bluuebunny/crossref_metadata_2025 huggingface dataset:
Physico-Chemical Studies on Dyeing Process. I. Theory of Dyeing Equilibrium and Half Dyeing Time of Direct Cotton Dyes on Viscose Rayon
Authors: Nakagaki Masayuki
Published: July 2006

The theory of dyeing equilibrium is treated generally. On the way of derivation, it is emphasized that the Donnan’s equation,

f_+f_-[Na][Cl]=f_+^φf_-^φ[Naφ][Clφ]

is correct only when Na+ and Cl− have no affinity to the fibre. An equation expressing dyeing equilibrium is obtained for finite liquid yarn ratio, and compared to the equation by Vickerstaff for infinite liquid yarn ratio. Moreover, data for both finite and infinite liquid yarn ratio could be plotted on the same straight line according to the newly derved equation. The deviation of the incilination of the straight line from the theoretical value is attributed to the deviation of the activity coefficient from unity. The latter was assumed as analogous to that of soap, and a reasonable conclusion could be obtained.

On the theory of dyeing rate, all data from widely different dyeing conditions are brought into a simple relation

(Remark: Graphics omitted.)

using the half dyeing time T proposed by Boulton. This equation was justified theoretically, and it was show that Hill’s complicated equation is replaced by this simple equation, without loss of accuracy, as far as x⁄x∞≤0.7. Then, Boulton’s relation, that the half dyeing time becomes longer when the equilibrium exhaustion ratio is smaller, is justified theoretically. The apparent diffusion coefficient in fibre agrees with that of Hanson and Neale.
Organic Semiconductors with High Conductivity. I. Complexes between Polycyclic Aromatic Hydrocarbons and Halogens
Authors: Akamatu Hideo , Inokuchi Hiroo , Matsunaga Yoshio
Published: July 2006

It was found that most polycyclic aromatic hydrocarbons form molecular complexes with bromine or iodine. Those complexes which are black behave as typical semiconductors with energy gaps for conductivity of 0.1–0.2 eV., as well as with low electrical resistivity ranging from 10° to 103 ohm-cm. The complexes are unstable and a substitution reaction of halogen takes place; when this is not the case, e. g. the violanthrene-iodine complex, and the complex itself is quite stable, so also is the electrical property. It is concluded that the origin of the high conductivity is due to the interaction between hydrocarbon molecules and halogen molecules, and this is presumably due to the overlapping of molecular orbitals stretching throughout the crystal.
Heats of Dilution of Polystyrene Solutions. I
Authors: Amaya Kazuo , Fujishiro Ryoichi
Published: July 2006

A calorimeter equipped with a thermister capable of measuring the temperature change down to 0.5 ×10−4°C was constructed. By this apparatus the heats of dilution of three polystyrene solutions were measured and the values of interaction parameters were derived. The μ values for toluene solution and chloroform solution were both negative and large, but that for ethylbenzene solution was zero.

In order to compare with the polymer solution, the heat of mixing of ethylbenzene, which may be regarded as the monomer-unit of polystyrene, with same solvents were also measured and it was found that the interaction parameters of polymer solutions have the same signs as that of the corresponding monomer-unit solutions.
The Crystal Structure of Potassium Tetranitro-diammine-cobaltiate (III), K[Co(NH3)2(NO2)4]
Authors: Komiyama Yoshimichi
Published: July 2006

The crystal structure of potassium tetrani-trodiammine-cobaltiate (III), K[Co(NH3)2(NO2)4], prepared according to the method of Jörgen-sen, has been determined by two-dimensional Fourier method. The orthorhombic unit cell has the dimensions a=11.38±0.02 Å, b=12.95±0.02 Å and c=6.76±0.01 Å containing four formula units in it (Fe Kα, λ=1.937 Å), and the space group is D24-P212121. The shape and size of a complex ion was found to be similar to the one found in crystals of silver salt, Ag[Co(NH3)2(NO2)4]. Two ammonia molecules are co-ordinated to the central cobalt atom in trans-positions, with Co–N distance 2.00 Å.

The average dimensions of the nitro groups were: N–O = 1.22 Å and ∠ONO = 118°, in agreement with the results obtained for other nitro-complex compounds of cobalt. Each potassium atom is surrounded by eight oxygen atoms of the nitro-groups with distances ranging from 2.79 Å to 3.26 Å.
Electrophoretic Studies of Tobacco Mosaic Virus
Authors: Watanabe Itaru , Ui Nobuo
Published: July 2006

The variations of the mobility of tobacco mosaic virus (TMV) in phosphate buffer at pH 7.7 with changes in concentration and ionic strength have been investigated. The mobility is essentially independent of the concentration and has an average value of −7.05×10−5cm2/sec. volt in the phosphate buffer of ionic strength 0.2. On the other hand, the mobility increases greatly with the decrease of ionic strength. The net charge on the TMV particle, calculated from the mobility data by the aid of Gorin’s equation, was found to be constant (about −1,800) all over the range of ionic strength examined. Although it is considerably lower than the theoretical valency calculated from the analytical data, this low value of the valency from the mobility is quite reasonable to explain the observation that there is no serious, divergence from the ideal behaviour in the electrophoresis of TMV solution.
Kinetics of the Oxydation of Red Phosphorus by Potassium Bromate
Authors: Venugopalan M , George K J
Published: July 2006

Kinetics of the oxidation of Red Phosphorus by Potassium Bromate in acid solution has been studied. Using varying concentrations of potassium bromate and the quantity of red phosphorus between 0.01 g. and 0.02 g., the reaction has been found to be bimolecular with respect to potassium bromate over a temperature range of 30–55°C. The energy of activation and temperature coefficient of the reaction have been calculated. Further work on the oxidation of red phosphorus by bromide-bromate mixture in acid solution is suggested.
Interaction between Surface Active Agents and Proteins. II. Electrophoretic Investigation of the System Sodium Dodecyl Sulfate and Egg Albumin
Authors: Aoki Koichiro
Published: July 2006

We studied electrophoretically the interaction of SDS and egg albumin in the pH range between 5.4 and 10.8, higher pH’s than that of the isoelectric point of egg albumin. Results obtained are as follows.

