bluuebunny/crossref_metadata_2025 huggingface dataset:
Chemical Studies of the Western Pacific Ocean. III. Freezing Point, Osmotic Pressure, Boiling Point, and Vapour Pressure of Sea Water
Authors: Miyake Yasuo
Published: July 2006

(1) The freezing point of sea water from the Western Pacific Ocean has been measured and a new empirical formula for the relation between freezing point and chlorinity has been obtained, which seems to be more adequate than Knudsen-Hansen’s equation.

(2) The osmotic pressure, the boiling point elevation and the depression of the vapour pressure of sea water have been calculated.

The author wishes to express his hearty thanks to Prof. T. Okada, Director of the Central Meteorological Observatory of Japan, for his kind guidance and the permission of publishing this report. He is also indebted to Mr. H. Matui for his earnest assistance throughout this work.
The Nature of the Complex Formation between Boric Acid and Organic Polyoxy Compounds
Authors: Tsuzuki Yojiro
Published: July 2006

By polarimetric observations with regard to the effects of H3BO3, Na2B4O7 and KBO2 on various polyoxy compounds the following results and conclusion were obtained.

Boric acid has a very feeble ability for complex formation with non-ionizable polyoxy compounds, such as mannit and glucose, while alkali borates show strong activity upon them. The order of the strengths is H3BO3<<Na2B4O7<KBO2. Complex is formed between borate ion and polyhydric alcohols. Its quantity increases with increasing BO2′.

The effects of boric acid and alkali borates on ionizable polyoxy compounds, like tartaric acid and its salts, appear somewhat complicated. In this case complex formation is possible to a large extent between free boric acid and free tartaric acid (complex I). Complexes are also formed between alkali borate and alkali tartrates (complex II), but they (II) are different in structure from those formed in acidic medium (I). The complex I is formed by the action between BO2′ and alcoholic OH groups, but complex II between B(OH)3 molecule and COO′ ion.

Calcium gluconate behaves toward boric acid and borates like alkali tartrates. H3BO3 combines with the COO′ group of the gluconate, while BO2′ reacts with its alcoholic OH groups.

Thus it has been shown that the complex formation is in general based upon the reaction between molecule and ion, and not between neutral molecules nor between ions.
Studies on the Reactions between Oxides in Solid State at Higher Temperatures. I. The Reaction between Magnesium Oxide and Titanium Oxide
Authors: Tanaka Yasuo
Published: July 2006

(1) It has been confirmed that three titanates, i.e., magnesium orthotitanate (2MgO·TiO2), metatitanate (MgO·TiO2) and dititanate (MgO·2TiO2), are formed by the solid reaction between MgO and TiO2; 2MgO·TiO2 is soluble in 4 N HCl and MgO·TiO2 in 12 N HCl, while MgO·2TiO2 is scarcely soluble even in 12 N HCl.

(2) By following the course of the reaction analytically, it has been found that the first reaction product is MgO·2TiO2, whatever the mixing ratio of the two components may be; MgO·TiO2 is formed gradually when an excess of MgO is present; and 2MgO·TiO2 is formed similarly, but with difficulty.

(3) The reaction has been proved to proceed, under various ex？erimental conditions, in the same manner, and MgO·TiO2 can never be regarded as the first reaction product.

(4) The reaction between MgO·TiO2 and TiO2 to form MgO·2TiO2 has taken place more easily than the formation of MgO·TiO2 from MgO 2TiO2 and MgO.

(5) It has been concluded that, although there exists a notable rapid initial reaction, a further reaction is controlled by the diffusion of the two components through the reaction product. The energy of activation of the diffusion process of MgO·2TiO2 formation has been estimated to be 36.0 Kilocalories per mole.
The Synthesis of Iso- and Normal Butyl Alcohols in the Presence of Calcium Carbide. (B) III. Experimental Details and Preliminary Investigations on Methanol Catalysts in the Presence of the Carbide. Dry System
Authors: Negishi Ryoji
Published: July 2006

The experimental procedure and the preparations of the catalysts used are given in detail. The effects on the activity of the carbide and of the reaction products are found to be small—if at all.

The results of the runs in dry system are tabulated, and each run is briefly described. Short discussions on the results are also given. A fuller discussion on them is reserved for a subsequent paper.
Studies on the Reactions between Oxides in Solid State at Higher Temperatures. V. The Reaction between Magnesium Oxide and Aluminium Oxide
Authors: Tanaka Yasuo
Published: July 2006

(1) It has been found that pure MgO·Al2O3 is formed at first in this reaction, and the solid solution rich in A12O3 is formed gradually when an excess of Al2O3 is present.

