,ζ-dioxopelargonic acid (VI) by refluxing with alcoholic hydrochloric acid and subsequent hydrolysis.

The dioxocaboxylic acid (m. p. 83∼84°), obtained by the ring-opening of the furfurylidene ketone (b.p. 126°/19 mm.) in alcoholic hydrochloric acid which was considered to be 1-(2-furyl)-1-penten-3-one (VII) in the previous reports, was identical with this γ,ζ-dioxopelargonic acid (VI). It was confirmed, therefore, that the ideas in the previous reports6) was correct.
Influence of Substituent Groups on Nuclear Reactivity in Formation of Substituted Biphenyls through Reactions of Aromatic Diazo and Cognate Compounds with Aromatic Liquids. III. The Substitution of Nitrobenzene by the p-Anisyl Radical
Authors: Simamura Osamu , Migita Toshihiko
Published: July 2006

The decomposition of N-nitroso-p-acetanisidide in nitrobenzene at room temperature yielded 4-methoxy-4′-nitrobiphenyl and 4-methoxy-2′-nitrobiphenyl in a ratio of 1: 1. 6. From the result of a similar experiment in a mixture of nitrobenzene and benzene, which compete for the p-anisyl radical produced from N-nitroso-p-acetanisidide, the relative reactivities of the ortho, meta and para positions of nitrobenzene towards the p-anisyI radical are found to be 7.24, 0, and 8.95, respectively, the reactivity of one nuclear position of benzene towards the same radical being taken as unity.
On the Relation Between Viscosity and Critical Micelle Concentration of Detergent Solutions. II. Viscosity and Diffusion Coefficient of Non-ionic Detergent Solutions
Authors: Okuyama Haruhiko , Tyuzyo Kiyoshi
Published: July 2006

(1) Partial specific volume, viscosity, diffusion coefficient of the aqueous solutions of non-ionic detergents are measured.

(2) ηsp/C becomes minimum at CMC and this concentration is quite consistent with the concentration where diffusion coefficient varies suddenly. It is interesting that this is the common phenomenon for ionic and non-ionic detergents.

(3) The form of ηsp0/C0 vs C0-Curve is analogous to that described in the first report and the second CMC (C2) is also obtained but some abnormality occurs in the part of low concentrations for the substance of which CMC is high.

(4) After the completion of micelle formation, diffusion coefficient stays constant and is independent of concentration which suggests that micellar volume is constant and independent of concentration.

(5) The influence of an electrolyte on the diffusion is examined and a new idea of the mechanism of “salting out” is proposed.

(6) Micellar molecular weight is calculated from the diffusion coefficient assuming that a micelle is spherical.
Studies on the Degradation of Yeast Ribonucleic Acid by Lanthanum Hydroxide. On the Existence of a Resistant Fraction
Authors: Shimomura Michio
Published: July 2006

1. Yeast ribonucleic acid is, as reported in the previous paper, hydrolysed almost completely into nucleosides and inorganic phosphate by lanthanum hydroxide, but the remaining fraction is considerably resistant to the action of the hydroxide.

2. Purine-bound ribose/RNA-p ratio of the resistant fraction is about 1.

3. Even after the treatment with ribonuclease, dephosphorylation of the resistant fraction by lanthanum hydroxide is not easy.

4. The ribonuclease resistant fraction is dephosphorylated by lanthanum hydroxide as easily as ribonucleic acid itself.
Stoichiometric Investigations of the Liquid State. I. The Relation between the Sound Velocity and the Chemical Structure. (1). The Physical Meaning of the Molar Sound Velocity of the Unassociated Liquid
Authors: Tyuzyo Kiyoshi
Published: July 2006

(1) The physical meaning of Rao’s molar sound velocity (K) is given.

(2) It is found that K-values calculated from the theory are independent of temperature in the case of normal liquids.

