bluuebunny/crossref_metadata_2025 huggingface dataset:
Analytical Chemistry by means of Oxalic Acid. II. On the Quantitative Analysis of Barium
Authors: Matsumoto Tamotsu
Published: July 2006

(1) Quantitative precipitation of barium as its oxalate hemihydrate was made possible by employing 50% alcohol as washing solution and by drying the precipitate at 100°—105°C. for 2 hrs.

(2) Sod. chloride, pot. chloride, pot. nitrate and amm. chloride produce little influence on this determination, while amm. nitrate positively effects the estimation.

(3) It was found that barium can be determined volumetrically by titrating with potassium permanganate the oxalic acid which is formed when the barium oxalate is decomposed with nitric acid.
On the Thermal Dissociation of Organic Compounds. II. The Dissociation of the Urea Linkage in Sym-dimethylurea, Asym-dimethylurea and Asym-phenylethylurea in Butyric Acid
Authors: Hoshino Toshio , Mukaiyama Teruaki , Hoshino Hiroko
Published: July 2006

(1) The rate constants and the activation energies of the thermal dissociation of symdimethylurea, asym-dimethylurea and asymphenylethylurea were determined.

(2) It was demonstrated that the substituents have great influence on the dissociation reaction.
Fractionation of Cellulose Acetate and Distribution of Non-Cellulosic Components between the Fractions
Authors: Matsuzaki Kei , Fukuhara Setsuo , Hatano Akira , Sobue Hiroshi
Published: July 2006

1. Three cellulose acetates from cotton linters, Kayaceta and a domestic pulp were fractionally precipitated from acetone solution with ethanol, and viscosity measurements in acetone solution and pentosan determinations by paper chromatography of the individual fractions were made.

2. Another acetate from Rayaceta was again fractionated into five fractions and viscosities in acetone and cupriethylene diamine solution and pentosan contents of the individual fractions were determined.

3. The results showed a close relationship between the initial acetone-insoluble fractions or in acetone haze-producing fractions and their pentosan content. These fractions include abnormal materials which show low viscosity (probably low D. P.) in cupriethylene diamine solution as well as in acetone. They are in-cluded much in the acetates from wood pulps.

4. It could not be decided whether these acetone-insoluble fractions were due to association by salt bridge effect of calcium ions between carboxyl or sulfuric half-ester groups, or due to the remaining structure of wood tissues.

5. The chain-length distributions of the cellulose acetates from wood pulp seem to be more heterogeneous than those from cotton linters.
The Relation between the Geometrical Configurations of Inorganic Complexes and their Absorption Bands. II. The Configurations of Two Isomers of Sodium Disulfono-tetrammine-cobaltiate
Authors: Shimura Yoichi
Published: July 2006

The visible and ultra-violet absorption spectra of Na[Co(NH3)4(SO3)2]·2H2O (brown salt) and Na[Co(NH3)4(SO3)2]·4H2O (yellow salt) have been measured. The results have proved that the SO3=-radical coördinates around the central cobalt (III) ion by the lone pair electrons of its sulfur atom, and that the brown salt has trans-configuration concerning the positions of the SO3=-radicals and the yellow salt cis-configuration.

The absorption spectrum of NH4[Co(NH3)4(SO3)2]·3H2O (dark brown form) has also been studied and it has been assumed that the salt is trans-isomer contrary to several investigators’ assignmints of cis-strusture.
Electrolytic Reduction of Aromatic Carboxylic Acids. II. Electrolytic Reduction of Cinnamic Acid
Authors: Ono Shin-ichi , Hayashi Tadao
Published: July 2006

The electrolytic reduction of cinnamic acid at a Pb, a Hg, a Hg-Zn or a Pt-Pt cathode in acid solution was studied.

It was found that the formation of bimolecular compounds depended on the nature of cathode materials and the condition of the reduction. It was confirmed that the γ-phenylpropyl alcohol could not be produced by the electrolytic reduction of cinnamic acid. It was found that the reduction of cinnamic acid at a Pt-Pt cathode gave cyclohexyl propionic acid.

The effect of high pressure of hydrogen in the course of reduction was discussed.
The New Method of Polymerization of Vinyl Compounds. I. On the Polymerization of Methyl Methacrylate with Copper or Cuprous Chloride and Acids at Room Temperature
Authors: Inoue Ryozo , Yamauchi Takashi
Published: July 2006

(1) It has been that the polymerization of methyl methacrylate happens catalytically with Cu or Cu2Cl2 and acids at room temperature. Polymerization products were obtained as fine powder easily separable from the reaction mixture.

(2) It has been pointed out that the polymerization is initiated by free radicals of hydrogen.

(3) Calculating from the degree of polymerization products polymers and consumed Cu2Cl2, the efficiency of the produced H· for the polymerization is not so good.
The Catalytic Action of Organic Peroxides on the Polymerization of Ethenoid Compounds. I. The Activity of Substituted Benzoyl Peroxides in the Polymerization of Styrene
Authors: Takebayashi Matsuji , Shingaki Tadao
Published: July 2006

(1) The rates of polymerization of styrene with m- and p-substituted benzoyl peroxides have been found to be inversely proportional to the square root of the dissociation constants of the corresponding substituted benzoic acids.

(2) The thermal decomposition of the peroxides in styrene has been observed to be of first order in all cases.

(3) It has been found that the rate of decomposition of peroxides is in a parallel relation with the rate of polymerization of styrene.

(4) The relation between the amounts of radicals derived from the peroxides and the rates of polymerization has been studied.