(2) Although there exists a rapid initial reaction, the later reaction is controlled by the diffusion process with an energy of activation of 41.1 Kilocalories per mole.

(3) The reaction proceeds more easily with the mixtures containing an excess of MgO than with the other mixtures.
The Oxygen Effect in the Hydrogen Bromide Catalysis of the Addition Reaction of Bromine to Cinnamic Acid in Carbon Tetrachloride Solution
Authors: Simamura Osamu
Published: July 2006

It has been found that a joint action of hydrogen bromide and oxygen accelerates the addition of bromine to cinnamic acid in carbon tetrachloride solution in the dark, whereas the reaction is retarded by either of them. The catalyzed reaction is prevented by catechol, and hydrogen chloride cannot be substituted for hydrogen bromide without the dis？ppearance of the accelerating effect. On the basis of these observations the nature of the alleged catalysis of the addition of bromine by hydrogen bromide has been elucidated. The elimination of the induction period, which is certainly attributable to the inhibitory action of oxygen, is not due to the removal of the latter. The explanation offered is that hydrogen bromide and an ethenoid compound in co-operation with the very oxygen starts a rapid chain reaction involving bromine atoms and free radicals. Also for the uncatalyzed addition of bromine to cinnamic acid in carbon tetrachloride a possibility of a mechanism involving chains has been suggested.
On the Metallo-organic Compounds. XII. Dialkyltin Sulphide R2SnS (or tri-thio-anhydro-tris-dialkylstanne-dithiol (R2SnS)3)
Authors: Harada Taichi
Published: July 2006

Dialkyltin sulphide has been prepared by treating dialkyltin dihalide with KSH in absolute alcohol, saturated with hydrogen sulphide. The six-membered hetero-cyclic structure

(Remark: Graphics omitted.)

and the term tri-thio-anhydro-tris-dialkylstanne-dithiol are suggested for the compound from the results of the molecular weight determination.
ON THE PRESERVATION OF THE STANDARD SOLUTION OF OXALIC ACID AND ON THE READING OF THE BURETTE
Authors: Ishimaru Saburo
Published: July 2006

(1). The standard solution of oxalic acid should always be kept in a reagent bottle carefully wrapped with black paper. The solution thus preserved does not change its strength, irrespective of the presence or absence of sulphuric acid. Hence the old standard solution kept in a black bottle can as well used for titration.

(2). The method of preservation of the oxalic acid solution, described in Treadwell’s “Analytical Chemistry” is not appropriate; the addition of sulphuric acid is not only unnecessary but objectionable, because the velocity of decomposition of the oxalic acid solution kept in a colorless bottle, becomes greater with the increase in the concentration of sulphuric acid added.

(3). A convenient device for the correct reading of the burette is described.
SPECTROSCOPICAL STUDY OF AMINO-ACID ANHYDRIDES. II. LIGHT ABSORPTIONS OF SOME AMINO-ACIDS, THEIR ESTERS, PEPTIDES AND ANHYDRIDES
Authors: Shibata Yuji , Asahina Tei-ichi
Published: July 2006

(1) Glycocoll, alanine, leucine, phenylalanine, tyrosine, glycocoll ester, tyrosine esters, glycylleueine, glycyl-l-phenylalanine, glycyl-d,l-phenyl alanine, glycyl-l-tyrosine anhydride, tyrosine anhydride, glycyl-l-leucine anhydride, leucine anhydride, glycyl-l-phenylalanine anhydride and phenylalanine anhydride were spectrochemically studied in aqueous, alcoholic or glacial acetic acid solutions.

(2) Among these compounds only those which contain phenyl and oxy-phenyl groups in their molecules show selective light absorptions ; i.e., tyrosine, phenylalanine and their derivatives, except phenylalanine, anhydride absorb selectively.

(3) Although two phenyl groups exist in its molecule, phenylalanine anhydrid show only end absorption, perhaps due to the mutual effect of these two chromophores symmetrically situated to each other.

(4) Derivatives of either tyrosine or phenylalanine absorb identically with their mother substances.

(5) Other amino-acids, their esters, pepetides and anhydrides show no selective absorptions, as in the cases of glycocoll anhydride, alanine anhydride and sarcosine anhydride which were described in our previous paper.