(3) It is found that the calculated K-values are satisfactorily coincident with the observed ones for normal liquids (aliphatic and aromatic hydrocarbons, ether, acetone, esters, alkyl halides).
Studies on the Condensation Polymers of Aromatic Acetoxy Carboxylic Acids
Authors: Hasegawa Hajime
Published: July 2006

We carried out a fundamental research for synthesizing high polymers of aromatic acetoxy carboxylic acid, and observed the influence of the position of the acetoxy group, and found that m-acetoxy benzoic acid, 3, 5-diacetoxy benzoic acid and 2, 4-diacetoxy benzoic acid, are superior as the monomer for the preparation of high polymers of aromatic acetoxy carboxylic acid.
Surface Chemistry of Synthetic Protein Analogues. IV. On the Monolayers of Electrolytic Synthetic Polypeptides, Poly-l-Glutamic Acid and the Copolypeptide of l-Lysine, l-Leucine and l-Glutamic Acid
Authors: Isemura Toshizo , Hamaguchi Kozo
Published: July 2006

The surface pressure and surface viscosity of the spread monolayers of the copolypeptide of l-lysine, l-leucine and l-glutamic acid and of poly-l-glutamic acid were measured in relation to substrate pH.

The copolypeptide of l-lysine, l-leucine and l-glutamic acid.—The F—A curves in the range of pH 5.8 and 9.4 were of condensed type, but at both outsides of this pH range they were of expanded type. The area at constant pressure or surface viscosity against pH curves were of W-shape and a maximum appeared at pH 7. That the iso-electric point of the copolypeptide may lie at pH 7 was concluded from the observations of the monolayer properties. The W-shaped curve could be interpreted in terms of the ionization degree of amino and carboxyl groups. At the isoelectric point, pH 7, the surface viscosity became maximum. This is in contrast to the bulk viscometric behaviour of polyampholytes.

Poly-l-glutamic acid.—The area at constant pressure or surface viscosity and the pressure at constant area decreases rapidly if the pH of the substrate exceeds 4.6. This fact corresponds to the viscometric behaviour of electrolytic polypeptides in solution, i. e., when the elongation of a molecule by the electrical repulsion of ionized groups occurs, the rapid increase in viscosity and in solubility appears in solution and at monolayer, respectively.
Investigation on the Molecular Structure of Monochloroacetamide by Gas Electron Diffraction and Dipole Moment
Authors: Kimura Masao , Aoki Michiro , Kurita Yukio
Published: July 2006

1) The structure of monochloroacetamide was determined by gas electron diffraction as follows: C–Cl = 1.75Å, ∠=113°, N···Cl=2.89Å, and the twisted angle from the cis configuration is about 15°. The structure of the part corresponding to acetamide is nearly equal to that of aceta-mide with an intermolecular hydrogen bond. This suggests that a monochlorocetamide molecule has an intra molecular hydrogen bond.

2) The dipole moment of monochloro-acetamide was estimated to be 2.2D∼2.8 D from the measurement in benzene solution. The observed value was compared with the calculated one. The result agrees with that obtained by electron diffraction in regard to the position of C–Cl bond. The agreement becomes better if the effect of an intramolecuar hydrogen bond is taken into account.
Studies on Foams. VIII Effects of Alcohols on the Foaminess of Soap Solutions
Authors: Nakagaki Masayuki , Shinoda K\={o}z\={o}
Published: July 2006

Foaminess of soap solution increases with the increasing concentration up to the C.M.C., and then becomes nearly constant. In homologous series, K-C12 or K-C13 show the greatest foaminess at ordinary temperature. Foaminess of alcohol solution is much smaller than the soap solution. In homologous series of alcohols higher than C5-OH, the higher foams poorer. For the mixed solution of two soaps, the foaminess becomes smaller when the ratio of lower soap is larger.

