bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies on Reactions Between Gas and Solid. VIII. The Mechanism of Nitrogenation of Calcium Carbide
Authors: Aono Takeo
Published: July 2006

In this paper the theories of nitrogenation of calcium carbide were summarized and discussed, and the mechanism of these catalytic action was explained.

1. The mechanism of nitrogenation was ascertained as follows:

I. activated adsorption of nitrogen on active positions of carbide, (at comparatively lower temperatures);

II. formation of an intermediate compound, Ca(CN)2, temporarily,

III. breaking up of Ca(CN)2 into CaCN2 and C,

IV. further propagation of the CaCN2—formation.

2. The action of catalysts can be classified also in four kinds:

I. catalysts which affect the adsorption of nitrogen on the carbide surface and make the start of the reaction easy, (active carbon or nascent carbon and carbon separating material such as phosphate-slag,)

II. catalysts which favor the cyanide formation as well as the pro？ession of cyanamide formation, (alkali and alkali-earth chlo？ides), they also affect the equilibrium Ca(CN)2\ightleftarrowsCaCN2+C,

III. catalysts which activate the carbide and facilitate the cyanamide formation, (Ca(CN)2 and CaCN2 formed by the reaction or co-melted previously with the carbide; CaS being a negative catalyst in this class,)

IV. catalysts which accelerate the propagation of the reaction diminishing chemical resistance phvsically as well as chemically, (CaF2, CaCl2 etc.)

Of course some of these catalysts have combined actions affecting on two or three stages simultaneously.

3. The depression of melting points, heat of activation, dissociation pres？ure of the cyanamide and the CaC2–CaCN2 system by these catalysts were also discussed.

4. Some chemical interpretations for the action of some catalysts were also proposed, (hypothetically).
The Formation of Polyhydroxy-dialdehydes. II. d-Lyxo-trihydroxy-glutaric Dialdehyde and its Derivatives
Authors: Iwadare Koichi
Published: July 2006

(1) Monoacetone-d-mannose was now obtained as colourless crystalline needles and its structure was established as 2,3-monoacetone-d-mannofuranose (III). Melting point, 80.5–82°. [α]D15=+4.5° (5 minutes)→−3.7° (40 hours) in water. And triaeetyl-monoacetone-d-mannose was ascertained to have the constitution (VI).

(2) Bis-phenylhydrazone of d-lyxo-trihydroxy-glutarie dialdehyde was obtained as colourless needles, starting from 2,3-monoacetone-d-mannofuranose. Melting point, 168.5–169°. [α]D15=−72° in pyridine. Equilbrium rotation of d-lyxo-trihydroxy-glutaric dialdehyde was measured. [α]D15=+5° in water. Bis-p-nitrophenylhydrazone of d-lyxo-trihydroxyglutaric dialdehyde was obtained as orange-yellow leaflets. Melting point, 207–207.5°.

Strontium salt of d-lyxo-trihydroxy-glutaric acid was obtained by oxidizing the dialdehyde with bromine in presence of strontium carbonate.
Studies on the Adsorption at the Solid—Liquid Interface. I. On the Adsorption of Some Fatty Acids by Glass
Authors: Akamatu Hideo
Published: July 2006

(1) A method of determining relatively small amount of adsorption has been devised. To measure the change of concentration of solution before and after the adsorbing procedure, the density determination using the float method is applied.

(2) The experiments are described on the adsorption of some fatty acids from the toluene solution by the glass powder.
Studies on the Reactions between Oxides in Solid State at Higher Temperatures. VI. Discussion of the Reaction Mechanism with a Special Reference to the Effect of Particle Size on the Reactions
Authors: Tanaka Yasuo
Published: July 2006

(1) The main characteristics of the solid reactions between the oxides, studied in the present investigations, have been summarized. These reactions can be classified into the following two types: (1) the reactions of the systems, MgO–TiO2, CaO–TiO2 and MgO–Al2O3, which have a rapid initial reaction period and a small energy of activation, and (2) those of the systems, MgO–SnO2 and CaO–SnO2, in which no rapid initial reaction and a large energy of activation are observed.

(2) The rapid initial reaction is probably due to the existence of a rapid surface diffusion, and when the reaction proceeds chiefly by the inner diffusion, no rapid initial part may be observed.

(3) The effect of the particle size of each of the components on these reactions has been discussed. In the reactions without distinct surface diffusion, the effect of the particle size of the component, of which total surface area is smaller, should be great, while that of the diffused component becomes remarkable when the sufrace diffusion takes place rapidly.

(4) For the three reactions, MgO-SnO2, MgO-Al2O3 and CaO-TiO2, the above discussions have been proved experimentally by changing the particle size of each of the components.

(5) Technical importance of the effect of particle size on solid reactions has been stated.

(6) Some further considerations on the diffusion mechanism have been given, and the difference in the energies of activation has been interpreted.

(7) Finally, the phenomenon of sintering due to solid reactions has been discussed. It is considered that the sintering occurs by the reactions in which a rapid surface diffusion takes place.

In conclusion, the author wishes to express his sincere thanks to Dr. R. Yoshimura for his interest, to Mr. K. Hirota for criticizing and discussing the problem willingly, and also to Dr. R. Negishi and to the other colleagues. He is also indebted to Messrs. S. Takasago and T. Sugawa for their assistances in the experiments.
The Addition of Hydrogen Bromide to Crotonic Acid in Carbon Tetrachloride Solution and the Oxygen Effect
Authors: Simamura Osamu
Published: July 2006

(1) Hypotheses suggested to explain the orientation of hydrogen bromide in the addition to the ethenoid compound have been briefly reviewed and critisized.