(1) The electrophoretic patterns of the system egg albumin-SDS can be divided into three groups. This method of division is different from that in the system SDS-horse serum albumin by Putnam and Neurath. The first group of the division contains the patterns obtained when the mixing ratio albumin/SDS is between 100/0 and 80/20, and here the complex ADn (n=40, A: albumin, D : detergent) and egg albumin coexist. The second group contains the patterns obtained when the mixing ratio albumin/SDS is between 80/20 and 35/65 and in this region the composition of the complex changes continuously from ADn to AD8n, The third region appears when the mixing ratio albumin/SDS is between 35/65 and 0/100 and here the complex ADSn and SDS coexist. The above mixing ratio values are obtained at pH 6.8, and they change somewhat as a function of pH.

(2) Below pH 7, a number n of the first complex ADn equals the number of positive charges on one egg albumin, but above pH 7, this relation cannot hold.

(3) In the reaction between egg albumin and SDS, it is not assumed that SDS reacts only in a micellar form but that SDS existing as a single ion can react.
Rheological Properties of Some Polymerized Oils
Authors: Nakagawa Tsurutaro , Sen\={o} Manabu
Published: July 2006

(1) A method for measuring the dynamic visco-elasticity of liquid by the torsional oscillation is described.

(2) The visco-elastic oils produced by the thermal polymerization of linseed oil to various, degrees were studied by this rheometer.

(3) The amplitude effect of the dynamic properties was negligible ; so that these materials are supposed to be linear in their visco-elastic behavior.

(4) The dynamic visco-elasticity of these oils was measured in the very low frequency region (period : 10 seconds-5 minutes).

(5) The temperature dependence of the dynamic viscosity was discussed.

(6) Weissenberg effect of these oils was tested in a qualitative way.
Dielectric Polarization of Some Aliphatic Amines in the Liquid State
Authors: Shirai Michio
Published: July 2006

For diethylamine, i-propylamine, and tri-ethylamine, Debye’s formula holds as the relation between dielectric constant and dipole moment over a wide range of temperature. This fact can be attributed to the absence of the dipolar interaction on account of the screening of the permanent dipole by non-polar alkyl groups.
Distribution of Boron in Natural Waters
Authors: Muto Satoru
Published: July 2006

On the basis of the data and discussions in the preceding chapters, the distribution and migration of boron in natural waters are summarized in Figure 1. And the data in the figure were confirmed mainly with the samples from Kanto District, whereas the author is of the opinion that the distribution of boron and chlorine in natural waters is generally illustrated as here shown.

The water of rain and snow at Kiriu District contain 0.1 mg. B/1, and 2.4 mg. Cl/1., and the ratio of boron to chlorine is 0.04. (these values might be lower at high mountainous area) Being affected by the biological and geological influences of the drainage, the original water becomes to contain 0.2 mg. B/1. and 0.16 mg. Cl/1. The ratio of boron to chlorine amounts to 1.31 as in the Kiriu River. At this stage, the increase of boron content or decrease of chlorine content are remarkable. When these branches of tributaries are affected by the mineral springs (123.3 mg. B/1, 11747 mg. Cl/1. and 0.0105 of B/Cl) and the thermal springs (6.55 mg. B/1, 334.6 mg. Cl/1. and 0.0196 of B/Cl) the boron and chlorine contont change their value to 1.97 mg. B/1, 84.2 mg. Cl/1. as well as the ratio of boron to chlorine 0.0234 as respectively in the Okuresawa River and the Agatsuma River. And the values of 0.197 mg. B/1, 10.4 mg. Cl/1. and boron to chlorine 0.0190 are obtained for the Watarase River which is affected by communities. Of course the actual condition will not be so simple and many complicated factors may exist before they join the river water. The main stream collects various kinds of tributaries and comes to have the value of 0.345 mg. B/1, 6.16 mg. Cl/1. and the ratio of boron to chlorine 0.0560. Then the stream flows down to the ocean while it is affected by many kinds of things during the way.
The Electronic Structures of Azine Compounds. II. The General Considerations on the Electronic Structures of Azine and Dihydroazine Compounds
Authors: Akimoto Yûmi
Published: July 2006

1) The absorption spectrum of quinoxaline was observed in anhydrous methanol solution.

2) The longest wave-length π-π transition was observed near 31000–33000 cm−1.

3) The MO calculations were made on ten odd aza, azine, and dihydroazine compounds.

4) Comparing the vertical delocalization energies, the most stable isomer was decided as follows.

(Remark: Graphics omitted.)

5) Concerning the stabilities of each dihydroazine isomers, the following tendency was observed. The stabilities of dihydroazine isomers increase according to the certain order of molecular symmetry: C2VX→C2h→Vh.

6) The reduction rates of the delocalization energies, azine to dihydroazine compounds, could be a criterion to predict the stabilities of dihydroazine compound as compared with the corresponding azine compounds. When the rate was less than 6%, only the dihydroazine form could exist steadily; more than 17%, the only stable form was the azine form; and between 6-17%, both forms could exist, while the stability of the azine form was surpassed by that of the dihydroazine form near the rate of 9%.

7) The positions of the longest wavelength absorption were predicted or compared with the observed ones. Agreements were satisfactory in the permissible ranges.