The effects of homologous series of alcohols on soap solution are measured and three types are observed: defoaming by solvent effect (by C2-∼C4-OH for K-C10) is observed at logCOH/Cs = 0∼2; foam promoting action (C5-∼C10-OH for K-C10 and C2-∼-C6-OH for K-C6) at logCOH/Cs = 3∼0: and defoaming by preferential adsorption (C11-OH for K-C10 and C8-∼C10-OH for K-C6) at log COH/Cs=\bar5∼\bar3. These three effects are correlated with each other.
Enzymatic Reduction of Aromatic Nitro, Nitroso and Hydroxyl amino Compounds
Authors: Yamashina Ikuo , Shikata Shogo , Egami Fujio
Published: July 2006

1) A cell-free enzyme preparation of a halotolerant bacterium activates aromatic nitroso and hydroxylamino compounds as well as nitro compounds and accelerates their reduction by hydrogen donator systems.

2) The enzymatic reduction of nitroso and hydroxylamino was more strongly inhibited by cyanide and azide than that of nitro.

3) Methylene blue, which can not be used as an intermediary hydrogen carrier in the case of nitro reduction, can be used in the cases of nitroso and hydroxylamino reduction.

4) From these facts, we have been led to the consideration that there exist special enzymes such as nitroso-reductase and hydroxylamino-reductase besides nitro-reductase.

5) Azoxy, azo, and hydrazo compound cannot be reduced by the enzyme preparation.

6) From the studies of reaction velocity and paper chromatography of the intermediates and the end products, we proposed a scheme concerning the enzymatic reduction of nitro to amino, namely:

(Remark: Graphics omitted.)
Alkylalkoxypolysiloxanes. I. Ethylethoxypolysiloxanes
Authors: Okawara Rokuro
Published: July 2006

(1) Ethylethoxypolysiloxanes have been prepared by a thermal reaction of ethylethoxychlorosilanes and ethyltriethoxysilane.

(2) Linear ethylethoxypolysiloxanes containing from 2 to 4 silicon atoms have been prepared and characterized.

(3) Certainly, a small amount of ethylethoxycyclopolysiloxanes were formed by the thermal reaction but they could not be isolated.
Rheology of Surface Films. III. A New Type of Surface Rheometer using Electromagnetic Driving Technique
Authors: Inokuchi Kiyoshi
Published: July 2006

In order to establish the standard set of surface rheometry, which involves the rheological measurement of films at liquid surface, a new type of surface rheometer was devised using electromagnetic driving technique. The advantage of this apparatus lies not only in its ease of operation and simplicity of construction, but also in its accessibility to various sorts of measurement. In addition, the wide range of measurement and remote control of operation provide a practical advantage for the experiment of surface films.
Sorption of Gases on Evaporated Nickel Films. I. Sorption of Oxygen
Authors: Oda Zenjir\={o}
Published: July 2006

While the sorptions of oxygen on the evaporated nickel films are very fast at the early stage and become slow at the later independently of the temperature, oxygen is suppoted to invade the interior even at the early stage of sorption. On the other hand, at the later stage the rate-determining step of low-temperature-sorption is different from that of room-temperature-sorption.
Studies on Dimethylglyoximo cobalt(III) Complexes. 1. The Preparation and Some Properties of Tris-(dimethylglyoximo)-cobalt(III)
Authors: Nakahara Akitsugu
Published: July 2006

Tris-(dimethylglyoximo)-cobalt(III) was newly synthesized by making use of dipotassium dimethylglyoximate. The crystals are quite stable in the atmosphere similarly to other so-called luteo-complexes, and orangeyellow in color. It is soluble in organic solvents, e.g., chloroform, alcohol and dioxane, as well as in water, but insoluble in benzene and acetone.

The absorption spectrum of this compound in aqueous solution was measured, and it was concluded that dimethylglyoxime is a considerably hypsochromic ligand.