(2) Allowing the mixture of hydrogen bromide and oxygen to react with crotonic acid in carbon tetrachloride, three products, β-bromobutyric acid, crotonic acid dibromide and α-hydroxy-β-bromobutyric acid, have been isolated.

(3) Oxygen has been found not to accelerate the addition of hydrogen bromide to crotonic acid in carbon tetrachloride solution in the dark.

(4) It is concluded that in the addition of hydrogen bromide to crotonic acid in the presence of oxygen, this participates in the reaction producing free bromo-radical acid and bromine atoms, the latter being attached to the β-carbon atom of crotonic acid, but that the chains involving these cannot develop because of the ready reaction of the bromo radical acid with oxygen rather than with hydrogen bromide.
The Formation of Polyhydroxy-dialdehydes. III. l-Lyxotrihydroxy-glutaric Dialdehyde and its Derivatives
Authors: Iwadare Koichi
Published: July 2006

Following compounds were obtained in crystals: 2,3,5,6-Diacetone-l-mannofuranose, m.p., 122–122.5° and [α]D=−27° (in acetone). Bis-phenylhydrazone of l-lyxo-trihydroxy-glutaric dialdehyde, m.p., 165–165.5° and [α]D=+73° (in pyridine). Bis-p-nitro-phenyl-hydrazone of l-lyxotrihydroxy-glutaric dialdehyde, m.p., 203.5–204°. Potassium diacetone-l-mannonate, [α]D10=+32.2° (in water). And diacetone-l-mannopolactone, m.p. 124–124.5°.
Hydrogenation and Polymerisation Reactions of Acetylene II. Polymerisation Reaction by Use of the Thermal Diffusion Column
Authors: Kimura Osamu , Hirota Kozo
Published: July 2006

(1) The possibility of polymerisation reaction of acetylene with a good yield by use of the thermal diffusion column as reaction vessel has been discussed theoretically.

(2) The polymerisation of acetylene has been carried out with tungsten wire as heating filament at 700°C–1000°C.

(3) The experimental results have shown that acetylene is converted into liquid hydrocarbons almost perfectly, and that the amount of hydrogen, methane, and ethylene are small in the resulting gas, and moreover the deposition of carbon is scarcely observed.
Synthesis and Octane Number of tert-Butyl Cyclohexane and 1,4-Di-tert-butyl Cyclohexane. Alkylation of Benzene with Isobutylene into tert-Butyl Benzene and p-Di-tert-butyl Benzene and their Hydrogenation
Authors: Katuno Masaharu , Suwa Teturo
Published: July 2006

1. Benzene has been alkylated with isobutylene using sulfuric acid of various concentrations, and some of the results of V. N. Ipatieff, B. B. Corson and H. Pines have been reconfirmed. The alkylation takes place predominantly with 91–96% sulfuric acid.

2. Using 91% sulfuric acid as catalyst, benzene has been alkylated with varied amount of isobutylene against benzene. The increase of the yield of tert-butyl benzene caused by the decrease of the amount of isobutylene against benzene is not remarkable, forming a considerable amount of p-di-tert-butyl benzene fraction. By the increase of the amount of isobutylene against benzene, the yield of p-di-tert-butyl benzene fraction increases to the main reaction product, with the decrease of tert-butyl benzene fraction. The reaction of excess isobutylene with benzene causes the mere polymerisation of isobutylene with 91% sulfuric acid to yield high-boiling olefinic polymer after complete alkylation of benzene.

3. tert-Butyl benzene and p-di-tert-butyl benzene have been readily hydrogenated into tert-butyl cyclohexane and 1,4-di-tert-butyl cyclohexane, respectively, using nickel-kieselguhr catalyst. 1,4-Di-tert-butyl cyclohexane is a mixture of cis and trans isomers, and is partially crystal？ised at room temperature and melts completely at 31°C.

4. Octane numbers. of 1,4-di-tert-butyl cyclohexane, tert-butyl cyclohexane and the high boiling aromatic hydrocarbon CF2R have been measured. 1,4-Di-tert-butyl cyclohexane has high octane numbers as predicted, the 20% blending octane number amounting to 113. It has the flash point of 80.5°C., and is highly soluble in hydrocarbones, and there？ore may be used as a constituent of safety fuels.
Synthesis of Tertiary Butyl Alcohol by the Hydration of Isobutylene. II. Separation of Tertiary Butyl Alcohol by the Distillation of Diluted Sulphuric Acid Solution, and on the “Porous Substance Effect”, “Stirring Effect” and “Agitation Effect”
Authors: Katuno Masaharu
Published: July 2006

1. The separation of tert-butanol by the distillation from diluted aqueous sulphuric acid solution has been studied as the method of separation of tert-butanol from the absorption product of isobutylene with sulphuric acid without neutralising acid with alkali. By the suitable dilution of the absorption product, tert-butanol can be separated in the theoretical yield of about 68–80%, with small regeneration and polymerisation of isobutylene. The regeneration of isobutylene increases and the polymerisation takes place in a considerable extent with increasing concentration of acid. The increase in the absorption of isobutylene with a definite amount of acid, or the use of fractionating column in the distillation increase the regeneration of isobutylene.

2. The distillation in the presence of pumice powder increases markedly the formation of isobutylene with the decrease in the yield of tert-butanol. An explanation has been given.