(5) In respect to the small activity of dinitro-benzoyl peroxides, a tentative theory has been made.
Sterols and Other Unsaponifiable Substances in the Fats of Shell Fishes, Crustacea and Echinodermata. XI. Sterols in the Fat of Clam
Authors: Toyama Yoshiyuki , Takagi Toru , Tanaka Tatsuo
Published: July 2006

(1) Steryl acetate obtained from clam fat was recrystallized from several different solvents, and it was found that the acetate recorded in the previous report as pure meretristeryl acetate, m. p. 149.5°, was not a pure single compound. Final recrystallization gave an acetate of m. p. 173–174°, though in a very small yield.

(2) Acetate mixture after removal of the fraction of m. p. 173–174° was fractionated by way of bromide, and it was found that brassicasterol, poriferasterol, clionasterol and cholesterol are present among the sterol components of clam fat.

(3) Bromination of the acetate of m. p. 173–174° and debromination of the bromination product yielded acetate having considerably lower melting points than the original acetate. Accordingly, there must have occurred isomerization or other changes in bromination and debromination cycle.
Estimation of the Amount of Hydration of Alcohols
Authors: Sasaki Tunetaka , Yasunaga Tatuya
Published: July 2006

The amount of hydration for alcohols in aqueous solution was estimated, assuming that the molecular sound velocity of a solution can be calculated from that for each constituent of the solution and their molal fraction, thereby regarding the water of hydration as the third component different from the free solvent and rather resembling ice as far as the sound velocity is concerned. The quantities thus calculated showed the general behavior of hydration water and also proved to be proportional to the heat of hydration.
The Oxygen Equilibrium of Hemerythrin and Bohr Effect
Authors: Kubo Masaji
Published: July 2006

The oxygen equilibrium of hemerythrin and its Bohr effect were studied by spectrophotometric method. It was found that the oxygen combining centers in this molecule are not completely independent but the stabilizing effect is weak. The value of n in Hill’s equation is equal to 1.37. The partial pressure of oxygen in equilibrium with the solution of 50 % saturated hemerythrin is 2.9 mm. Hg. Within the pH. range of stable hemerythrin solution, there is no dependence of oxygen equilibrium upon pH, hence no oxygen-linked acid groups are present in hemerythrin molecule.
The Co-ordinate Compounds of Iron with Some Hydroxycarboxylic Acids
Authors: Shibata Kazuo , Noguchi Tazuhiko
Published: July 2006

Chelating action of salicylic, sulphosalicylic and 2-hydroxy-3-naphthoic acids towards iron was investigated quantitatively, and it was found that they combine with one-to-one molecular ratio with iron. In order for these substances to be used as colorimetric reagents for the determination of iron, it is desirable that the reagents as well as their complexes be well soluble in water, and that the equilibrium contants of the complexes be sufficiently large so that the proportionality between the absorbance caused by complex and the concentration of iron or chelating agent may hold in a wide range. In this respect sulphosalicylic acid may be regarded as most suitable, among the three hydroxycarboxylic acids studied, as a reagent for iron determination. In view of the fact that the introduction of sulphonyl group into salicylic acid caused the increase of K, it may be expected that a more suitable iron reagents would be obtained by further introduction of sulphonyl group in salicylic acid.
Sedimentation Volume of Alginic Acid Powder in Electrolyte Solution
Authors: Miyamoto Shigeru , Sasaki Tunetaka
Published: July 2006

The sedimentation volume and swelling degree of alginic acid in electrolyte solutions were measured and the coagulation degree was calculated from these values. It was observed that the coagulation degree showed large values, giving maxima at relatively low concalculated from these values. It was observed nitrate. These maxima corresponded to the isoelectric points shown on the electrokinetic potential curve. A close correlation was seen among coagulation degree, electrokinetic potential and cation exchange amount.
Electrolytic Reduction of Aromatic Carboxylic Acids III. Reduction of Phenylacetic Acid
Authors: Ono Shin-ichi , Hayashi Tadao
Published: July 2006

(1) The electrolytic reduction of phenylacetic acid at a Pb, a Hg-Zn, a Hg or a Pt-Pt cathode was studied. It was confirmed that phenylethyl alcohol could be produced from phenylacetic acid using Pb, Hg-Zn and Hg cathodes. The Pt-Pt cathode was observed to behave catalitically in the course of reduction and gave rise to cyclohexylacetic acid.

(2) The relative ease of the reduction of the carboxylic acid to alcohol was closely-related to the nature of the group which lies between phenyl and carboxyl radical.

(3) The effect of high pressure of hydrogen was discussed on the electrolytic reduction of phenylacetic acid.
Mechanical Properties of Concentrated Hydrogels of Agar-agar. III. Relaxation of Stress in Compression
Authors: Fujita Hiroshi , Ninomiya Kazuhiko
Published: July 2006

As the third report of the series of papers concerning the viscoelastic behavior of concentrated hydrogels of agar-agar, the results of an experimental investigation of the relaxation of stress in an agar-agar gel of a concentration 4 g./100 cc. have been presented, which are summarized as follows:

(1) The general type of the relaxation curves obtained may be seen in Figure 2, in which particular attention must be drawn to the behavior that the plotted curves fall across the zero stress base after running certain finite intervals of time. An adequate interpretation of this has been presented in the last section of the text.

(2) As was illustrated in the second paper of this series, an agar-agar gel block decreases spontaneously and gradually its volume under the experimental conditions adopted in this series of experiments. Taking into account he spontaneous volume contraction, a system of equations for representing the viscoelastic deformation of an agar-agar gel column subject to compressive load has been presented, in which as a mechanical model of the material two Maxwell relaxation elements connected in parallel have been assumed.