Some discussions concerning the stabilities of bis-(dimethylglyoximo)-cobalt(III) complexes were given and they reached the following conclusions: (1) the distinguished stability of bis-(dimethylglyoximo)-derivatives is probably due to the O–H–O hydrogen bonds which are expected for the planar configuration of two dimethylglyoximic ions, and (2) the synthesis of tris-(dimethylglyoximo)-cobalt(III) can be successfully achieved only by interrupting the formation of those hydrogen bonds in the course of co-ordination of the ligands.
Reactivity of Coke. III. Effects of Some Metallic Additions on the Surface Area of Cokes from Humic Acid and on the Absolute Reaction Rates of the Coke-Carbon Dioxide System
Authors: Kawana Yoshio
Published: July 2006

The surface area of cokes from humic acid and metal-humates and the absolute reaction rates of these cokes to carbon dioxide at various temperatures have been determined by the same method and procedure as those described in the first paper.

The specific surface area of cokes from metal-humates are about two or five times larger than the coke from humic acid, and this increase is expected from the well-known fact that when carbonaceous materials are carbonized with inorganic salt an increase in the surface area is obtained.

The specific reaction rates per unit surface area Ka of these cokes and carbon dioxide can be expressed by an equation

K_a=A exp. (-E/RT),

and the values of A and activation energies E have been determined. The activation energies of cokes from humic acid, Ca- and Mg-humates are about 95 kcal./mol. and a large difference is not seen among them, but those of cokes from Fe-, Al- and Na-humates are about 25-40 kcal./mol. smaller than H-coke. The experimental values of A for cokes from humic acid, Ca- and Mg-humate are in satisfactory agreement with those expected from the application of the absolute reaction rates theory to the reaction mechanism already presented in the first paper, but those of A for cokes from Fe-, Al- and Na-humate are much smaller than expected from the theory. These results may be considered to indicate that the more complicated reaction must be occurring for cokes from Fe-, Al- and Nahumates. Calcium and magnesium impurities have effects of decreasing the specific reaction rates per unit surface area of the coke from humic acid to carbon dioxide and on the other hand, aluminium, especially iron and sodium impurities at lower temperatures have great effects of increasing the specific reaction rates. The effects of these sodium and iron impurities agree well with the earlier results and the present results also confirm that the catalytic effects of impurities in coke play an important role in the absolute reaction rates of the coke-carbon dioxide system, which was assumed in previous papers.

By considering the effects of metallic impurities on both the specific surface area of cokes from humic acid and the specific reaction rates per unit surface area of the coke with carbon dioxide, all metallic impurities investigated increase the relative reactivity of the coke from humic acid and for example, sodium impurities increase the apparent reactivity of the coke about 103 times at 700°C.
Thermionic Emission from Catalyst for Ammonia Synthesis. I. Electron Microscopic Images of the Catalysts
Authors: Uchida Hiroshi , Todo Naoyuki
Published: July 2006

The electronic images have been observed on 5 types of the catalysts for ammonia synthesis, which are different in promotercomposition. On heating the oxides from 750 to 900°C, the images of different kinds which were characterized by their respective promoters compositions appeared after a few minutes. On reduction, some of the images remained, while the others disappeared, and during the periods of five to thirty minutes of the reduction, the images turned to the respective characteristic ones again, sometimes being quite different from those of the oxides. On the additional observations, a part of the images weakened or disappeared and rather the homogeneous images over the whole sections became to be observed by raising thetemperature.

Comparing the image with the optical, the net work of the emission after the reduction corresponds to cracks on the section. When the microscopic structure of the section thoroughly polished and etched with hydrochloric acid is adopted for comparison with the above optical image, grain boundaries in the oxide always correspond to the cracks. Therefore, the electronic images on the oxide are not always related to the grain boundaries.

Qualitative explanations on respective promoting effect of alumina, lime and silica are yielded from view point of the electronic image.