3. The marked increases in the formation of gaseous product from liquid reaction mixture by the addition of powder of porous substances, such as pumice powder, and by the vigorous mechanical stirring have been named as “the porous substance effect” and “the stirring effect” respectively, both being named generically as “the agitation effect”. Some examples of the “agitation effect” observed hitherto have been summarized.
The Synthesis of Higher Alcohols in the Presence of Calcium Carbide. (B.) VI Normal Butyl Alcohol from Ethyl Alcohol and Carbide
Authors: Negishi Ryoji
Published: July 2006

The various substances synthesized have been separated into a number of fractions by distillation, and the properties of them have been described briefly.

The following factors which affect the synthesis of butanol have been considered: The effects of (1) the carbide concentration in the paste, (2) the temperature, (3) the rate of alcohol charged, (4) the pressure, (5) the rate of effluent gas, (6) the carbide content, (7) the solid diluents, and (8) miscellaneous factors, such as the species of the introduced gases and the paste vehicles.

Under the optimum conditions, two parts by volume of ethyl alcohol give one part of normal butanol, 0.2 parts of higher alcohol, and 0.3 parts of so-called hydrocarbons, boiling up to 165°C.

It has been concluded that the non-catalytic synthesis of normal butanol from ethyl alcohol in the presence of calcium carbide is not only theoretically interesting, but it may possess also some practical significance.
Hydrocarbon Conversion with Special Reference to the Thermodynamical Calculations for the Isomerization Reactions. II
Authors: Hamal Senzo
Published: July 2006

(1) For the discussion of the general trend of isomerization reactions of unsaturated hydrocarbons, the free energy equations as a function of temperature, convenient for practical calculations, are derived, based on some of the more recent data available.

(2) With the aid of these simple free energy equations, ΔF’s at 0°, 25°, 100°, 200° and 300°C. are computed and tabulated.

(3) Some correlations in connection with these thermodynamical calculations for isomerization reactions are presented.

(4) In general, isomerization reactions of hydrocarbons with a few exceptions are favoured thermodynamically at a lower temperature, as found in the case of saturated hydrocarbons.

(5) As we have already stated in the case of saturated hydrocarbons, isomerization reactions from those of simpler structure to the more complicated and branched are favoured thermodynamically, more or less, at a lower temperature.

(6) As in the case of saturated hydrocarbons, the conclusion given by Rossini that isomeric form is more stable than the normal form is also found to be reasonable, as far as our calculation indicates.
Studies on the Equilibrium between the Dilute Solution and Solute Vapour. II
Authors: Uhara Ituro
Published: July 2006

(1) Various factors affecting condensation coefficient of solute vapour on the liquid surface of solvents (chiefly α of I2) were studied.

(2) α has no parallelism with many physical quantities of solvents (surface tension, solubility etc.).

(3) Effects of addition of electrolytes, surface active non-electrolytes, reactable substances were discussed.

(4) α decreases with rising temperature.
Hydrogenation and Polymerisation Reactions of Acetylene. III. Kinetics of Polymerisation by Use of the Thermal Separation Column. I
Authors: Kimura Osamu , Hirota Kozo
Published: July 2006

(1) In order to investigate the kinetics of the polymerisation reaction of acetylene, a thermal separation column has been used as reaction vessel, and the superiority of this device has been stressed, both theoretically and experimentally.

(2) The results of experiment have shown that the reaction is of second order, and that the apparent activation energy is 44.8 kcal.
Studies on Synthetic Fibers (I). Decomposition and Synthesis of “Nylon”
Authors: Hosino Kôhei
Published: July 2006

(1) “Nylon” yields hexamethylene diamine hydrochloride and adipic acid upon hydrolysis with hydrochloric acid, so it is proved to be polyhexamethylene adipamide.

(2) Superpolyamide was synthesized from adipic acid and hexamethylene and an excellent synthetic fiber was spun from this polymer.
The Quantum Mechanical Treatment of Viscosity by Use of the Rigid Elastic Sphere Model. II. The Sutherland Constant
Authors: Hirota Kozo
Published: July 2006

1) According to the conclusion of the previous paper, the “Sutherland constant” in the viscosity coefficient for various substances has been calculated quantum-mechanically by a simple procedure.

2) The Sutherland constant C0 thus calculated has been found to obey Rankin’s and Vogel’s rules even in the substances of low molecular weight.

3) The disagreement in the Debye’s formula between electric moment and Sutherland constant has been shown to disappear if C0 was used instead of the classically determined Sutherland constant.
A SIMPLE PROCEDURE OF SEMI-QUANTITATTVE SPECTRAL ANALYSIS OF CALCIUM, STRONTIUM, BARIUM AND LITHIUM
Authors: Hukuda Kunizô
Published: July 2006

1. A simple procedure of the semi-quantitative spectral analysis has been described.

2. This procedure consists in observing salt solutions fulgurated in a special fulgurator, with the electrodes reversed, i. e. the anode in the solution.

3. Accuracy and limit of application of this method were carefully studied and it was found that this is especially suited for the analysis of minute quantities of lithium, calcium, strontium and barium.
ON THE OXIDATION OF THE MIXTURE OF STANNOUS CHLORIDE AND SODIUM SULPHITE IN ALKALINE SOLUTION WITH AIR
Authors: Miyamoto Susumu
Published: July 2006

1. The oxidation velocity of the mixture of sodium sulphite and stannous chloride in alkaline solution with air was studied.

2. When the initial concentration of stannous chloride is not small, the oxidation velocity is independent of their concentrations and is smaller than that of each.

3. When the initial concentration of stannous chloride is small, the oxidation of the mixture takes place at a slow rate first, and increases with time.
THE VISCOSITY OF LIQUIDS ABOVE THEIR BOILING POINTS. PART. III
Authors: Titani Toshizo
Published: July 2006

1. The volume relation of molecular or specific fluidity holds good even when the viscosity changes remarkably with pressure.