(3) All the data of relaxation obtained have been considered in the light of this set of equations. In this way, the numerical results listed in Table 1 have been obtained.

(4) The activation energy for relaxation has been calculated for each individual mechanical element by the use of the Arrhenius equation. It has been found that the activation energies so calculated are constant below about 40°C. for both elements, amounting to nearly equal values, the average of which is estimated at about 9 kcal./mole. Above 40°C., for both relaxation elements, deviations from the Arrhenius equation appeared, which are gradually marked with increase in temperature. We have ascribed these deviations to the decrease in the frequency factor in the Arrhenius equation.

(5) Finally, the set of equations presented above has been solved for the case of compression creep under constant load, resulting in a creep equation coinciding exactly in form with the empirical creep equation derived in the previous paper II of this series. In addition to this formal agreement of the present theoretical and the previous empirical creep equations, quantitative agreement of them has-been demonstrated by showing that the viscosity values from the previous creep test can be well reproduced by the sum of the individual viscosity values obtained from the present relaxation test.
Dipole Moments of Bromotropolones, Thujaplicins and Related Compounds
Authors: Kurita Yukio , Nozoe Tetsuo , Kubo Masaji
Published: July 2006

The dipole moments of seven tropolone derivatives were measured in benzene solution at 25°C. The values obtained are: bromotropolone (m. p. 190°C, 5-bromo-), 2.07 D; bromotropolone (108°C., 3-bromo-), 3.91 D; tribromohinokitiol (90.5°C., 3,5,7-tribromo-), 3.05 D; α-thujaplicins, both A (34°C.) and B (25.5°C.) form, 3.37 D; dibromo-α-thujaplicin (80°C., 5,7-dibromo-), 2.82 D. By analysing the results obtained, the position of substituents in these molecules were determined and are given immediately after each name of these compounds in parentheses. The two crystal forms of α-thujaplicin with different melting points give an identical moment in solution. α-Dinitrohinokitiol of m. p. 155°C. is 5,7 (or po′) - dinitrohinokitiol.
Physicochemical Properties of the Surface of Aqueous Solutions. IV. Classification of Mechanical Behavior of Several Aqueous Surfaces
Authors: Kimizuka Hideo
Published: July 2006

1. Mechanical behaviors of surfaces of aqueous solutions were studied, and were explained by the three-parameter model with various relaxation times and retardation times.

2. The mode of change of mechanical models with the increase in concentration of the solution were classified into two groups; a change from the dashpot through the Voigt model to the three-parameter model, and a change from the dashpot through the Maxwell model to the three-parameter model. Saponin, crystal violet and sodium stearate belonged to the former, and egg albumin, horse serum albumin, peptone, gum arabic and polyvinyl alcohol, to the latter. It was presumed that this difference was due to the difference in the state of aggregation of their molecule.
The Visible Absorption Spectra and Binding Energy of Quinhydrone-Type Molecular Compounds
Authors: Tsubomura Hiroshi
Published: July 2006

The absolute intensities of the visible absorption spectra and the binding energies of quinhydrone-type molecular compounds have been determined by the measurements of their absorption intensities in solutions. The visible absorption spectra of these molecular compounds can be explained as the charge-transfer spectra of the π -electrons of quinone and the B compounds. The intensity of these chargetransfer spectra can be calculated roughly by setting up linear combination of the lowest unfilled MO of quinone and the highest filled MO of the B compound, and the results agree qualitatively with the experimentally derived absorption oscillator strengths. This chargetransfer resonance is thought to be the most characteristic part of the intermolecular binding energy in these molecular compounds.
Theoretical Study on the Polarographic Limiting Currents. I. Revised Equation for the Diffusion Currents
Authors: Matsuda Hiroaki
Published: July 2006

In order to integrate the MacGillavry-Rideal differential equation, representing the diffusion process at the dropping mercury electrode, the present author employed the von Kárman-Pohlhausen method. Thus the following revised expression of the Ilkovic equation showing the mean diffusion current is derived, in which the shielding effect due to the capillary tube is also treated theoretically.

\bari_d=608 n^*CD^1/2m^2/3τ^1/6{1+20.6(D^1/2m^-1/3τ^1/6)+49.0(D^1/2m^-1/3τ^1/6)^2-···}

The analogous treatment is also applied to the case of amalgam polarography, and the following equation for the mean diffusion current is obtained.

\bari_d=-608 n^*C_MD_M^1/2m^2/3τ^1/6×{1-30.5(D_M^1/2m^-/3τ^1/6)+155(D_M^1/2m^-1/3τ^1/6)^2-···}
Theory of Monolayer. II. Vibration of Molecule in the Monolayer Normal to the Surface
Authors: Hotta Hiroshi
Published: July 2006

The author has assumed in the previous paper that the vibrational term of the partition function of the molecule normal to the surface is equal in both gaseous and liquid films. This assumption was verified at the surface vaporization point in the present paper with the dynamics of material points. The derived relation between frequency and intermolecular distance or potential energy is (12) or (13).
On the Ring-opening Reactions of the Furan Compounds. III. On the Condensation of Furfural with Methyl Ethyl Ketone by Alkali
Authors: Midorikawa Hiroshi
Published: July 2006

It seems that furfural can react with methyl ethyl ketone in two ways by alkali.

In the condensation at 0∼3°, the main product was 4-(2-furyl)-3-methyl-4-butanol-2-one. This aldol was easily dehydrated to 4-(2-furyl)-3-methyl-3-buten-2-one, which was oxidised to α-methyl-2-furanacrylic acid by sodium hypochlorite.