(6) As for the constitution of amino-acid anhydrides, the same conclusion as was previously mentioned, may be applied again to the substances now studied, that is to say, all these anhydrides are in keto-form.
On the Equilibrium of the Radioactive Elements in the Hydrosphere. I
Authors: Kuroda Kazuo , Yokoyama Yuji
Published: July 2006

The equilibrium relationships of the radioactive elements in the hydrosphere was studied. The radium, radon, radium A, radium B, radium C, radium F (polonium), thorium X, thoron, and thorium B content of mineral springs of Masutomi was estimated, and discussed from geochemical point of view. It was found that spring B7 shows the high content of thorium X and thoron. Spring A49, on the other hand, showed the high content of radon and polonium. It was also found that the decay products of radon are contained in fresh mineral springs in considerably lower amounts compared with those expected from the radon contents.

The authors take this opportunity of heartily thanking Prof. Ken-jiro Kimura for his kind guidance in the course of this study. The cost of this research was defrayed from the Scientific Research Encouragement Grant from the Department of Education, to which our thanks are due.
On the Equilibrium of the Radioactive Elements in the Hydrosphere. II
Authors: Kuroda Kazuo , Yokoyama Yuji
Published: July 2006

(1) The equilibrium relationships of the radioactive elements in the hydrosphere were studied.

(2) The radioactivity of the rain water and the fumarole vapour was measured.
Mechanisms of Agglomeration of Red Cells by High Polymer Compounds
Authors: Inokuchi Kiyoshi
Published: July 2006

The mechanisms of agglomeration of erythrocytes caused by hydrophilic negative polymers were investigated and the following views were proposed.

(1) Among the negative colloids, fibrous colloids show the erythrocyte agglomeration, while spherical ones do not cause it.

(2) Agglomeration by the negative colloids is caused by two actions, i. e., adsorption of these polymers upon cells and their action to join cells together. Those substances which lack either or both of these actions fail to cause the agglomeration.

(3) Fibrous structure of macromolecule favors these actions on account of the large extension of molecule and adequate flexibility of each part of the molecule in solution.

(4) The dissociated or dipol radicals of the negative polymers and amino groups of the protein of cell surface are considered to be the centres of adsorption respectively.
The Crystal Structure of Alpha-amino Isobutyric Acid
Authors: Hirokawa Sakutaro , Kuribayashi Shunsuke , Nitta Isamu
Published: July 2006

X-ray examination of crystals of α-amino isobutyric acid shows them to be built upon a composite monoclinic unit having a=10.59 kx, b=8.97 kx, c=11.34kx, and β=94°, containing eight molecules. The space group is C2/c with all atoms being in the general positions with the following parameters which were determined by the three-dimensional Fourier analysis; nitrogen: x=0.154, y=0.100, z=0.388; carboxylic carbon: x=0.178, y=−0.025, z=0.199; α-carbon: x=0.212, y=−0.031, z=0.331; methyl carbon 1: x=0.355, =−0.027, z=0.365; methyl carbon 2: x=0.148, y=−0.167, z=0.382; oxygen 1: x=0.112, y=0.083, z=0.159; oxygen 2: x=0.224, y=−0.121, z=0.138. Bond distances are 1.26 and 1.20 kx. for carbon-oxygen, 1.52, 1.53 and 1.54 kx. for carbon-carbon and 1.49 kx. for carbon-nitrogen. There are observed a considerably close intramolecular approach between nitrogen and oxygen atoms and also close contact between two methyl groups.
The Bitter Substance, Produced in Black-rotten Sweet Potato. II. On the Constitution of Ipomoeamarone. Part 1
Authors: Ohno Takashi
Published: July 2006

Ipomoeamarone is an open-chain ketone with two oxide rings and two ethylenic linkages. It gives a liquid keto-acid and oxalic acid by oxidation with potassium permanganate at room temperature, and acetone, acetic acid, oxalic acid and a liquid acid by oxidation with the same reagent at 100°.
The Crystal Structure of “Dichrochloride”, [Co(NH3)3H2OCl2]Cl
Authors: Tanito Yoshimichi , Saito Yoshihiko , Kuroya Hisao
Published: July 2006