8) The molecular diagrams were drawn on several azine and dihydroazine molecules, which could possibly explain the higher stabilities of dihydroazines, the larger skeletons of molecules.
Studies on the Graphitization. I. Changes of Crystallinity, Diamagnetic Susceptibility and Electrical Conductivity in the Process of Graphitization
Authors: Akamatu Hideo , Inokuchi Hiroo , Takahashi Hiroshi , Matsunaga Yoshio
Published: July 2006

Three sorts of carbon black, two sorts of pitch coke, violanthrone, and polyvinyl chloride have been subjected to heat treatment up to 3000°C. Changes in crystallinity during the graphitization have been studied by X-ray referring to inter-layer spacings and growth of crystallites. It was found that pitch cokes are graphitized with more facility than carbon blacks, and the other two substances are intermediate.

The magnetic susceptibility is determined solely by the size of plane molecules (La) irrespective of the sort of carbons, and tends to a limiting value −6.5×10−6 per gram which is coincident with the value of natural graphite, when La grows above 130 Å.

The electrical resistivity decreases as growth of crystallites, but there is a region when La becomes above 40 Å, where it tends to a nearly constant value for each carbon. Those values are different among the groups of carbons, and graphitized pitch cokes have less resistivity than graphitized carbon blacks. It was discussed that fine structures of multi-crystalline states are reflected on the resistivity.
Kinetic Studies on Hydrogenation of Fat. An Effect of Poison Formed in Catalysis on the Rate of Hydrogenation
Authors: Miyake Ryoichi , Shimamura Yoshizo
Published: July 2006

Estimation of the volume of hydrogen consumed by a static method with Cu-Cr-O under atmospheric pressure of hydrogen at 180°C by hydrogenation of whale oil was-studied kinetically.

It was observed that the reaction is zero order to the concentration of the molecule to be hydrogenized, and, in spite of it, the reaction velocity gradually decreases due to the reversible poisoning of catalyst. An assumption was made that a poisonous substance is formed in the process of catalysis, and that its amount is proportional to the degree of hydrogenation. The following formula is presented.

dx/dt=K_1(N_o-K_2x)
Behavior of Surface Active Molecules at Interface. I. Statistical Mechanical Studies on Head Contact and Chain Contact
Authors: Nakagaki Masayuki , Iida Saiichi
Published: July 2006

The idea of head contact and chain contact proposed by Adam was formulated by statistical mechanics, introducing the energy required to dip one end group into water, w. It is concluded that the value of w is less than 1 kcal./mol. for most of molecules examined, and it is greater when the length of the group is longer. The cross sectional area of the end group, Ap, is concluded to be smaller than that estimated by Adam. As for a mixed monolayer, the value of w and Ap were almost equal to the average of components.
A Thermistor Method for the Determination of Velocity Coefficients of Vinyl Polymerization. I
Authors: Miyama Hajime
Published: July 2006

To measure the rate of vinyl polymerization, a thermistor method was devised and better results were obtained compared with the thermocouple method, in the points of sensitivity of temperature, adiabatic time period, instrument’s lag in response and saving the space of the reaction vessel. The kp/kt value of styrene at 30°C obtained by this method was 2.02×10−6 and reasonable in comparison with other values obtained by different methods.
A Thermistor Method for the Determination of Velocity Coefficients of Vinyl Polymerization. II
Authors: Miyama Hajime
Published: July 2006

The kp/kt value of styrene, vinyl acetate and methyl methacrylate was obtained by using thermistor method reported in the first paper of this series. Moreover from the kp/kt values at various temperatures, the activation energy difference between propagation and termination processes was calculated-They were 3.71, 3.25 and 3.54 kcal./mol. for styrene, vinyl acetatjand methyl methacrylate respectively. The characteristics of this apparatus were almost the same as described in the first paper, although various monomers-were used.
A Thermistor Method for the Determination of Velocity Coefficients of Vinyl Polymerization. HI
Authors: Miyama Hajime
Published: July 2006

The author used a thermistor method to study the later stages of polymerization of vinyl acetate, which was photosensitized with 1,1’-azobiscyclohexanecarbonitrile and obtained the variation of kp/kt, Ep and Et with conversion.

From these results it was observed that the value of kp/kt increases gradually until about 50% conversion is reached and beyond this point increases rapidly. At the same time, the extent of conversion effects Et in the region of 20–30% conversion, but the effect upon Ep is not so marked in these stages and becomes appreciable at high conversions.
A New Method for Radiochemical Prospecting of Uranium Ore. I. Estimation of the Amount of Uranium
Authors: Yokoyama Y\={u}ji
Published: July 2006

A radiochemical method for the prospecting and the estimation of the amount of uranium layer under the ground based upon the determination of radium in mineral waters is described. Results show, 700 to 7,000 ton of uranium may occur in Hot Spring Tamagawa and 200 to 2,000 ton of uranium in Hot Spring Arima. The natural radioactive elements in mineral waters will give valuable information on the geological structures, especially the nature of the underground radioactive strata.
Dielectric Studies on Colloidal Solutions. II. The Behavior of Small Counter Ions in the Aqueous Solutions of the Hydrochlorides of Homologous Long-chain Amines
Authors: Shirai Michio , Tamamushi Bun-ichi
Published: July 2006

The high-frequency and low-frequency equivalent conductivities and transference numbers for aqueous solutions of octyl-, decyl-, tetradecyl-, and hexadecylamine hydrochlorides have been measured.

For the latter three solutions a considerable increase of the high-frequency concuctivity was observed, and for these three solutions-it has been shown that the transference numbers of cations abruptly rise at the critical concentration for the micelle formation, and then tend towards a constant value.