In the condensation at 60∼3°, the main product was the furfurylidene ketone, which gave the semicabazone melting at 182∼4° and the dioxocarboxylic acid by ring opening in alcoholic hydrochloric acid. It is presumed that this ketone is 1-(2-furyl)-1-penten-3-one, and the dioxocarboxylic acid resulting from it is γ,ζ-dioxopelargonic acid.

It is also interesting that two species of 2,4-dinitrophenylhydrazone were obtained with respect to 4-(2-furyl)-3-methyl-3-buten-2-one.
The Catalytic Action of Organic Peroxides on the Polymerization of Ethenoid Compounds. II. The Activity of Substituted Benzoyl Peroxides on the Polymerization of Vinyl Acetate
Authors: Takebayashi Matsuji , Shingaki Tadao , Ito Yasumasa
Published: July 2006

(1) The activity of symmetrical m- and p-substituted benzoyl peroxides on the rate of polymerization of vinyl acetate has been investigated at 40°C. and 60°C. in the absence of air.

(2) The peroxides have been divided into two groups according to their activities. The activity of peroxides in each group is nearly inversely proportional to the square root of the dissociation constants of the corresponding substituted benzoic acids in the experimental conditions.

(3) The thermal decomposition of the peroxides in vinyl acetate has been observed to be of first order at 40°C, but not always exactly so at 60°C.

(4) In the decomposition of the peroxides at 40°C, carbon dioxide was not generated from all the peroxides excluding p,p-dimeth-oxybenzoyl peroxide; while in the decomposition at 60°C, carbon dioxide was produced from effective peroxides, such as dimethoxy-, dimethyl-, and p,p′-dichloro-benzoyl peroxides.

(5) It has been confirmed that the velocity of the polymerization is affected not only by the rate of decomposition of the peroxides but also by the activity of radicals derived from the peroxides.

(6) The results have been compared with those obtained in the polymerization of styrene.
The Effect of the Substituents (Alkyl-groups) on the Thermal Dissociation of Carbaminic Acid Esters
Authors: Mukaiyama Teruaki , Motoki Shinichi , Hamada Yasushi
Published: July 2006

The rate constants of the thermal dissociation of carbaminic acid esters in fatty acids were determined. In the case of phenylcarbaminic acid alkylestees, the rates showed the following order. tert-Bu>>isoPr≥Me

The relative rates may be considered to denote the ability of —OR groups as proton acceptors and the results of the experiment can be explained by the inductive effect of the substituted alkyl-groups.

In the case of alkylcarbaminic acid phenyl-esters, the rates showed the following order. Acetyl>>isoPr>Me

The relative rates may be considered to denote the ability of (Remark: Graphics omitted.) groups as proton donors. In acetylcarbaminic acid phenylester, because of the resonance effect of the (Remark: Graphics omitted.) and COOR groups, the intervening nitrogen aquires a positive potential. The phenomenon will make the hydrogen attached to nitrogen have more tendency to transfer, hence the reaction. That isopropylcarbaminic acid phenylester dissociates faster than methyl-carbaminic acid phenylester will be explained by the steric effect of alkyl-groups.

The rates of the thermal dissociation of esters depend on the nature of the solvent acids.
Studies on Unsaturated Organosilicon Compounds. I. Syntheses of Organovinylsilanes by Wurtz- Fittig Reaction
Authors: Kanazashi Motonori
Published: July 2006

(1) Vinyl chloride and organohalosilanes were shown to react with finely divided metallic sodium in ethyl ether, and trimethyl-, dimethyldi-, triethyl- and dimethylphenyl- vinylsilanes were prepared. Of these, dimethyldi- and dimethylphenyl-vinylsilane are new compounds and their physical constants were given.

(2) Infrared spectra of these four organovinylsilanes were obtained and certain characteristic absorption bands were discussed.

(3) Trichlorosilane was found to add to these vinylsilanes at the presence of diacetyl peroxide and four new β-trichlorosilylethyl-silanes were prepared and characterized.
Microscopic Studies on Fused Catalysts for Ammonia Synthesis. III. Weak Ferromagnetic Inclusions and Their Isolation for X-ray Study
Authors: Osumi Yoshio
Published: July 2006

On the basis of our new finding that B grains on the polished surface (Report 1 and 2) of usual iron synthetic ammonia catalysts are less ferromagnetic than A grains, we attempted to separate magnetically B grains from A grains. The more magnetic fraction (called A powder) and the less magnetic fraction (called B powder) have the following properties:

1. B powder as observed by the surface-electron microscope is as strongly electron-emissive as B grains on the polished surface. This suggests a successful separation.

2. Chemical analysis shows that B powder is far richer in K2O and CaO than A powder.

3. X-ray diffraction patterns of A powders separated from usual doubly or triply promoted catalysts are identified with that of magnetite, and those of B powders are all similar and complicated, whether they contain CaO or MgO or not. The product of potash fusion of Fe3O4 with 5 per cent Al2O3 gave the same diffraction pattern as B. Some relation of this new crystal structure to the spinel lattice of magnetite was discussed.

In the next paper will be reported the results of ammonia decomposition tests carried out with A and B powders under atmospheric pressure.
On the Nature of Built-Up Film. III. Effect of Dissolved Anion on Mono- and Multilayers of Octadecylamine
Authors: Sasaki Tunetaka , Muramatsu Mitsuo
Published: July 2006

Attempts were made to transfer the monolayers of octadecylamine on distilled water both onto the metal surface and onto the optical gauge of barium stearate. They did not adhere to the former surface, while with the latter it was shown that the homogeneous film was obtained when the substrate pH. and the piston pressure were favorable for preventing the film from aggregating.