An X-ray diffraction study of crystals of dichloro-aquo-triammine-cobalt (III) chloride eads to a hexagonal unit of structure with a=7.37 a. and c=8.75 a., containing two formula units in it. The most probable space group is D6h4−C6/mmc. For an accurate determination of the structure, the method of three dimensional Fourier series was used. The determined structure is most easily described as NiAs type, consisting of [Co(NH3)3H2OCl2]+ and Cl− ions. Two chlorine atoms are coordinated to a cobalt atom in trans-positions with respect to each other, each being 2.33 A. from the cobalt atom. The Cl-Co-Cl direction being parallel to the c-axis, the octahedral complex ions seem to have statistical azimuthal orientations in the crystal and the apparent, symmetry of the complex ion is D3h− 6m2. Such an arrangement of the complex ions in the crystal may well account for the marked red-blue dichroism of the crystals.
The Relation between the Geometrical Configurations of Inorganic Complexes and their Absorption Bands. III. A General Rule for the First and Second Bands of Co (III) Complexes
Authors: Shimura Yoichi
Published: July 2006

A survey of the absorption data of the tetrammine- or bisethylenediamine-Co(III) complexes available in previous literature as well as in the author’s measurements has shown that the frequency differences of the first bands (or second bands) of the cis- and trans-isomers are closely related to the spectrochemical series of the ligands which coördinated in cis- or trans-positions. This correlation has been interpreted as the result of a trans-influence of the ligands, i.e., a trans-substitution causes a greater shift of the first band (or second band) than corresponding cis- substitution. The visible and ultraviolet absorption spectra of two isomers of [Co(NH3)4NO2·NCS]+ have been measured and the steric configurations of both ions have been determined.
The Structure of Surface-Denatured Protein. I. Molecular Weight and Surface Area of Horse Serum Albumin Molecule
Authors: Imahori Kazutomo
Published: July 2006

1. The molecular weight of the surface denatured serum albumin molecule is measured from the FA–F curve. The experiment has shown it to be about 70,000.

2. The surface area covered by one surfacedenatured serum albumin molecule is determined to be 9820 Å.2 from the compressibility measurement.
Influence of Substituent Groups on Nuclear Reactivity in Formations of Substituted Biphenyls through Reactions of Aromatic Diazo and Cognate Compounds with Aromatic Liquids. II. The Bromine Atom
Authors: Simamura Osamu , Inukai Takashi , Kurata Masaya
Published: July 2006

The reaction of N-nitrosoacetanilide or benzenediazo hydroxide with bromobenzene gives all three isomerides of bromobiphenyls, the yields decreasing in the order ortho > meta > para. All the nuclear positions of bromobenzene are more reactive than benzene towards attack by the phenyl radicals.
Dephosphorylation of Nucleic Acids, Mononucleotides and Casein by Lanthanum and Cerium Hydroxide Gels
Authors: Shimomura Michio , Egami Fujio
Published: July 2006

1. The dephospkorylation reaction of RNA by lanthanum hydroxide gel was further studied. The activation energy of the reaction is 20,200∼20,400 cal. Optimal pH is between 8 and 9.

2. RNA is hydrolysed almost completely into nucleosides and inorganic phosphate at 90° in 40 hours at pH 8. The formation of nucleosides as the final product of hydrolysis was shown from the reducing power measurements and periodate consumption of products.

3. DNA is not dephosphorylated at all under conditions where RNA is almost completely dephosphorylated. This may be related to the structural difference of DNA and RNA.

4. Preparative method for ribonucleosides from RNA under catalytic effect of lanthanum hydroxide was described. Ribonucleosides are obtained in good yields.

5. Desoxyribo-, a-ribo-, b-ribo-, and 5′-ribocytidylic acid are all subject to catalytic dephosphorylation. 5′-Ribocytidylic acid is dephosphorylated most slowly.

6. Cerium hydroxide can be used as catalyst of the reaction in the same way with lanthanum hydroxide.

7. The dephosphorylation of casein is considerably accelerated by lanthanum hydroxide at 70° but not at 25°.
Derivatives of dl-Aminopropanediols
Authors: Urakami Chieko , Kakeda Kasumi
Published: July 2006

Derivatives of 1-aminopropanediol, 2-aminopropanediol and the halogenated acyl esters of glycerol have been prepared. The amino group has been acylated with haloalkylacyl group and one or both hydroxyl groups with aliphatic acids of various chain lengths. Preliminary experimental results have shown that these compounds exhibit bacteriostatic activity in vitro against mycobacterium tuberculosis, avian. The chemical constitution of the isomeric products, the 1-amino and 2-amino derivatives, has been confirmed. The preparation of the optical active forms of the aminopropanediols are now in progress.
On the Ring-Opening Reactions of the Furan Compounds. I. The Synthesis of 1,4-Pentadien-3-one-1, 5-dicarboxylic Acid from 2-Furanacrylic Acid
Authors: Midorikawa Hiroshi
Published: July 2006