These experimental facts have been accounted for from the electrostatic point of view of the micelle structure. It has been inferred from the experimental results that the counter ion association may be essential to the formation of the micelle.
Preparation of Carrier-Free Yttrium-90 by Paper Chromatography
Authors: Kiba Toshiyasu , Ohashi Shigeru , Tada Satoshi
Published: July 2006

(1) Carrier-free yttrium-90 can be separated rapidly and simply from strontium-90 by paper chromatography. The most suitable solvent is a mixture of ethyl alcohol and 10% solution of ammonium thiocyanate (5:3 or 5:2). The Rf value of carrier-free yttrium-90 is 0 and that of strontium is 0.7 to 0.8.

(2) Carrier-free yttrium-90 having a radiochemical purity more than 99.9% can be prepared within forty minutes.

(3) If yttrium-carrier is present, when it is developed with the above mentioned solvent, it is distributed upward from the original position on the paper. Its distribution pattern depends upon the amount of yttrium-carrier and the developing time and it may be caused by the adsorption of yttrium on the paper.
The Studies on Micelles of Surfactants. I. The Phase in the interior of Micelles of Surfactants
Authors: Sasaki Hiroji , Okuyama Haruhiko , Saito Sh\={u}ji
Published: July 2006

From the spectral changes of the n, π, and B bands, it is concluded that the surfactant micelle, at least until 10% concentration, contains some water molecules.
Interaction between Surface Active Agents and Proteins. III. Precipitation Curve of the System Sodium Dodecyl Sulfate-Egg Albumin at Various pH’s and the Determination of the Concentration of Protein by the Titration Using Surfactant
Authors: Aoki Koichiro , Hori Joji , Sakurai Keiko
Published: July 2006

(1) The precipitation curve of the system egg albumin-SDS was studied in the pH region between 4.2 and 2.3, and at constant ionic strength 0.30. It was found that the number of SDS molecules bound to one molecule of egg albumin is constant and this is considered to be a verification of the fact that the number of positive charges on one egg albumin molecule is constant in this pH region.

(2) A rapid determination of the protein concentration by the titration using SDS is possible within an error of ±2%.

(3) Egg albumin and horse serum albumin react in different ways with SDS in distilled water and in sodium chloride solution.
Addition of Trichlorosilane to Styrene, 2 Vinylpyridine, Allylcyanide and Octene-1
Authors: Nozakura Shun’ichi
Published: July 2006

Addition reactions of trichlorosilane to styrene, 2-vinylpyridine, allylcyanide, and octene-1 were attempted in the presence of bases such as pyridine and in the presence of tetrapyridine nickel(II) chloride. The structures of the reaction products were established. In the presence of bases, trichlorosilane was added to 2-vinylpyridine and allylcyanide, yielding 2-β-trichlorosilylethylpyridine and β-trichlorosilylbutyronitrile, respectively. On the other hand, in the presence of tetrapyridine nickel chloride, the addition was effected for all the vinyl compounds examined. (2-vinylpyridine was not attempted.) In this case, however, the addition products proved to be composed of two position isomers, the occurrence of which was due to the difference in the orientation of addition, for each of the starting vinyl compounds.
Polarographic Studies of Metal Complexes. V. Ethylenediamine Complexes of Cadmium, Nickel and Zinc
Authors: Morinaga Ken-ichi
Published: July 2006

1. The reduction of cadmium-ethylenediamine complexes is reversible. In the concentration range of 0.1 to 2.0 m ethylenediamine [Cd en3]++ predominates in the solution, of which complex formation constant is equal to 1012.01.

2. The reduction of nickel-ethylenediamine complexes is irreversible. With the aid of the theoretical treatment developed by Matsuda and Ayabe, it was found that at the concentration of 1 m ethylenediamine [Ni en2]++ participated in the electron transfer process with the forward rate constant nearly equal to 1017.6cm./sec. and the transfer coefficient nearly equal to 0.5.

3. The reduction of zinc-ethylenediamine complexes is irreversible. It was found that in the concentration range of 0.1 to 2.0 m ethylenediamine [Zn en]++ participated in the electron transfer process with the forward rate constant nearly equal to 1031.2cm./sec. and the transfer coefficient equal to 0.86.

4. The decrease of the diffusion currents are due to the increase of the viscosities of the solutions. The apparent polarographic diffusion coefficients of these complex metal ions are ca. 8% smaller than those of the simple metal ions.
Mechanism of the Exchange Reaction of Oxygen Atoms between Gaseous Oxygen and Water Vapor Catalyzed by Calcium Oxide
Authors: Sakata Sadahiro , Morita Noriyoshi
Published: July 2006

Employing a high-feed rate of reacting gaseous reactants where the rate of reaction did not depend upon the feed rate, measurements of the dependence of the exchange reaction rate of oxygen atoms between gaseous oxygen and water vapor catalyzed by calcium oxide on the mixing molar ratio of reacting gases were made, and the results analyzed by the method of Hougen. The most probable among twenty postulated mechanisms is mechanism II-A where oxygen is adsorbed with dissociation and the rate of dissociative adsorption of oxygen is ratecontrolling or II-B where oxygen is adsorbed with dissociation and the recombination of adsorbed oxygen atoms to desorption is ratecontrolling. According to these mechanisms, the activation energy of adsorption of oxygen with dissociation or recombination to desorption is about 33 kcal./mol., which is in good agreement with the activation energy 30.6 kcal./mol. for the over-all rate of exchange reaction.
Studies on the Synthesis of Metal Complexes. II. Synthesis and Absorption Spectra of Hydrogen Ethylenediaminetetraacetato-cobaltate (III) and Sodium-hydrogen Chloro-ethylenediaminetetraacetato-cobaltate(III)
Authors: Mori Motoshichi , Shibata Muraji , Kyuno Eishin , Nakajima Hiroshi
Published: July 2006

Two new compounds, H[Coedta]·4H2O and Na[Co(Cl) (edtaH)]·2H2O were synthesized, and their chemical formulae were confirmed by means of potentiometric titration and by examination of the infrared spectrum.