Effects of organic anions upon the monoand multilayers of amine were investigated. The increase of the distance between the ionic groups of dicarboxylic acids caused the corresponding expansion and change in thickness of amine monolayer spread on the solution containing these anions. The solution of sodium alginate caused a somewhat large expansion and gave a remarkable rigidity towards the amine monolayer spread on it.

The built-up film of amine transferred from the substrate of various organic acids showed a variety of resistance for wettability when treated with aqueous sodium alginate solution. It was found that the resistance for wetting increased with the increasing complexity of the two-dimensional network formed in the film prior to the treatment. These results were discussed with regard to the easiness of overturning.
On the Electronic Absorption Spectra and the Dipole Moment of the Molecular Compound between Stannic Chloride and Naphthalene
Authors: Tsubomura Hiroshi
Published: July 2006

The 1:1 form of the molecular compound between stannic chloride and naphthalene in dilute solution has been confirmed by the measurements of electronic absorption spectra. The exaltation of the molecular polarization of this molecular compound has been determined from both optical and dielectric measurements and the dipole moment has been calculated from it. The absorption spectra of other similar molecular compounds have also been measured. It has been proposed that the intermolecular linkages may be explained as the charge-transfer bond.
Formation and Aging of Precipitates. I. Electron Microscopic Studies of the Formation of Barium Sulfate Precipitate
Authors: Suito Eiji , Takiyama Kazuyoshi
Published: July 2006

The shape and the size of barium sulfate precipitate prepared within the range of the total concentrations from 1.0000 to 0.0001 m were observed by an electron microscope. The particles were observed to precipitate in various forms (spherical, spindle, diamond and rectangular) in response to the total concentration of barium sulfate. It was confirmed that the precipitation law advocated by von Weimarn was still substantiated so far as the particles of the same shape were concerned.
Visco-Elasticity Measurement by the Torsional Rheometer. Simple Treat ment by the Application of the Four-Terminal Network
Authors: Nakagawa Tsurutaro
Published: July 2006

(1) The four-terminal electrical network is shown to be useful in the schematic representation of various mechanical systems.

(2) A simple review on various types of torsionally oscillating rheometers is given according to the theory of four-terminal networks.

(3) It is shown that complicated viscoelastic systems are easily solved so far as their formalistic treatment is concerned.
Photoconductivity of the Condensed Polynuclear Aromatic Compounds
Authors: Inokuchi Hiroo
Published: July 2006

Photoconductivity and optical absorption in the solid state of the organic semi-conductors, that is, isoviolanthrone (I), violanthrone (II), isoviolanthrene (III), violanthrene (IV), pyranthrone (V), pyranthrene (VI), ovalene (VII), flavanthrone (VIII), indanthrone (IX) and indanthrazine (X) were measured. From the threshold values of the spectral response of the photoelectric current and optical absorption in the solid state, the energy gap between the full band and the empty band were estimated as (I) 0.93 eV, 0.7 eV, (II) 0.84 eV, 0.75 eV, (III) 0.85 eV, —, (IV) 0.88 eV, 0.8 eV, (V) 1.14 eV, 0.85 eV, (VI) 0.85 eV, 0.8 eV, (VII) 1.20 eV, 1.2 eV, (VIII) 0.76 eV, 0.75 eV, (IX) 0.74 eV, 0.65 eV, (X) 0.80 eV, 0.7 eV respectively. Also from the experimental facts that the photocurrent is proportional to the applied potential arid to the light intensity, the author thinks that the photocurrent observed here is a primary current. These results, photoconductivity and absorption spectra, are in good agreement with that estimated from the temperature dependence of the electrical resistivity. It may be reasonable that this agreement is due to the fact that the organic semi-conductors studied here are intrinsic ones having molecular lattice.
The Michael Addition of Diethyl Methylmalonate to Ethyl Crotonate-(carbonyl C14). A Contribution to the Elucidation of the Mechanism of the Abnormal Addition
Authors: Simamura Osamu , Inamoto Naoki , Suehiro Tadashi
Published: July 2006

The Michael addition of diethyl methylmalonate to ethyl crotonate-(carbonyl-C14) was carried out with one equivalent of sodium ethoxide; the addition product, diethyl α-ethoxycarbonyl-β,γ - dimethylglutarate, was hydrolyzed and the resulting acid decarboxylated by heating. The evolved carbon dioxide contained 42 % of the radiocarbon of the original ethyl crotonate. Thus it was demonstrated that the migration of an ethoxycarbonyl group took place in the course of the reaction from the methylmalonate moiety to the carbon atom α to the labelled ethoxycarbonyl group. The mechaism of the reaction is discussed.
Immunochemical Studies on Oxidized Ovalbumin
Authors: Maekawa Kazuyuki , Kitazawa Kaoru
Published: July 2006

Using the oxidized ovalbumin, quantitative precipitin reactions were brought forward. There was some difference between the homogeneous reaction and the cross one in the precipitin reaction upon ovalbumin- and oxidized ovalbumih-serum only in the case of the less antigen region. The serological specificity of ovalbumin diminished considerably by the periodate-oxidation.
Studies on Some Physico-Chemical Properties of Ion-Exchange Resin. I. Heat of Wetting
Authors: Matsuura Tatsuo
Published: July 2006

(1) The measurement of heats of wetting of strongly acidic and weakly acidic cation exchange resins and strongly basic anion exchange resins was made by a simple method and their great dependence on the adsorbed ion species was found.