2-Furanacrylic acid gave 1,4-pentadien-3-one-1,5-dicarboxylic acid in a fairly good yield by treatment with aqueous hydrogen peroxide containing hydrochloric acid. This acid underwent the same photochemical change by direct sunlight as its methyl ester. This acid was reduced to γ-ketopimelic acid hydrazones of the acid by aluminium amalgam, and oxidised to fumaric and oxalic acids by potassium permanganate. It is assumed that the two double bond have the trans structure. The phenyl-hydrazones of the acid and the methyl ester were obtained.
The Dielectric Constant of Dispersion of Spherical Particles
Authors: Kubo Masaji , Nakamura Sankichi
Published: July 2006

The dielectric constant of the dispersion, in which spherical particles of dielectric constant ε1 are dispersed in a medium of dielectric constant ε0, has been worked out theoretically without employing Wiener’s proportionality postulate. The following equation has been derived for the relation between the dielectric constant ε of the dispersion and the volume fraction φ of the disperse phase.

(Remark: Graphics omitted.)

Where c=1−4π/9√3
The Action of Hydrogen Bromide and Oxygen on α,α′-Dimethylstilbene and Related Compounds
Authors: Suzuki Hiroshi , Simamura Osamu , Ichihashi Toshiko
Published: July 2006

The action of hydrogen bromide on cis- or Trans-α,α′-dimethylstilbene in the presence of a peroxidic substance or of bromine in carbon tetrachloride in the dark below room temperature caused a partial isomerization to the respective geometrical isomers. The reaction was inhibited by catechol. When oxygen was allowed to react simultaneously under otherwise the same experimental conditions, the cleavage of the central double bond took place yielding acetophenone and α-bromoacetophenone along with 1,4-dibromo-2,3-diphenyl-2-butene. Similar experiments with α-methylstilbene and α,α′-diethylstilbene were conducted. The action of oxygen and bromine on α,α′-dimethylstilbene caused the same oxidative cleavage of the double bond as with hydrogen bromide and oxygen. It was pointed out that an ethylenic compound which is sterically hindered to such an extent that it is unreactive towards molecular reagents can be reactive enough towards radical reagents.
The Effect of Conversion on the Mechanism of Vinyl Polymerization. II. Methyl Methacrylate
Authors: Fujii Saburo
Published: July 2006

The usual photochemical method and the rotating sector technique have been used to study the effect of conversion on the termination mechanism in the polymerization of methyl methacrylate. The strong rate acceleration, the extreme increase in kinetic chain lifetime and some decreases in the overall activation energy and the reaction order of chain termination have been detected with increasing conversion of the reaction system. These results are in good agreement with those reported on styrene in the first paper of this series and with the available data on this polymerization. These results have been discussed under several assumptions and confirmed to be due to a large change in the termination mechanism, i. e., from the activation-controlled termination of polymer radicals in the initial stages to the predominant diffusion-controlled termination in the later stages.
On the Molecular Rotations of Polypeptides of Alanine
Authors: Murakami Hideo
Published: July 2006

Molecular rotations of a series of polypeptides of alanine have been calculated theoretically. We have assumed the molecular model which is constructed by sevenmembered rings due to intra-molecular hydrogen bonds (α-type configuration). Calculations are carried out for the both effects of one-electron theory and dynamical coupling theory, and the results correspond relatively well to experimental results. This fact probably indicates the appropriateness of the assumed model. In order to obtain a decisive conclusion, however, it is necessary to proceed with the calculations for other models and compare the results quantitatively. This is a task for future study.
The Spatial Configurations and the Ultraviolet Absorption Spectra of Biphenyl and Some Related Compounds
Authors: Suzuki Hiroshi
Published: July 2006

The quantitative relations between the degree of deviation from coplanarity of the molecular configuration and the ultraviolet absorption spectrum as well as the extent of conjugation for the biphenyl-type compounds have been determined by calculations based on the molecular orbital method. On the basis of the results, the spatial configurations of biphenyl, o-methylbiphenyl, o,o′-dimethylbiphenyl, fluorene, 9,10-dihydrophenanthrene, 4,5-methylene-9,10-dihydrophenanthrene, 2, 7-dihydro-3,4-5,6-dibenzoxepin, and 2, 7-dihydro-3,4-5,6-dibenzazepinium-1-spiro-1'″piperidinium bromide have been discussed.
Surface Chemistry of High Polymers, IV. The Monolayer of Polymeth-acrylic Acid and its Copolymers with Diethylaminoethyl Vinyl Ether at the Air/Water Interface
Authors: Isemura Toshizo , Hotta Hiroshi , Otsuka Seinosuke
Published: July 2006