It has been proved from the observations of the electronic as well as the optical images that there are the following 3 types of regions which are rich in potash, i.e. the grain boundaries, particular interfacial grains and some of the sub-grains into which the parent grains are divided. When references are made to the results of the activity for ammonia synthesis, surface area and etc., together with that by H. Kobayashi who has described that the activity is greatly enhanced by the larger amount of potash insoluble in water, the estimation shows that probably potash existing in the sub-grains above may most contribute to the activity for ammonia synthesis.
The Alternating Current Polarisation with Respect to Hetero-Pair Electrodes
Authors: Nagaura Shigeo , Sasaki Kazuo
Published: July 2006

1) We attempted to prove that the polarisation characters, being measured as to a whole cell, can be attributed to each single electrode. This attempt was verified by most of the experiments.

2) The above success may be one of the experimental justifications to use a simple series circuit as the equivalent circuit of a conductivity cell.

3) Discordant results appearing in “n/100 measurements” are to be studied in more details.
Deformation of the Regenerated Cellulose Fibers III. Deformation and Refractive Indices of Air-Dried Filament
Authors: Okajima Saburo , Hayama Shigeru
Published: July 2006

Deformation of the dried filament can be expressed in the term of the first theory of Kratky on the whole as in the case of swollen filament. And this behavior is not affected by the slight change of the spinning conditions of the filament such as the temperature and the composition of the cellulose solution. But in the case of the filament dried in the less humid air the orientation occurs more prominently in the early stage of the stretching but soon follows the above deformation mechanism.

This drying effect will illustrate the variation seen in the previous paper. Of course it is noteworthy that the value of l0d changes a few percent with the variation of the air humidity during measuring and, therefore, this factor must be taken into consideration when l0d and l2d are read under the different air conditions. Some of our older data are thought to contain small fuctuations due to this fact.
Studies on the Molecular Structures of Some Cyanuric Compounds by Electron Diffraction
Authors: Akimoto Yûmi
Published: July 2006

1. The molecular structure of cyanuric chloride and melamine were investigated by the electron diffraction. The following values were obtained by the analysis based on D3h symmetry of the molecules: C-Nr=1.33±0.02 Å, C-Cl=1.68±0.03 Å, and ∠Nr-C-Nr=125±3° for cyanuric chloride: C-Nr=1.34±0.01 Å, C-N0=1.37±0.03 Å, and ∠NrC-Nr=123±3° for melamine assuming No-H=1.04 Å, ∠C-No-H=∠H-N0-H=120°, and the coplanarity of all atoms.

2. Simple MO calculations were applied for both molecules as well as for sym-trichlorobenzene and sym-triaminobenzene. The resulted molecular diagrams were discussed together with the data obtained in the present experiment.
Polarographic Studies on Heterocyclic Compounds. II. Saponification of Isonicotinic Acid Methyl Ester
Authors: Nagata Yoshinosuke , Tachi Isamu
Published: July 2006

(1) Isonicotinic acid methyl ester gives a single reduction wave and the half-wave potential shifts to more negative potential with increasing pH.

(2) Isonicotinic acid methyl ester is saponified in the alkaline medium and the velocity constant of saponification is determined polarographically on the basis of the second order reaction equation.

(3) The velocity constant is scarcely influenced by the addition of neutral salts, but increases with rising temperature. The activation energy of saponification is calculated according to the Arrhenius equation.
A Physico-chemical Study on the Hydrolysis of Thorium Nitrate
Authors: Pan Kuan , Hseu Tong Ming
Published: July 2006

1) The dilution effect on the pH change in a dilute solution and in the presence of sodium perchlorate was followed by a glass electrode.

2) A linear relationship is held between pH and −logC. The curves plotting pH vs. −logC run parallel with each other at varying ionic strengths, and the slope is nearly equal to 1/2 by which the most possible existence of Th(OH)+3 is pressumed.

3) The equilibrium constants for ion species, ThOH+3 and Th(OH)2+2, are calculated stoichiometrically from the data of hydronium ion concentration observed and the total concentration of thorium nitrate.