The absorption spectrum of Na[Coedta]·4H2O in solution was measured to investigate the pH effect. The absorption curves in acid solutions (pH>2) were wholly identical with that in aqueous solution of the salt, but those of alkaline solutions (pH<10) wrre not identical and further showed deviation from Beer’s law.

The absorption curves of Na[Co(NO2) (edtaH)]·H2O, Na[Co(Br) (edtaH)]·2H2O and Na[Co(Cl) (edtaH)]·2H2O were also measured. The first band for the chloro-complex and that for the bromo-complex occupied the similar position and shifted bathochromically as compared with the corresponding maximum for the common complex [Coedta]. These results may be explained on the basis of the so-called “spectrochemical series”. The absorption spectra of the complexes [Co(X) (edtaH)] were found to have two absorption maxima in the ultraviolet region. This phenomenon may be attributed to the “trans effect” of negative ions.

By oxidation of an alkaline solution containing cobaltous and edta ions with hydrogen peroxide, a blue complex was produced. Although an attempt to isolate it ended in failure, existence of cobalt (III) complex containing hexadentate EDTA was assumed on the basis of the absorption spectrum.
A Kinetic Study of the Reaction of Substituted Benzyl Chlorides with Tertiary Amines
Authors: Mukaiyama Teruaki , Tanaka Hiromi
Published: July 2006

(1) The rate constants, the activation energies and the entropies of activation of the reaction of benzyl chlorides with tertiary amines in benzyl alcohol were determined.

(2) In the single stage process for the bimolecular nucleophilic substitution, the polar effects of the substituents are not clearly shown.

(3) Both steric and solvent effects play important roles on the reaction studied in this experiment.
Investigation on the Molecular Structures of Titanium Tetrachloride and Zirconium Tetrachloride by Gas Electron Diffraction
Authors: Kimura Masao , Kimura Katsumi , Aoki Michiro , Shibata Shuzo
Published: July 2006

1) The molecular structures of TiCl4 and ZrCl4 were determined by electron diffraction as follows : Ti–Cl = 2.185 ±0.01 Å in TiCl4 and Zr–Cl = 2.32 ±0.01 Å in ZrCl4, and both molecules have the tetrahedral form. At the same time a in exp (−aq2), the term relating to molecular vibrations, was determined. aClCl–aMCl is 0.0004–0.0006 for TiCl4 and 0.0007-0.0010 for ZrCl4.

2) The mean-square amplitudes of SiCl4, TiCl4, GeCl4, ZrCl4 and SnCl4 were calculated using the frequencies of the normal modes of vibrations. aClCl–aMCl thus obtained is 0.00045 for TiCl4 and 0.00094 for ZrCl4. These values are in satisfactory agreement with those obtained by electron diffraction.

3) Almost all physical properties of tetrahalides of the 4th group elements including molecular vibrations are classified into two groups, Si, Ge, Sn and Pb tetrachlorides and Ti, Zr, Hf and Th tetrachlorides. This will be due to the difference in bond character.
The Adsorption of Non-polar Gases on Alkali Halide Crystals. I. The Low-temperature Adsorption of Non-polar Gases on Cubic Sodium Chloride
Authors: Hayakawa Teruo
Published: July 2006

The low-temperature adsorption of non-polar gases (argon, oxygen, nitrogen and carbon dioxide) on cubic sodium chloride was investigated. The present results on the isosteric heats of adsorption for these four gases indicate that the non-uniformity of the surface considerably predominate in the low coverage region and the mutual interaction between the adsorbed molecules is also distinguished in the region of the comparatively high coverage.

The entropies of the adsorbed materials (argon, oxygen and nitrogen) were experimentally determined and compared with the calculated values of the two-dimensional gas. These results show that the adsorbed molecules have the nature of the two-dimensional gas at least in the region of θ=0.3∼0.9.

The present results indicate that the phase change (a gaseous film→a condensed film) of argon or oxygen may occur at about θ=0.9, but this fact is somewhat uncertain.
The Stabilities of Metal Ammine Complexes. I. The Absorption Spectra of a Series of Hexammine Ni(II) and Tetrammine Pt(II) Complexes
Authors: Yoneda Hayami
Published: July 2006

The absorption spectra were measured about a series of hexammine Ni(II) and tetrammine Pt(II) complexes having various amines as ligands. These amines were hydroxylamine, ammonia, ethanol-amine, methylamine, ethylamine and ethylenediamine. The results of the measurement indicate that the weaker the basic strength of an amine is, the more the absorption bands of the produced complex appear in the shorter wavelength. This fact was connected with crystal field theory, and the following rule was drawn: In the complex of a transition metal ion having an unsaturated d-shell, the weaker the basic strength of an amine is, the more stable the produced complex is.
Photochemical Reactions between Methylene Blue and Tri-, Di- and Monomethylamine. I
Authors: Obata Hiroshi , Koizumi Masao
Published: July 2006

The photobleaching of the evacuated aqueous solution of methylene blue by dint of tri-, di- or monomethylamine was studied. The reaction products were identified to be leuco dye and amine oxide, the former by a spectroscopic method and the latter by a chemical one.