As the result of the measurements of the surface pressure and surface potential of polymethacrylic acid and its copolymers with diethylaminoethyl vinyl ether on the aqueous phase at various pH, their surface moment was constant up to pH 4.0, then rapidly fell down to zero between pH 4.0 and 5.5, and finally their stable film could not be found at the higher pH range than 5.5, but the surface pressure decreased with increasing pH even up to pH 4.0. These tendencies are discussed in the light of Katchalsky’s interpretation in regard to the relation between the shape of molecules and the degree of ionization.

The important conclusions from the present experiments are :

(1) all the side chains of the present polymer are immersed in the aqueous phase;

(2) the degree of ionization of amine groups may be of about 20% even at its maximum; and

(3) the isoelectric point of the present copolymer at the interface exists at about pH 5.0 of the aqueous phase.
Lower Electronic States of the Free NH2 Radical
Authors: Higuchi Jiro
Published: July 2006

LCAO MO’s and ionization potentials have been calculated for the 2B1 state of the free NH2 radical by using the LCAO-SCF method. The interactions of all electrons have been explicitly considered, but the orthogonal relationship between the 1s orbitals of nitrogen and hydrogen was assumed. Using these MO’s the lower electronic states have also been investigated without configuration interaction. The calculated value of a 2B1→2A1 transition is 1.8 ev in fairly good agreement with the observed one of the α bands of ammonia in the region of 4500 to 7400 Å. The calculated bond angles of the 2B1 and the 2A1 state are about 110° and 150°, respectively. These results are in good agreement with the observation and the opinion by Herzberg and Ramsay and the estimation by Luft.
Studies on Hydration by Ultrasonic Interferometer. V. The Change of Hydration of Inorganic Electrolytes with Temperature
Authors: Sasaki Tunetaka , Yasunaga Tatuya
Published: July 2006

Sound velocity was measured at the temperature ranging from 0° to 60°C for water and the aqueous solutions of NaCl.

The amount of hydration was calculated from the sound velocity data for NaCl, which was shown to change linearly with the square root of temperature.

Volume contraction due to the dissolution of NaCl was also calculated at various temperatures which was found to change proportionally with the amount of hydration. The proportionality constant (0.10) was the same as obtained when the nature of the salt was changed. The mean hydration pressure was estimated to be about 4000 atmospheres.

A part of the cost of this study has been defrayed from the Scientific Research Expenditure of the Ministry of Education, given to one of the authors.
Internal Rotation in n-Propyl Chloride and Bromide
Authors: Komaki Chizuko , Ichishima Isao , Kuratani Kenji , Miyazawa Tatsuo , Shimanouchi Takehiko , Mizushima San-ichiro
Published: July 2006

Infrared spectra of n-propyl chloride and bromide have been measured in the gaseous, liquid and solid states. The Raman measurement was also made in the liquid state. From the normal vibration calculation and by comparison with the spectra of ethylene chlorhydrin it has been concluded that in the liquid state both the trans and gauche forms are present and of these only the trans form persists in the solid state. The energy difference between the trans and the gauche forms has been determined by the absorption intensity measurement.
Magneiochemical Study of Violanthrene-iodine System
Authors: Matsunaga Yoshio
Published: July 2006

The magnetic susceptibility of violanthreneiodine complex was measured as a function of iodine concentration. This complex shows the large discrepancy between the observed susceptibility and the estimated one which was derived by direct application of the additivity law. Perylene-bromine, peryleneiodine, and violanthrene-bromine show a similar behavior also. The susceptibility-composition curve in violanthrene-iodine system suggests the existence of molecular complex containing one molecule of violanthrene and two of iodine. At that composition, the discrepancy exceeds 35 per cent. This depression of diamagnetism is so large that we can not explain it by the localization of π-electrons in aromatic molecule. The occurrence of paramagnetic state is taken into consideration, and the nature of this state is discussed. The large difference between observed and estimated susceptibilities is attributed to the partial cancellation of diamagnetism by the paramagnetic contribution of free electrons produced by the intermolecular charge-transfer force which spreads out widely and strongly in this solid complex.
Determination of Carbon in Organic Compounds by the Iodic Acid Decomposition Method
Authors: Ohashi Shigeru
Published: July 2006

(1) A new wet combustion method for the determination of carbon in organic compounds has been developed.