2. The volume and temperature relations give results which agree well with each other in all respects.

3. From the two sorts of relations concerning the viscosity, the following equation was obtained,

(Remark: Graphics omitted.)

\oindentwhich was found to hold with good accuracy.
ON THE SO-CALLED DIETHYL DICYANOGLUTACONATE AND SOME OF ITS DERIVATIVES
Authors: Urushibara Yoshiyuki
Published: July 2006

1. The so-called diethyl dicyanoglutaconate has the composition (C11H12O4N2)2H2O and the constitution is considered to be represented by the formula (C10H12O4N)–CO–NH–C(NH)–(C10H12O4N).

2. The diethyl sodiodicyanoglutaconate is colourless when pure.

3. By the action of bromine on the so-called diethyl dicyanoglutaconate an addition product is obtained, which has the composition (C11H12O4N2)2·H2O·HBr·Br6. This is changed into the diamide hydrobromide, C11H16O6N2·HBr, in ether containing water.

4. The picrate of the diamide, C11H16O6N2·C6H2(NO2)3OH, is obtained from the diamide hydrobromide, from the bromine addition compound, and from the so-called diethyl dicyanoglutaconate. These three compounds are all changeable into the diethyl dihydroxydinicotinate.
SPECTROCHEMICAL STUDIES OF HYDROXYAZO-COMPOUNDS. PART III
Authors: Uemura Taku , Yokojima Naomichi , Endo Tamimatsu
Published: July 2006

1. Tautomeric transpositions may take place in these hydroxyazo-compounds by the addition of a potassium hydroxide solution, with an accompanying change in colour.

2. We can respectively assign A(azo)-, R(red)-, and B(blue)-forms to these tautomers. (Sometimes we recognise more readily the mixture of these forms.)

3. Tautoinerism is due to the labile hydrogen atoms in hydroxyl-groups which take the ortho- or para-position with respect to the azo-group.

4. The hydrogen atom which is in the meta hydroxyl-group with regard to the azo-group does not only move by itself, but moreover hinders the transposition of the other hydrogen atoms.

5. When there are many labile hydrogen atoms, mutual hindrance may occur.

6. B-form is sometimes produced only when there is a para nitroradical with regard to the azo-group.

7. Nitro-groups which take the ortho- or meta-position with respect to the azo-group do not change into the isonitro-structure.

8. The nitro-group has considerable bathochromic influence upon these hydroxyazo-compounds.

9. Generally only one absorption band exists in the solutions, of these substances, but there are two bands when methyl-group is included.
THE PHOTOCHEMICAL REACTIONS OF COLOURING MATTERS. I. THE REVERSIBLE PHOTOCHEMICAL REACTION OF MALACHITE GREEN
Authors: Ariga Teru
Published: July 2006

1. The photochemical reversible reaction of the alkaline solution of malachite green was studied with the quartz-mercury-lamp, and its nature was discussed.

2. The reaction velocities were determined both in the light and the dark reaction, using Nutting’s spectro-photometer. The former is proportional to the intensity of light and the latter to the concentration of the alkali added.

3. The temperature coefficient of the reaction velocity of the light reaction was found to be unity at the interval between 25° and 35°C.

4. Equation of the reaction of first order was derived with approximation for the light reaction.
The Extraction of Germanium and Gallium from Germanite
Authors: Saito Kazuo
Published: July 2006

The author has succeeded to extract germanium and gallium of satisfactory quality almost quantitatively in small scale. Germanium oxide can be refined by redistillation and hydrolysis, and the product is applicable as the standard substance for the chemical study. It is confirmed that Rothe’s extraction is a suitable method for the preparation of gallium from germanite.
The Seperation and Purification of Rare Earth Elements from Monazite (I)
Authors: Arakawa Hisaichi
Published: July 2006

(1) The rare earths, free from thorium, could be separated as the earths sulphate double compound (yield 93%).

(2) The method of separating thorium from the filtrate, which was obtained by separating about 63% of rare earths salt from the extracted solution, gives better result than a method of direct fractional precipitation from the extracted solution.

(3) Cerium can be separated from a solution as rare earths ammonium double compound with a purity of 92–96% (yield 70–75%).

(4) In the separation of cerium, a maximum point of purity is obtained when sufficient quantity of ammonia is added just to remove the colour of Ce ion from the solution. The purity and yield of cerium is not strictly in an inverse proportion, but a point of maximum purity of precipitate is obtained when a certain definite amount of ammonia is added.
A New Chemical Method for Measuring the Ultra-violet Ray
Authors: Miyake Yasuo
Published: July 2006

The author has contrived a new instrument to measure the relative intensity of the ultra-violet radiation using the leuco-base of crystal violet. A quartz glass ampule containing the leuco-base solution is exposed to light and the dyestuff thus produced is determined colorimetrically with a series of a standard solution of crystal violet contained in ampules of the same size. The method of measurement is explained.
Actinomycin J2, a By-product from a Strain of Actinomyces
Authors: Hirata Yoshimasa , Nakanishi Koji
Published: July 2006

The constitution of actiomycin J2 obtained from actinomyces flavus has been studied and idenified to be the dodecyl ester of 5-ketostearic acid by means of hydrolysis of the original substance, followed by the Beckmann rearrangement and hydrolysis of the oxime of 5-ketostearic acid into myristic acid, γ-aminobutyric acid and a small amount of n-tridecyl-amine. Next, the 5-ketostearic acid was synthesized according to two methods, which were concluded respectively by the hydrolysis of condensation products of the type: CH3(CH2)mC(COCH3)(COOC2H5)CO(CH2)nCOOC2H5 and CH3(CH2)n+1CO(COCH3)(COOC2H5)(CH2)n−1COOC2H5, of which the latter gave a considerable yield, while that of the former was very poor owing to the undesired direction of hydrolysis. The condensarion products of 5-ketostearic acid chloride and dodecyl alcohol showed no depression of meltihg point when mixed with actinomycin J2, thus proving the constitution of actinomycin J2 to be the dodecyl ester of 5-ketostearic acid.