It was found that a long lived metastable intermediate is produced and this intermediate slowly returns to the original dye even in the dark. Furthermore it was found that this intermediate has its own absorption near infrared region. On the basis of the above observations, the following scheme was proposed for the reaction.

(Remark: Graphics omitted.)

in which the process IV can be neglected in the present experimental conditions.

From the above scheme, ths following rate formula was derived which can represent all the experimental results satisfactorily.

x=Ae^-(k+s)t+Be^-(k-s)t

where x is the concentration of methylene blue.
The Surface of Copper-Nickel Catalyst. I. The Reaction between Hydrogen Chloride and the Catalyst
Authors: Takeuchi Toyosaburo , Sakaguchi Masakazu
Published: July 2006

(1) The reactions of hydrogen chloride with copper, nickel and copper containing 1% nickel, and the observation by means of an electron microscope were carried out to determine the state of the nickel contained in the copper-nickel catalyst.

(2) The numbers of copper ion gained from the copper-nickel catalyst per g., after the reaction with hydrogen chloride, increase with the amount of consumption of hydrogen chloride used, whereas that of nickel ion is in the range of 1019–1020/ g., practically constant, independent of the amount of the consumption of hydrogen chloride.

(3) The electron micrograph shows that the copper-nickel catalyst has a conspicuously rough surface, and many particles of several hundred angstroms in diameter are scattered on the surface of the catalyst.

(4) The results of the hydrogen chloride reaction experiment suggest that about 3% of the total amount of nickel contained in the catalyst exists adhering to the surface of the catalyst, in the state of metallic nickel particles.

(5) The ratio of the total surface area of nickel particles on the surface of the catalyst to the total surface area of the copper-nickel catalyst is given as 17%, by the calculation using the assumption that the size of the nickel particle is the same as that of the pure nickel catalyst prepared in the same way.
The Studies on Micelles. II. The Relation between Surfactant Concentration and Micellar Concentration in Aqueous Surfactant Solutions
Authors: Sasaki Hiroji , Saito Sh\={u}ji , Okuyama Haruhiko
Published: July 2006

From the spectral change of π band, caused by the association of azobenzene solubilized in aq. surfactant solutions, we have reached the conclusion that in a certain wide range of surfactant concentration, the micellar concentration is constant and only the number of surfactant molecules forming every micelle increases with increasing surfactant concentration. These values of the number of micellar molecules, obtained by spectral method, are in good agreement with those reported previously, in low concentration of surfactants.
Molecular Rotations of Glucides in Relation to their Structures. I. The Absolute Configuration of γ-Lactones
Authors: Yamana Shukichi
Published: July 2006

The changes in optical rotatory power of γ-lactone due to orientation-changes of a unit group in the molecule were calculated by using the Kirkwood’s polarizability theory with regard to molecular model, derived from Haworth’s perspective formula. The Fischer convention was presumed to be the structurally correct representation of absolute configuration.
The Adsorption of Non-Polar Gases on Alkali Halide Crystals. III. The Low-Temperature Adsorption of Non-Polar Gases on Cubic Potassium Chloride
Authors: Hayakawa Teruo
Published: July 2006

The low-temperature adsorption of non-polar gases (argon, oxygen, nitrogen and carbon dioxide) on cubic potassium chloride was investigated. The present results-on the isosteric heats of adsorption for these four gases indicate that the non-uniformity of the surface considerably predominates in the low coverage region and this is partly attributed to the lattice imperfection or the defects of the crystals.

The entropies of the adsorbed molecules were experimentally determined and compared with the calculated values of the perfect two-dimensional gas. These results show that the adsorbed molecules of argon, oxygen and nitrogen have the nature of the two-dimensional gas at least in the range of θ=0.3∼0.9 The present results also suggest that the phase change of adsorbed argon or oxygen from a gaseous film to a condensed film may occur at about θ=0.9. These results on the freedom of the adsorbed molecules are similar with those on cubic sodium chloride previously reported.
Studies on Antibiotics and Related Substances. V. Synthesis of 5-Methylenecyclopentanone-3-carboxylic Acid, an Antitumor Isomer of Sarkomycin
Authors: Umezawa Sumio , Kinoshita Mitsuhiro
Published: July 2006

1) 5-(Dimethylaminomethyl)cyclopentanone-3-carboxylic acid hydrochloride (I) has been synthesized from cyclopentanone-3-carboxylic acid by means of the Mannich reaction.

2) Methyl 5-(dimethylaminomethyl)cyclopentanone-3-carboxylate hydrochloride (II) has been degraded to give methyl 5-methylenecyclopentanone-3 -carboxylate (III), which has been hydrolyzed into 5-methylenecyclopentanone-3-carboxylic acid (IV), an isomer of sarkomycin.

3) The structures of III and IV have been proven.

4) It has been found that III possesses significant antitumor and antibacterial activities and IV shows also antibacterial activities.
Effect of Emulsifier upon the Compositions of Emulsion Copolymers of Acrylonitrile and Water-soluble Monomers
Authors: Uchida Moriya , Nagao Hideo
Published: July 2006

The following facts are found from emulsion copolymerizations of acrylonitrile and water soluble monomers such as methyl methacrylate, vinyl acetate and methyl acrylate.

(1) The compositions of copolymer are independent of the concentration of the emulsifiers used.

(2) The monomer-polymer composition curve of emulsion copolymerization of acrylonitrile and methyl methacrylate is made consistent with that of bulk copolymerization, when the composition of emulsion oil phace is used in place of that of the monomer.