(2) The series of heat of wetting with ion forms is almost parallel with the lyotropic series of ions, thus it has been shown that this penomenon has an important relation to the hydration of the ions. The acid form of the weakly acidic resin occupies a special position, and this is attributed to the undissociative nature of carboxylic radical.

(3) The result on the partially wetted samples supports the view that only a few water molecules which may be called “bound water” take part in the heat of wetting or hydration of ions.

(4) A theoretical interpretation based on a few assumptions was attempted and a fair agreement with the experimental results was obtained.
The Thermal Polymerization of Acetylene. On the Formation of Cyclooctatetraene
Authors: Kuri Zenichiro
Published: July 2006

C.O.T. was found polarographically to exist in the thermal polymerization products of acetylene at the flow method. There did not occur any thermal cracking process below the temperature 570°C. on the experimental conditions. The polymerization of acetylene is fundamentally a bimolecular reaction and the dimer is supposed to be cyclobutadiene from the point of view of the steric factors of the reaction. Benzene is formed by the combination of cyclobutadiene and acetylene. C.O.T. is formed by the dimerization of cyclobutadiene; the rate of C.O.T. formation is of the second order in respect of acetylene. The activation energy and frequency factor of the rate is 46900 cal/mol and 1.50×1011 cc. mol−1·sec−1., respectively.

The ratio of yield of C.O.T. and benzene is independent of the pressure of acetylene and dependent of the temperature. In order to increase the ratio the activation energy E1 must be lowered. The high yield of C.O.T. in the Reppe reaction was considered qualitatively.
Reactivity of Coke. II. Effects of Heat Treatment of Cokes on Their Specific Surface Areas and Absolute Specific Reaction Rates with Carbon Dioxide at 950°C
Authors: Kawana Yoshio
Published: July 2006

The effects of heat treatment of cokes on their specific surface areas and absolute specific reaction rates of cokes with carbon dioxide at 950°C have been obtained by the same procedure as stated in the first paper.

Generally, the specific surface area of cokes decreases with heat treatment temperature, and the values for cokes from non-caking coals are much greater than those for cokes from caking coals in lower heat treatment temperatures, and there is a close relationship between the manner of decrease of the specific surface area of coke by heat treatment and the caking property of the original coal.

The changes by heat treatment of absolute specific reaction rates of cokes with carbon dioxide at 950°C are very irregular for all the temperatures. There are some effects, which are much greater than those of the difference of the crystallographic structure of cokes, on the absolute specific reaction rates of cokes with carbon dioxide. These effects have been assumed as the catalytic effects of the ash in coke, which may also be larger than those of the surface area of coke on the reactivity of coke.
Studies on Nitration of Furan Derivatives. Part I. On the Nitration of Furan-carboxylic Acid
Authors: Sasaki Tadashi
Published: July 2006

From the preparative point of view, the nitration of furan-carboxylic acid after sulfonation was studied with the following results:

(1) In order to obtain nitrofuran-carboxylic acid, the nitration of furan-carboxylic acid after sulfonation was carried out without separating the sulfonation product at several temperatures and the yield at 0° was about 32%, the highest ever known.

(2) In order to obtain nitrofuran-sulfonic acid, indirect nitration of sulfofurancarboxylic acid should be carried out at a low temperature, such as below 10°; the yield of which amounts to 20–22%. However, in this case, nitrofuran-carboxylic acid is produced simultaneously as a by-product.

(3) When the nitration of sulfofuran-carboxylic acid was carried out by using acetic anhydride and fuming nitric acid, nitrofurancarboxylic acid and dinitrofuran were obtained, but not nitrofuran-sulfonic acid. This showed that desulfo-nitrosubstitution took place more easily than decarboxy-nitrosubstitution.
Studies on Nitration of Furan Derivatives. Part II. On the Nitration of Furfurylidene-type Compounds
Authors: Sasaki Tadashi
Published: July 2006

The nitration, by using both fuming nitric acid mixed with acetic anhydride and fuming nitric acid alone, was carried out on 13 kinds of furfurylidene compounds,

C4H3O–CR1R2.

(1) These furfurylidene-type compounds in which R1 and R2 are electro-groups are stable against both acidic reagents and can be nitrated without formation of the nitration intermediate.

(2) In the case qf a group being—CHO or—COCH3, the nitration temperature must be kept low enough to avoid decomposition.
On the Distribution and Variation of Nutrient Salts in the Adjacent Water to the Aleutian Islands in the North Pacific
Authors: Fukai Rinnosuke
Published: July 2006

The author was engaged in the oceanographical observations carried out in a region adjacent to the Aleutian Islands in 1952 and obtained a number of data, on which the present discussions are based.

As the results, slight differences in distributions of nitrate-nitrogen, phosphate-phosphorus and silicate-silicon were found between the northern and southern areas separated by the Aleutian Ridge, although distributions are almost the same in the two areas.

Characteristic features in distributions of these nutrient salts are that the high concentrations were found even in the surface layer, increasing further with maximum gradients in depths within 100–300m.

The ratios of N:P in the region under study are lower than the normal ratio given by Cooper; and deficiencies in dissolved oxygen were recognized in the subsurface layers. These facts seem to be related to the characteristics of the decomposition processes in the Aleutian region.