These experiments were begun since it seemed that actinomycin J2was an antibiotic, but considering the fact that the synthesized specimen demonstrated no such activity, it must be conculded that the original activity was probably due to a minute amount of actinomycin J1 existing as an impurity, and that actinomycin J2 is a mere by-product.
On the Equilibrium of the Radioactive Elements in the Hydrosphere. V. A Simple Method for Distinguishing Uranium and Thorium in Radioactive Minerals
Authors: Kuroda Kazuo
Published: July 2006

It was found that the uranium and thorium in radioactive by measuring the radioactivity of mineral are easily distinguished radium emanation and thorium emanation in the minerals with I.M. fontactoscope.
On the Diamagnetism of Perylene. II
Authors: Hazato Genjiro
Published: July 2006

Applying London s theory of diamagnetic anisotropy, computations have been performed on the structure of perylene molecule. In this problem, the theory gives no definite value if we choose such a model constructed with the same, five regular hexagons as we usually do in the conventional method. Introducing a simple parameter, this difficulty is removed with the result that the relative diamagnetic anisotropy of this molecule is about twice as large as that of naphthalene, showing a good agreement with experiment. A model as a peripheral form gives a divergent result from experiment.
A New Method of the Colorimetric Determination of Small Amounts of Manganese with Silver Peroxide
Authors: Murakami Yukio
Published: July 2006

In face of several defects noted by the oxidation agents hitherto used in the determination of manganese by the colorimetric method a new reagent, so-called “Silver peroxide,” has been proposed. This new reagent has been found to excel other reagents in the following respects: a) easy preparation and easy decomposition of the excess reagent, b) strong oxidizing power not reduced by long standing and cheap availability for routine work, c) no noticeable interference by other reagents during action and accuracy in results obtained.

Thus by its use the procedure is exceedingly simplified and the time required is considerably less than that in the method used hitherto.
Studies on Foams. III. The Foam Formation of Some Dyestuff Solutions
Authors: Nakagaki Masayuki
Published: July 2006

The foam formations of the aqueous solutions of methyl violet 5B, brilliant green, malachite green, crystel violet, Hofmann’s violet and congo red have been measured. The foaming ability, that is the product of foaminess and foam strength, is considered as the measure of the foam formation. This scarcely changes by the long period’s storage of the solution. The foaming ability of them is nearly parallel with the surface activity. This is interpreted with structural formnlae of dyestuffs.
On the Equilibrium of the Radioactive Elements in the Hydrosphere. III. On the Ratio of Thorium Emanation to Radium Emanation in the Hydrosphere
Authors: Kuroda Kazuo , Yokoyama Yuji
Published: July 2006

The ratio of thorium emanation to radium emanation in natural waters was measured. Following three methods were used: (1) with the I. M. fontactoscope, (2) with the Lauritsen-type K. Y. fontactoscope, and (3) the indirect method, in which the radioactivity of the decay products of thorium emanation and radium emanation is measured with the Lauritsenetectroscope.

It was found that thorium emanation is considerably widely distributed in the mineral springs and hot springs of Japan.
The Diffusion of Dye Solutions
Authors: Nakagaki Masayuki
Published: July 2006

The apparent diffusion coefficient of congo red in water, obtained by Auerbach-Ostwald’s method, changes with concentration. Solving the Fick’s equation with the assumption that the. diffusion coefficient is a function of concentration, the apparent diffusion coefficient can be recalculated to differential diffusion coefficient. From the value extrapolated to infinite dilution, the particle radius of congo red was calculated using Einstein-Sutherland’s equation. On the assumption that the particle is spherical and not hydrated, the particle weight and association degree were obtained. The diffusion coefficient, obtained by this method for congo red solution containing various concentration of NaCl, agrees well with the data reported by others. With the increase of salt concentration, the particle size increases gradually. No decrease was observed in the particle size with a small addition of electrolyte.
A Contribution to the Equilibrium of the System of Sea Salts at 110 °C
Authors: Tanaka Yasuo , Takasago Shozo , Komatsu Takashi
Published: July 2006

1. The solubility of magnesium sulfate in magnesium chloride solution at 110°C has been studied with a special reference to the crystallization velocity. In this system, it seems that the formation of the nuclei of kieserite is very difficult, and, when they are once formed, further crystallization takes place smoothly.

2. In the system, NaCl-MgSO4-MgCl2-H2O, at 110 °C, it has been found that the point K lies at about Na2 17.5, Mg 63, Cl2 67 and SO4 13.5 mols per 1000 mols of H2O. The content of magnesium is much larger than what has been estimated by D’Ans, and, accordingly, the löweite field of him should be enlarged.