(3) The monomer-polymer composition curves of emulsion copolymerization of acrylonitrile and vinyl acetate or methyl acrylate fall on that of bulk copolymerization.
The Adsorption of Non-polar Gases on Alkali Halide Crystals. IV Calculations of the Adsorption Behaviour of Non-polar Gases on Cubic Potassium Chloride and Cubic Potassium Bromide
Authors: Hayakawa Teruo
Published: July 2006

The potential energy of each isolated atom or molecule (argon, nitrogen, or carbon dioxide) adsorbed on the (100) plane of cubic potassium chloride and cubic potassium bromide has been theoretically calculated at four representative positions on the surface.

According to the present theoretical calculations, it seems reasonable to consider that the high initial heat of adsorption experimentally found for nitrogen or carbon dioxide is mainly attributed to the quadrupole interaction of each molecule with the surface of the crystals. The present results suggest that the surface may be influenced by the different types of the surface heterogeneity due to the defects of the crystals and the distribution of sites grouped in patches. The present theoretical calculations also suggest that adsorbed atoms or molecules of these non-polar gases easily migrate two-dimen-sionally. These results on the surface migration are qualitatively in good agreement with the experimental entropy curves.
The Adsorption of Non-polar Gases on Alkali Halide Crystals. V. The Low-temperature Adsorption of Non-polar Gases on Cubic Potassium Bromide
Authors: Hayakawa Teruo
Published: July 2006

The low-temperature adsorption of non-polar gases (argon, oxygen, nitrogen and carbon dioxide) on cubic potassium bromide was investigated. According to the results of the present experiments and the theoretical calculations given in the preceding paper, the high initial heat of adsorption experimentally found for nitrogen or carbon dioxide is mainly attributed to the quadrupole interaction of each molecule with the surface of the crystal. The present results also indicate that the non-uniformity of the surface is considerably predominant at lower coverage and this is partly attributed to the lattice imperfection and the defects of the crystals.

According to the present results on the entropies of the adsorbed atoms or molecules, the adsorbed phase of argon has the nature of the two-dimensional gas at least in the range of θ=0.3–0.9, while the adsorbed phase of oxygen or nitrogen shows a similar nature in the range of θ=0.3–0.8. The present results suggest that the phase change of argon from a gaseous film to a condensed film has occurred at about θ=0.9. In the case of oxygen or nitrogen, it is also suggested that the phase change of each adsorbed phase from a gaseous film to a condensed film has occurred at about θ=0.8.
The Adsorption of Non-polar Gases on Alkali Halide Crystals. VI(1). The Low-temperature Adsorption of Non-polar Gases on Octahedral Potassium Chloride
Authors: Hayakawa Teruo
Published: July 2006

1. The low-temperature adsorption of non-polar gases on octahedral potassium chloride was studied. The present results were compared with those already obtained for cubic potassium chloride.

2. The initial heats of adsorption of non-polar gases on the (111) plane of potassium chloride are all considerably greater than the corresponding values on the (100) plane.

3. The surface heterogeneity due to the imperfection of the crystal for octahedral potassium chloride is more predominant than that for cubic crystals.

4. The present results on the isosteric heat of adsorption and the entropies of the adsorbed phase indicate that the low-temperature adsorption of non-polar gases on the (111) plane of potassium chloride is practically localized.
Amino Acid Synthesis from Nitromalonic Ester. II. Synthesis of Proline and Glutamic-γ-semialdehyde
Authors: Okuda Tôru
Published: July 2006

1. A synthesis of Dl-proline from diethyl nitromalonate and acrolein by intramolecular reductive alkylation is described.

2. A new method for preparation of the dimethyl acetal of glutamic-γ-semialdehyde from the same starting materials in an over-all yield of 38% (based on diethyl nitromalonate) is also presented.
Hydrogen Bonding Effect on the Fluorescence of Some Nitrogen Heterocycles. I
Authors: Mataga Noboru , Tsuno Shizuyo
Published: July 2006

1. The hydrogen bonding effect on the fluorescence of quinoline and acridine was studied in non-polar solvent mixed with various proton donors.

2. The equilibrium constants of hydrogen bonding calculated from the absorption and fluorescence data were the same for these molecules, in contradistinction to the case of naphthols. Possible mechanisms for this experimental fact were proposed.

3. The larger the relative fluorescenceyields of hydrogen bonded nitrogen heterocycles become, the stronger the donating powers of proton donors are, and from this fact, discussions were given on the role of non-bonding electrons in the inner-quenching of these molecules.

4. The difference between quinoline and acridine in their fluorescence quenching caused by the existence of a halogen atom was ascribed to the different emitting π-electronic states in these molecules (1Lb in quinoline, 1La in acridine), and some considerations by means of analogy to the π-electronic structures of aromatic hydrocarbons were given.
An Electron Diffraction Investigation of the Molecular Structure of 1,4-Dichlorobutyne. II. A Study of Internal Rotation by Use of Halos in Small Angle Region
Authors: Kuchitsu Kôzo
Published: July 2006

The internal rotation of l,4-dichloro-2-butyne was investigated by the sector-microphotometer method of electron diffraction, examining the region of smaller scattering angles (q\lesssim15) ; photographs taken at a long camera length were analyzed using a criterion that the “background function” should have no sudden fluctuation. Free internal rotation is in good agreement with the observed scattering data, and a high potential barrier is inconsistent.
On the Thermal Dissociation of Organic Compounds. XII. The Effects of the Substituents on the Thermal Dissociation of Substituted Phenylureas
Authors: Ozaki Shoichiro , Nagoya Tsutomu
Published: July 2006

Eleven new ureas of the type, 1,1-diethyl-3-arylureas and 1-pentyl-3-arylureas were synthesized. The rate constants and ρ values of thermal dissociation of these ureas in fatty acids were determined. In 1,1-diethyl-3-arylureas, the ρ value of the dissociation reaction at 95°C. in chloro-acetic acid was −0.196, and it may be concluded that the protonation process seems to be the rate-determining step in the dissociation reaction of ureas in fatty acid. The activation energy was compared with those of other ureas.
Sedimentation of Spheres in a Suspension of Finite Concentration
Authors: Noda Haruhiko
Published: July 2006