(2) A sample is decomposed by heating with a mixture of potassium iodate and strong phosphoric acid. The liberated carbon dioxide is absorbed in 0.1 n sodium hydroxide, using a spiral type absorber. After adding barium chloride solution the excess sodium hydroxide is titrated with 0.1 n hydrochloric acid, using thymol blue as indicator, in the absorber.

(3) A part of the liberated iodine is absorbed into the tube filled with anhydrous sodium thiosulfate in order to avoid the absorption of the iodine in the alkali solution in the absorber.

(4) Analyses for several organic compounds gave satisfactory results. Using 10 to 60 mg. of samples, the accuracy was with in ±2%. Analysis time for one sample is about fifty minutes.
The Effect of Some Surface Active Substances on the Polarographic Reduction Process of Metallic Ions
Authors: Tamamushi Reita , Yamanaka Teruko
Published: July 2006

The effect of three detergents on the polarographic electrode reduction processes of Tl+-, Pb2+- and Ni2+-ions was studied together with the E-C curve of these detergents. It was shown that these detergents were very effective to suppress the polarographic maximum and their surface excess was shown to be very small at the concentration range of their MSP from the study of the E-C curve. The half-wave potential was shifted to the more negative and the shape of the c-v curve was distorted by the presence of these detergents, the degree of which was the largest in the case of Ni2+-ion and the least in the case of Tl+-ion. The anionic detergent seemed to have a larger effect than the cationic one on the electrode process with the half-wave potential more positive than the E-C max., and vice versa. It was shown that the effect of the detergents on the polarographic c-v curve was parallel to the result on their adsorption phenomena obtained from the E-C curve. From these results it was concluded that the polarographic electrode process is greatly influenced by the change in the structure of the electrical double layer and that it will be the electron-transfer process which is mainly affected by the presence of the adsorption layer of the surface active substances.
Effects of Quenching and Annealing in Manufacture of Fused Iron Catalyst upon Activity for Ammonia Synthesis and Potash Distribution
Authors: Uchida Hiroshi , Todo Naoyuki
Published: July 2006

Catalysts of four different promoter compositions…5% Al2O3, 1% K2O for catalyst No. 1; 4% Al2O3, 1% CaO, 1% K2O for No. 2; 3% Al2O3, 2% SiO2, 1%K2O for No. 3; and 3% Al2O3, 2% SiO2, 1% CaO, 1% MgO, 2.5% K2O for No. 4…were subjected, immediately after their fusion, to different cooling rates such as quenching, annealing and normal cooling.

Among the differently cooled catalysts, the annealed catalyst tended to reveal much lower activity for ammonia synthesis than the normally cooled one, but the quenched catalyst revealed the same.

The characteristic microscopic structures of catalysts of different promoter compositions were more or less markedly modified by annealing to develop large and structually more homogeneous grains, and part of the potash in these catalysts dissolved in water more or less remarkably according to the promoter composition as well as the cooling rate. In other words, the amount of insoluble potash in the catalysts was increased somewhat or considerably by the addition of lime or silica respectively, and the greatest quantity was found in the normally cooled catalysts while the smallest was in the annealed. After the reduction of differently cooled catalysts, the largest surface area was exhibited by the normally cooled catalyst, and the smallest by the annealed, but the surface concentration of potash (+lime) was nearly the same for three differently cooled catalysts. The catalysts of different promoter composition revealed also their characteristic electronic images. After annealing, the images from the interior of grains disappeared in the case of catalysts No. 1 and No. 2. but such disappearance was less remarkably found with catalysts No. 3 and No. 4.

From the results obtained, the interpretation of the decrease due to annealing of catalytic activity has been intended on the basis of the distribution state of the promoters. Some of the effects exerted by the addition of lime can be explained on the same basis, but the peculiar effects of the addition of silica on both activity and structure remains unexplicable despite the promising effect for manufacture of the highly active catalyst.
The Magnetic Susceptibility of Iodine in Various Solvents
Authors: Kondo Michio , Kishita Michihiko , Kimura Masao , Kubo Masaji
Published: July 2006