3. Preliminary experiment on the five component system of sea salts at 110°C has shown that langbeinite may have a larger field than expected from the diagram of D’Ans.
An Improved Method of the Colorimetric Determination of Chromium with Diphenylcarbazide
Authors: Murakami Yukio
Published: July 2006

The colorimetric method of determining chromium in silicate rocks with diphenylcarbazide has the defect resulting in a distinct tendency for producing slightly lower figures as recognized already. After a thorough study of the method the author pointed out the possible sources for the serious errors, especially for those which give negative results. Thus the oxidation method in an alkaline medium was proposed, which was compared with the widely used old method.

The accuracy and reproducibility of this method are not entirely satisfactory but so far it will serve as the most accurate method. The content of chromium in brown coal in Japan determined by this oxidation method with sodium peroxide will be reported in a later communication.
Effects of Hydrochloric Acid on the Paper Chromatography of Amino Acids
Authors: Ishii Shin-ichi , Ando Toshio
Published: July 2006

To explain what effect hydrochloric acid, contained in the sample to be analyzed, gives upon the paper chromatograms of amino acids, RF values of some amino acids dissolved in hydrochloric acid of various concentrations were observed with different kinds of solvent.

In case of n-butanol, hydrochloric acid was found to increase the RF value of each amino acid with an increase in the concentration of hydrochloric acid, while in isovalerianic acid, on the contrary, to decrease that. On the one hand, only the amino acids of lower RF values were affected by hydrochloric acid in the case of phenol. In butanol-acetic acid, on the other hand, some effect was also found, but in collidine-lutidine it was negligible. In all cases, the relation between thess effects and the diffused areas of hydrochloric acid on the chromatograms was observed with great interest.
On the Retardation of Catalysis. The Catalytic Reaction between Acetylene and Hydrogen
Authors: Tamaru Kenzi
Published: July 2006

(1) The retardation of hydrogenation of acetylene on the palladium-alumina (1:100) catalyst by the deposited polymers and some inorganic salts were investigated.

(2) By correcting the retardation of the polymers, which deposited on the surface of the catalyst during the reaction, it was found that the net hydrogenation rate of acetylene was expressed by the following equation,

(Remark: Graphics omitted.)

(3) It was suggested that both catalytic hydrogenations of acetylene and ethylene proceeded on a few “active regions” of the catalyst with different ratios, and taking some assumptions, the rôle of the various “active regions” on the two hydrogenations was considered.

(4) It was shown that lead acetate solution poispned the ethylene hydrogenation much more than the acetylene hydrogenation and this fact coincides with the result of the flow method.
Dispersity of Catalyst and Catalytic Activity. Catalytic Hydrogenation of Acetylene on the Pd-Kieselguhr Catalyst
Authors: Tamaru Kenzi
Published: July 2006

1) Hydrogenation of acetylene on the Pdkieselguhr catalyst of various dispersities was investigated.

2) It was shown that the hydrogenation of acetylene proceeded not only to ethylene, but also to ethane by all the catalysts of various dispersities, and that in two distinct steps quite similarly with the Pd-alumina (1:100) catalyst.

3) The ratio of the hydrogenation rate of acetylene to that of ethylene was affected by the dispersity, suggesting the appearance of the various “active regions” of the catalyst surface to be connected with the dispersity. It was large for the catalyst of larger dispersities and this fact explains the results previously obtained by the flow method.

4) Some considerations were given to the rate-determining step in the hydrogenation of ethylene.
Application of Cation Exchange Resin to the Determination of Phosphorus in Foods
Authors: Kubo Shohji , Tsutsumi Chuichi
Published: July 2006

A new volumetric determination of phosphorus in foods using a sodium type cation exchange resin was devised and critically investigated. The substitution of sodium for the hydrogen type exchanger eliminated errors resulting from the introduction of carbonate present in concentrated alkali. Moreover, the reduction of the resin particle size resulted in simplification of the procedure and reduced the skill necessary for its execution.

This method is accurate and applicable to the determination of phosphorus in ordinary foodstuffs, except when the sample contains unusually large amount of ferric iron. In such cases, the hydrogen type exchanger method must be employed.
Influence of Substituent Groups on Nuclear Reactivity in Formations of Substituted Biphenyls through Reactions of Aromatic Diazo and Cognate Compounds with Aromatic Liquids. I. The Nitro Group
Authors: Simamura Osamu , Inukai Takashi , Kanazashi Motonori
Published: July 2006

The reactions of both n-nitrosoacetanilide and diazobenzene hydroxide with nitrobenzene give all three isomeric nitrobiphenyls, whereas the formation of only the ortho and para isomerides has been reported in the literature. All the nuclear positions of nitrobenzene are more reactive than that of benzene towards the substituting phenyl radical.
Researches on the Polarographic Diffusion Current. I. Criticism of the Ilkoic Theory and Theoretical Revision of the Ilkovic Equation
Authors: Kambara Tomihito , Suzuki Makoto , Tachi Isamu
Published: July 2006

The integral equation representing the thickness of the diffusion layer surrounding a spherical electrode is derived; upon solving this equation, the formula for the polarographic diffusion current is obtained. It becomes clear that the Ilkovic theory is not right because of its ignorance of the curvature of drop and that our revised equation can elucidate many oscillographic recordings of the polarographic current-time curves.
Biochemical Studies on Vitamin B12. I∼II
Authors: Sahashi Yoshikazu , Mikata Masayuki , Sakai Heiichi
Published: July 2006

In part I, a simple method for isolating vitamin B12 concentrate was studied.