Experiments were performed in order to find out the relation between the volume fraction concentration and the sedimentation coefficient in a suspension of spheres. The polystyrene latex suspension, Dow Latex 580 G, was used as the suspension of spheres of known hydrodynamic properties. No theoretical equation proposed in the past corresponds well with the experimental result obtained here. Therefore an experimental equation,

S_0=S{1+φ^2/3/(1-φ^1/3)^2(1+2φ^1/3)}

is proposed. Using this equation the amount of solvation in solution of some proteins and other molecules was calculated. The amount of solvation found is nearly enough to explain the frictional ratio for such molecules.
Studies on Azeotropic Mixtures. III. Physical Basis of Azeotropic Correlation Rules
Authors: Yoshimoto Toshio
Published: July 2006

The physical meaning of four empirical correlation rules of azeotropic data, i.e. two types of Lecat’s, Denyer et al.’s and Skolnik’s rules, is clarified simultaneously with their mutual relations, by using the equations derived in part I and the assumption of constancy of molecular interchange energy for homologous azeotropes found in part II of the series of this study. The theoretically derived equations by Kuhn et al. are also given as a limiting case of ours.
Bromometric Oxidation of Red Phosphorus by Bromide Bromate Mixtures
Authors: Venugopalan M , George K J
Published: July 2006

Bromometric oxidation of red phosphorus using an acid solution of bromide-bromate mixture has been studied and applied in the volumetric determination of red phosphorus. The kinetics of the oxidation process show that the reaction is of the second order. The influence of temperature and concentration of the reactants, have been investigated and the energy of activation calculated. Further the applicability of this procedure for a bromometric determination of red phosphorus is emphasized and such determinations can be carried out over a period of three to four hours.
Interaction between Surface Active Agents and Proteins. IV. Heat of Interaction of Sodium Dodecyl Sulfate and Egg Albumin
Authors: Aoki Koichiro , Suzuki Yasushi
Published: July 2006

We measured the heat evolved when egg albumin and SDS solutions were mixed at pH 6.8 and at 25.00°C, and calculated the heat of interaction.
Studies on Antibiotics and Related Substances. VI. Configurations of Isomeric O-Methylphenylserines and a New Route for the Synthesis of Chloramphenicol
Authors: Suami Tetsuo , Umezawa Sumio
Published: July 2006

(1) Dl-threo-O-Methylphenylserine has been isolated through its N-formyl derivative from the diastereomeric mixture of O-methylphenylserines which was prepared by the route of Van Loon and Carter.

(2) Dl-threo-O-Methylphenylserine has been led to Dl-threo-2-amino-1-p-nitrophe-nyl-1,3-propanediol and further to Dl-chloramphenicol.

(3) The other diastereomer of O-methylphenylserine (m. p. 251–253°C) has been led to Dl-erythro-2-amino-1-p-nitrophenyl-l,3-propanediol hydrochloride.

(4) Several derivatives of the diastereomers of O-methylphenylserine and O-methylphenylserinol have been described.
Dielectric Investigation on Coals. III. On a Variety of Coals
Authors: Miyasita Isao , Higasi Keniti , Kugo Masao
Published: July 2006

By using a method of paraffin-wax mixture dielectric constants were determined for a variety of coals including five specimens from foreign sources. It was found that dielectric constants of lower rank coals are generally higher than those of bituminous coals of higher rank. Large difference in dielectric behavior was detected among the coal specimens (C % 87–90) from different sources. The present dielectric measurement supported the view that the nature of Japanese coals is particular as compared with European and American coals.
Anton Exchange Adsorption of Some Metals from Mixed Solvents
Authors: Yoshino Yukichi , Kurimura Yoshimi
Published: July 2006

1) It was found that the addition of some organic solvents such as methanolethanol, n-propanol and acetone to the hydrochloric acid solution of zinc(II) and copper(II) increases the anion exchange adsorption of the elements in the range of relatively low hydrochloric acid concentrations (less than 2 m). In the 0.1 m hydrochloric acid solution, the straight line relation between log Kd and concentration of organic solvent was observed up to ca. 60 %.

2) In the case of copper(II), this effect of increasing the adsorbability was observed up to higher hydrochloric acid concentrations i.e., at least 8 m, which seems to reflect that the adsorption maximum occurs at a higher hydrochloric acid concentration than in the case of Zn(II).

3) It was suggested that these solvent effects may be, as a first approximation, explained by the increase in the formation of negatively charged chloride complexes of the metals as a consequence of the decrease in the tendency for solvation of metallic ions in mixed solvents.
Solvent Selectivity of Liquid Ammonia for Pure HydrocarbonsTie-Line Data and Comparison of Selectivity with Other Solvents
Authors: Ishida Kiyoharu
Published: July 2006

Equilibria for the systems n-hexanebenzene-liquid ammonia (20°C), cyclohexane-benzene-liquid ammonia (20°C and 0°C), and ethylbenzene-styrene-liquid ammonia (0°C and −15.5°C) were determined. It was shown that the ability of a solvent would be most practically compared by the product of the maximum value of selectivity and the maximum concentration of the solute in the extract, i. e. maximum separation factor. Selectivity and solvent power of some solvents were compared by this definition and it was recognized that liquid ammonia is comparable to diethyleneglycol as a solvent for the separation of saturated hydrocarbons and aromatic or olefinic hydro-carbons, rather than liquid sulfur dioxide.