On the basis of the rate of phosphate consumption in the upper layers, the net production rate has been computed by introducing some simplifying assumptions; and has obtained the value of 56 mg. C/m3/day. This value is considered to be reliable, since it coincides with that derived from Riley’s data and with that calculated from the data concerning the diurnal variations of dissolved oxygen.
Theory of Substitution in Conjugated Molecules
Authors: Fukui Kenichi , Yonezawa Teijiro , Nagata Chikayoshi
Published: July 2006

A theory concerning the mechanism of substitution in conjugated molecules is stated. The energy of the whole system is divided into σ- and π-parts. When certain relations hold between some integrals of σ-electrons, the σ-part of the energy of the system has a maximum in the process of the reaction, by which the transition state is defined. In the transition state a hyperconjugation may take place between the initial π-electron system and the pseudo-π-orbital in the vicinity of the reaction center. By means of the perturbation method, the π-part of the energy of the system involving the pseudo-π-orbital is obtained. The perturbation energy is always negative and by the magnitude of its absolute value, the reactivity of conjugated molecules can be discussed in a definite type of reaction with a definite reagent. From an approximate expression of this perturbation energy, the frontier electron theory is derived, which has previously been proposed by the present authors, whose coincidence with chemical experiences has already been ascertained. The mechanism stated above, therefore may supply us with a key to grasp a feature of the transition state and at the same time may present us with a physical meaning of the frontier electron theory.
On the Synthesis of 8-Hydroxyquinoline
Authors: Inoue Akira , Sugiura Michio , Tsuzuki Yojiro
Published: July 2006

1) 8-Sulfoquinoline has been obtained with a yield of 80.3% by sulfonating quinoline with 50% oleum at 140°C for 2 hrs.

2) 8-Hydroxyquinoline has been synthesized by fusing 1 mole of 8-sulfoquinoline with 9 moles of NaOH at 300-315°C for 10 to 15 minutes, decomposing the with dilute sulfuric acid, neutralizing with sodium hydroxide and soda to a pH 7.2, and by distilling with steam for 1.5 hrs. The remaining 8-hydroxyquinoline in the residue and in the filtrate was collected in the form of its copper salt. The highest yield of 8-hydroxyquinoline including its copper salt was 84.14%.

3) Copper 8-hydroxyquinolinate has been obtained with a yield of nearly 100% by heating 8-hydroxyquinoline with 0.86 times its weight of crystalline copper sulfate together with a large quantity of water at 80° to 100°C.
A Microphotographic Research on Salt System: NaNO2–KNO3
Authors: Sakai Kaoru
Published: July 2006

(1) The phase diagram of the NaNO2–KNO3 system was constructed by the thermal analysis and the electric conductivity measurements. The solidus on the whole is the same as found by Kagan.

(2) By the microphotographic method it was ascertained that this system belongs to a case of soild solution just as Kagan had inferred and that the nature of dendrite crystals in solid solution of the salts closely resembles those of alloys and devitrified glass.

(2) By the improved technique the microphotographic method of studying salt systems has now become able to apply to almost all salt systems.
Polarographic Diffusion Current Observed with Square Wave Voltage. III. Applications of the Theory
Authors: Kambara Tomihito
Published: July 2006

The theoretical treatment given in the previous works on the electrolysis with square wave voltage is here applied to the elucidation of experimental results. Thus the experiment by Madame Fournier is satisfactorily explained, and further the findings obtained with Kalousek’s and Ishibashi-Fuji-naga’s apparatus are also rationally clarified.
Terminally Phenylated Conjugated Unsaturated Ketones II. Silver Acetate on Dibenzylidenecycloalkanone Tetrabromides
Authors: Yeh Ping-Yuan
Published: July 2006

The action of silver acetate on 2,6-dibenzylidenecyclohexanone tetrabromide and 2,5-dibenzylidenecyclopentanone tetrabromide was studied.
Studies on Santonin. II. Experiments on the Synthesis of Santonin. Part II. Preparation of a Stereoisomeride of Santonin
Authors: Matsui Masanao , Toki Katsuyuki , Kitamura Seiichi , Suzuki Yoshio , Hamuro Michiko
Published: July 2006

A new isomeride of santonin, santonin C, was synthesized. The route consists of condensation of 2,3,4,5,6,10-hexahydro-2-oxo-1,10-dimethyl-naphthalene and diethyl methylmalonate, hydrolysis, bromination and dehydrobromination by lutidine.
Critical Concentration for Micelle Formation and its Aggregation Number in Aqueous Solutions of Paraffin Chain Salts
Authors: Shinoda Kozo , Kinoshita Kyoji
Published: July 2006

The cylindrical double layer model for the micelle was adopted and the aggregation number was calculated by the condition that ∂2En⁄∂2n2=0, and by using the aggregation number given by the above condition, an equation for the critical micelle concentration was derived. This equation shows that the critical micelle concentrations depend on the number of carbon atoms in the hydrocarbon chains and not on the kind of gegen-ions of the same valency. Moreover, the effect of added salts, polar oil and nonpolar oil on the aggregation number and on the critical micelle concentration in aqueous solution of paraffin chain salts was discussed qualitatively.
Quantitative Separation of Copper by Thiourea from Homogeneous Solution
Authors: Washizuka Shigenari
Published: July 2006

Quantitative separation of copper as sulfide was made from homogeneous solution containing thiourea, together with urea and ammonium chloride. It was found, that with boiling, the solution adjusted to a pH 4.0 in forty minutes or more after the first appearance of black turbidity; the precipitate is obtained in an easily filterable and washable form. Addition of ammonium chloride was found very effective in the presence of some cations. The amount of 10 to 100 mg. of copper could be satisfactorily separated from calcium and magnesium, and the separabilities from nickel, cobalt, zinc, and manganese were examined in the presence of ammonium chloride, and their allowable amount of coexistence in quantitative separation was determined.
Reaction Rates in the Synthesis of Ammonia. I. Dependence upon Reaction Pressure and Hydrogen-Nitrogen Ratio
Authors: Uchida Hiroshi , Kuraishi Michio
Published: July 2006

This series of experiments presents the well known fact about the different concentration increases as well as the different decreases of the conversion efficiency with the increasing pressure depending upon the kinds of catalysts in greater detail. At extremely high space velocities, the ammonia concentration remains constant independent of the change of the total pressure when the mixture of a constant gas ratio (H2: N2=3: 1) is used; however, it increases with increasing nitrogen pressure when the mixtures of different initial compositions are used at a constant pressure.