In part II, (A) was decided to be a prosthetic group in natural (B) molecule biochemically, and the biosynthesis of (B) from synthetic (A) could be attained successfully.
Analytical Chemistry by Means of Organic Compounds XV Electrolytic Reduction of Organic Reagents at the Dropping Mercury Cathode and its Application to Amperometric Titrations — 8-Hydroxyquinoline (2)
Authors: Ishibashi Masayoshi , Fujinaga Taitiro
Published: July 2006

Magnesium was directy titrated by the amperometric method. The accuracy was 0.7% or better with 10−3  m concentration of magnesium. Its application to the analysis of alloy, brine and sea-water were studied. The interference of calcium and its elimination are described.
On the Porperties of Water Surface in Contact with Various Vapors
Authors: Ikeda Toshio , Ozaki Tokurô
Published: July 2006

The surface tension of water in various vapors were measured by the drop-volume method. As a result of the experiment, it was found that the “ Antonoff’s rule” holds good with some exceptions. In any vapors, a remarkable, but short ageing of water surface was found, which was 6 seconds in general, and which is prolonged by reduced pressure.
Separation of a Small Amount of Titanium from Iron by Ion-Exchange Resin
Authors: Yoshino Yukichi , Kojima Masuo
Published: July 2006

Separation of a small amount of titanium from iron with cation exchange resin was studied using alkali cyanide solution as eluting agent of iron. Successful results were obtained even in case of high iron concentration. This method enables us to remove the interfering effect of the iron on titanium colorimetry with hydrogen peroxide.

As an examle of practical application, this method was tried in determining the titanium content of a limonite. The result agreed with that of the ordinary method of separation.
Viscosities of the Solutions of Polyvinyl Acetate in Acetone-Water Mixtures
Authors: Yoshioka Koshiro
Published: July 2006

Viscosities of the dilute solutions of polyvinyl acetate have been measured in acetone-water mixtures of varying proportions. The experimental results are well expressed by the following equation η_sp/c=[η]+k[η]^2c. The intrinsic viscosity ([η]) shows a slight maximum at about 5% of water content, and decreases gradually for larger content of water. The value of k is close upon 0.4 and does not vary appreciably.
Fluorometric Microdetermination of Uranium. I. Fluorescent Material for the Determination
Authors: Nakanishi Masaki
Published: July 2006

As the most sensitive method for the determination of uranium, the fluorescence method is recommended. Fluorescent material of sodium fluoride containing a small amount of uranium (10−4 to 109g. per 20 mg. of sodium fluoride) was investigated in this paper from several sides.

Relation between fluorescence intensity and uranium content is described, and the fluorescence band spectrum was studied by speetrophotometry, regarding its spectral energy distribution.

Various interfering factors to this method were examined too, especially as to its analytical application.
Electronic Interpretation of Organic Reaction Mechanism. VII. Reactions and Structures of Organic Halides in Replacement Reactions
Authors: Murakami Masuo , Oae Shigeru , Takeuchi Sei
Published: July 2006

(1) It was observed in the reaction of organic chloride with silver nitrate that the irregular catalytic action can be avoided by carrying experiments in a dark room.

(2) Silver nitrate was interacted with several organic chlorides which were highly reactive in SN2 type reaction and the kinetic data obtained were fully discussed.

(3) Some organic polychlorides were reacted with silver nitrate and with potassium iodide and rates obtained in these reactions were discussed.
Amperometric Titration of Potassium with Sodium Dipicrylaminate
Authors: Yasumori Yoshikazu
Published: July 2006

In the amperometric titration of potassium with dipicrylaminate, the end-point located by the theory of Langer et  al. showed satisfactory results. The accuracy was within 1 mg. with more than 30 mg. K. In presence of 350 mg. Na, or aluminate and precipitate of ferric hydroxide the titration was not affected.
On the Etched Surfaces of Nickel Single Crystals Revealed by Means of Electron Diffraction and Microscopy
Authors: Yamaguchi Shigeto
Published: July 2006

(1) It was possible to assign the crystallographic indices to the etched surfaces of single crystals by the combination of electron microscopy and diffraction.

(2) The (110) plane of nickel crystal was most active and the (111) plane was most inactive among the principal planes of crystal.
Effect of Gelatin on the Polarographic Waves of p- and o-Nitroanilines
Authors: Tanaka Nobuyuki , Kobayashi Masako
Published: July 2006

The effect of gelatin on the polarographic waves of p- and o-nitroanilines has been investigated,

(1) Maxima of the polarographic waves of these compounds which occur in the supporting electrolyte without gelatin were supressed by adding 0.005-0.01% of gelatin to the supporting electrolyte.

(2) The wave of each of these compounds splitted into two waves when the supporting electrolyte contained more than 0.01% of gelatin.

(3) The ratio of the wave heights of the second wave to the first increased with increasing concentration of gelatin, and it was different between p- and o-compounds in the supporting electrolyte containing the same concentration of gelatin.

(4) The wave heights of the first and the second waves of each compound were proportional to the concentration.

(5) These double waves were applied to the simultaneous determination of both compounds, with the result that the procedure was available for rough estimation of content.
Magnetic Property and Resonance Character of Cycloöctatetraene (C8H8)
Authors: Shida Shoji , Fujii Saburo
Published: July 2006

We have obtained −53.9×10−6 at 30° as the molecular diamagnetic susceptibility of purified cycloöctatetraene, and its temperature dependence exceeding 0.5 percent over the temperature range 30° to 80° has not been detected. The diamagnetic anisotropy of this molecule has been estimated −12.6×10−6 per mole on some assumptions, and the resonanceenergy 2.9 kcal. per mole from the thermal data.

The relationship between the small anisotropy and the weak resonance character of this molecule has been discussed and explained qualitalively on the basis of the quantum mechanical considerations. Langevin’s theory and the original procedure of London’s method have been found to be unsuitable for the explanation of this small anisotropy.
On the Action of Carriers in the Catalytic Hydrogenation of Acetylene by Palladium Catalyst
Authors: Tamaru Kenzi
Published: July 2006

Aceytlene was hydrogenated by palladium deposited on such carriers as carbon black, active carbon (Merck), Japanese acid clay, French chalk, silica gel, granular active carbon, and quartz sand, and the functions of the carriers were considered for individual cases.

The catalysts deposited on the first four carriers catalyzed the hydrogenation in two distinct steps at 30° in the same manner as alumina and kieselguhr, that is, hydrogenation and polymerization of acetylene proceeded in the first step and then ethylene was reduced to ethane in the second step, showing a pronounced self-retardation of acetylene. It was suggested that the kind of carriers has connection with the appearance of various “active regions” with different ratios.

When the granular active carbon was used as a carrier, the hydrogenations of acetylene and ethylene proceeded not in two steps, but simultaneously. This phenomenon was explained by the slow diffusion velocity of acetylene into the inner part of the granule. Powdering the catalyst, the reflection point appeared in the hydrogenation curve and the curve was very similar to that of silica gel, suggesting a similar mechanism of the reaction.

When the quartz sand was used as a carrier, the hydrogenations of the two hydrocarbons occurred at the same time. This is explained by the retardation of the adsorption rate of acetylene by the deposited polymers to such an extent as the adsorption rate becomes to be rate-determining.

It was shown, therefore, that the granular active carbon and quartz sand are not to be used in practice for the selective hydrogenation of acetylene.
Studies on Monomolecular Films. IV. Stabilization of Monoparticle Films of Nonpolar Substances by Stearic Acid
Authors: Matuura Ryôhei
Published: July 2006

It was shown that stable surface films of nonpolar substances could often be formed on water by mixing them with stearic acid, and that in the resulting mixed films the nonpolar substance existed in the state of rather stable unit of particles, forming monoparticle films. The dimension of the surface particles could be calculated for some nonpolar substances. The mechanism of the film-stabilizing action of stearic acid was discussed and it was suggested that the different film-stabilizing substances would stabilize the film of nonopolar substance in a different manner.
Physicochemical Properties of the Surface of Aqueous Solutions. II. Foam Stability and Mechanical Properties of Surface
Authors: Kimizuka Hideo , Sasaki Tunetaka
Published: July 2006

1. The surface viscometer, the main part of which consisted of a fine vertical thread of glass carrying a horizontal platinum wire at its lower end, was devised for the measurement of the surface viscosity of solutions.

2. The measurements of the surface viscosity as well as some other surface properties of solutions of a number of dyes and saponin were carried out. The effect of coexisting alcohol and inorganic electrolyte for the saponin solution were also examined. The results showed a close correlation between the surface viscosity, the life of foam and so called membrane effect.
Structure of the “Structureless” Replica Film for Electron Microscopy
Authors: Yamaguchi Shigeto
Published: July 2006

The reason the oxide replica gives a more resolved image in electron microscopy than Formvar or collodium replica is because the small oxide particles (50-100 Å.) composing replica film are oriented according to the orientation of the metal crystals of substrates. The electrodeposited replica and sulphide film formed on metals give the resolved images in microscopy. This is explained in the same way as for oxide replica.
Statistical Thermodynamics of Solution of Rigid Rod-like Molecules
Authors: Kawai T\={o}ru
Published: July 2006

(1) A new thermodynamic relationship applicable to dilute solution of rigid rod-like molecules was derived, employing a lattice model.

(2) Small deviation from Zimm’s result for rigid rod was discussed here, considering the effect of size and shape of solvent and solute.

(3) Although quantitative discussion is impossible because of the difficulty of the estimation of the size of the submolecule, it may be said that the contribution of entropy of dilution to A2 (the second virial coefficient in osmotic pressure expression as power series in concentration) will be less for rigid rod-like molecules than for coiled molecules, and furthermore, the difference between such systems as cellulose derivatives in a series of solvents will be very small.
Studies on Foams. VII. Theory of Foam Formation of Dyestuff Solution
Authors: Nakagaki Masayuki
Published: July 2006

Considering the dynamic equilibrium of adsorption and desorption on the surface of water, Szyszkowsky’s equation is derived. Using the area of dye molecule calculated from the molecular structure, U0 and Γ2 are estimated to obtain the best conformity with the measurement of the surface tension. UΓ calculated by them is compared with the foam formation of these triphenyl methane dyes. Maximum observed in the foaming ability—concentration curve of methyl violet 5 B is explained by its large surface activity. The fact that the energy required to bring the unit area of dye molecule into the bulk solution is about 20 erg/cm.2 is justified using the correction of interfacial energy due to the fact that the thickness of the adsorption layer is nearly equal to the dimension of the range of molecular force.
The Wet Oxidation and the Structure of Carbon
Authors: Akamatu Hideo , Takahashi Hiroshi , Tamaru Kenzi
Published: July 2006

The reactivity of various kinds of carbon to the solution of potassium dichromate in phosphoric acid was examined. The samples investigated contained carbon blacks, graphite, pitch cokes, and charcoals. The rate of the reaction varied depending on the types of carbon, and the order of the reactivity was found to be in the order shown above. This is attributed to the modes of aggregation of crystallites. It was assumed that, in carbon blacks the crystallites are mobile individually for dispersing or swelling, on the other hand, in pitch cokes as well as charcoals there are some linkages to bridge the micelles with each other. This is supported by the results of the X-ray examination which was carried out following the steps of the wet oxidation.