As predicted by Temkin’s equation, the nitrogen percentage or hydrogen percentage, at which a maximum ammonia concentration or a minimum conversion efficiency is observed, shifts towards the higher percentage with the increasing space velocity; however, the nitrogen percentage corresponding to the maximum shifts further through the critical value predicted by Temkin. The shifting is-more or less rapid depending on the kind of catalyst. To the extent that the space velocity is very high and the total pressure remains constant the equation by S. L. Kiperman can represent the shifting in a better agreement together with the observed proportionality between the ammonia concentration and the reciprocal space velocity.

The rate equations of M. I. Temkin and M. Shindo, which are based on different concepts, have been compared with the present results, and neither M. I. Temkin’s nor M-Shindo’s (unimproved) is in satisfactory agreement with the results. An equation based on the concept by M. I. Temkin and provided with another factor characteristic of the kind of catalyst has been proposed. The equation is in better agreement with the experimental results concerning the ammonia concentration expressed as functions of the space velocity and the pressure. The maximum of the ammonia concentration or the minimum of the conversion efficiency related to the ratio of hydrogen to nitrogen is represented in a somewhat better agreement with the singly promoted catalyst, while yet unsatisfactorily with the triply promoted.
Irreversible Photobleaching of the Solution of Fluorescent Dyes. I. Kinetic Studies on the Primary Process
Authors: Imamura Masashi , Koizumi Masao
Published: July 2006

The irreversible photobleaching of eosine in the aqueous solution and in alcohol-water mixtures was studied and it was found that the rate of photobleaching depends only on and is proportional to the quantity of ab-sorbed light when the dye concentration is 10−5 mol./1.

The overall unimolecular rate constant k or the quantum yield, when the quantity of dissolved oxygen is varied, does not change over a wide region but begins to decrease below a certain critical point.

The values of k in water-alcohol mixtures were found to be expressed by the following equation in the low concentration region of alcohol.

(Remark: Graphics omitted.)

where k° is the rate constant of the pure aqueous solution and K is a certain constant.

The possible schemes were given particularly on the bases of the rate formula (6) and of the effect of the quantity of dissolved oxygen.

It is most probable that the irreversible photobleaching of eosine by oxygen is a successive reaction as represented by the following scheme

Ib) D\xrightarrowhνD*→Dt\xrightarrowO2Dt···O2\xrightarrowH2O··· Product.

In this case, the probability with which Dt···O2 is deactivated by alcohol is about 100 times greater than that of Dt···O2 being attacked by water.

There is some possibility that the reaction may proceed in the following way.

IIb) D\xrightarrowhνD*→Dt\xrightarrowH2ODt···H2O\xrightarrowO2··· Product

Two cases corresponding to this scheme are possible. When a moderate fraction of Dt contributes to the reaction, the intermediate Dt···H2O must be deactivated by alcohol far more frequently than it reacts with oxygen, while when a very small fraction of Dt participates in the reaction, the probability with which Dt deactivated by alcohol is much larger than that of the reaction with water. The former case is rather improbable, while, the latter one seems to conform to a newly discovered fact that eosine in alcoholic solution is photobleached quite easily under evacuated conditions.

The kinetic studies of the vacuum-state-photobleaching of eosine in alcohol, the comparison of the effects of various alcohols upon the rate of oxygen-water-bleaching and the measurement of the rate of the possible vacuum-bleaching in various alcohols, all these investigations now in progress will give a more definite conclusion.
Studies on the Oxy-acid Phosphors. IV. Application of Polarography to the Analysis of Activators, Especially, in Calcium Silicate Phosphors
Authors: Kotera Yoshihide , Yonemura Michiko , Sekine Tadao
Published: July 2006

The amount of activators, which are now used for the present phosphors, was determined by means of polarography. The results obtained shows that manganese or copper is not dissipated during firing, while antimony or lead is dissipated in that period.

As for calcium silicate phosphors activated by manganese and lead, the residual amounts of activators were analysed by polarography and, these amount being taken as the additional factorial effects, the analysis of covariance was carried out to see the effects of atmosphere and firing time on the brightness. The results obtained show that the amount of lead has a more significant effect upon the brightness than manganese and the change of atmosphere causes that of the amount of activators and the brightness.
Heats of Combustion and Formation of Some Organosilicon Compounds
Authors: Tanaka Toshio , Takahashi Ukiko , Okawara Rokuro , Watase Takeo
Published: July 2006

1. A bomb calorimeter has been used for the measurements of the heats of combustion of the following five compounds at 20°C and at constant volume: dimethyl diethoxysilane, di-n-propyl diethoxy silane, diethyl silanediol, hexamethyl cyclotrisiloxane and hexaphenyl cyclotrisiloxane.

2. From these experimental results the corresponding heats of combustion and formation at constant pressure have been calculated, and the latter values were compared with the calculated values of the heats of formation derived from the data of the bond energies.