The diamagnetic susceptibility per gram of iodine in solutions of various solvents was measured with a Gouy magnetic balance at room temperature. The value −0.363×10−6 in hexane solution was practically identical with that of iodine in pure phase. The values of diamagnetism of iodine in carbon disulfide, benzene, toluene, ethyl alcohol, and acetone ranging from −0.329 to −0.341 are only slightly smaller than the value in hexane, in disagreement with the data found in literatures. A qualitative support for the present writers’ result was afforded by theoretical considerations based on Mulliken’s theory of complexes formed in accordance with the mechanism of electron transfer from a donor molecule to an acceptor.
Studies on the Chemical Constitution of Agar-agar. XVIII. Isolation of a New Crystalline Disaccharide by Enzymatic Hydrolysis of Agar-agar
Authors: Araki Choji , Arai Kiyoshi
Published: July 2006

1. A new crystalline disaccharide has been isolated from enzymatic hydrolysates of agar. Its hexaacetate and phenylosazone have been prepared in crystalline states.

2. The name neoagarobiose has been assigned to the disaccharide isolated.

3. The structure of neoagarobiose has been shown beyond doubt to be 3-O-3′, 6′-anhydro-l-galactopyranosyl-d-galactose. It has been suggested that the glycoside linkage is of α′-configuration.
Ionization Potentials of Some Organic Molecules. I. Apparatus
Authors: Omura Itiro , Higasi Keniti , Baba Hiroaki
Published: July 2006

Instrumental details of electron impact method for determining ionization potentials are recorded. Further, it is shown that the potential values obtained by the present method are in good agreement with the data reported by the previous workers.
Studies on the Intramolecular Hydrogen Bond in Conjugated Systems by the Measurements of Dipole Moments. I. o-Nitrophenol
Authors: Eda Bunzo , Ito Kazuo
Published: July 2006

Dipole moments of o-nitrophenol, 4-chloro-2-nitrophenol, 4-methyl-2-nitrophenol, o-nitroanisole and 4-chloro-2-nitroanisole were measured in benzene solutions. Their values are 3.16, 2.35, 3.49, 4.83 and 4.60 D respectively. Instead of obtaining the directions of the dipole moments of phenol and anisole, μx and μy, the two components in x- and y- directions in the molecular plane, were evaluated from the moments of their derivatives. When the dipole moments of o-nitro-phenol, o-nitroanisole and their derivatives were calculated according to the vector addition using these components, the calculated moments for o-nitrophenol and its derivatives do not agree with the observed ones whereas fairly good agreement was found between the observed and calculated ones for o-nitroanisole and its derivative. The order of the discrepancy is 0.3–0.4 D in x-direction and 0.2–0.35 D in y-direction. The authors suggest that the cause of this discrepancy is due mainly to the formation of an intramolecular hydrogen bond.
Magnetochemical Study of Dianthraquinone and its Thermochromism in the Solid State
Authors: Matsunaga Yoshio
Published: July 2006

The magnetic susceptibilities of dianthraquinone and its seven related compounds were measured by the Gouy method. The effect of conjugation between the constitutional fragments of the molecule was discussed with the aid of theoretical values of diamagnetic anisotropies. The depression of molar susceptibility of dianthraquinone was attributed to the localization of π-electrons in the central ethylene linkage, owing to the large distortion of the molecule. The remarkable decrease of susceptibility and the complete vanishing of sharp diffraction patterns in X-ray diagram accompanying the color change on heating of dianthraquinone were shown. The author concluded that the net change occurring in the so-called thermochromism of solid dianthraquinone is an irreversible chemical reaction.
Spedrochemical Study of Microscopic Crystals. XII. Polarized Absorption Spectra of Cupric Complexes with Tropolone and Related Compounds
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Polarized absorption spectra of cupric complexes with tropolone, hinokitiol, acetylacetone and salicylaldehyde have been determined in the visible and ultra-violet by Tsuchida-Kobayashi’s microscopic method. The above compounds all exhibit two bands at about 40 to 55×1013/sec. (band A) and at about 70×1013/sec. or shorter wave-length (specific band). The following rules on the dichroism which are common for the above complexes, have been induced : For the band A, the absorption parallel to the complex plane is highly hyperchromic to the absorption normal to the complex-plane. For the specific band, the absorption parallel to the π-electron system is found considerably bathochromic to the absorption normal to the plane.

With different ligand ions, the wave-length of the band A of the cupric complexes have been compared, and the following hypsochro mic order has been derived: acetylacetone> salicylaldehyde> tropolone>, hinokitiol. The same order has been found for the wave-length shift of the specific band from the corresponding band of the free ligand.

The above results have been discussed in relation to the electronic state of the complexes and the ligands.
Physical Properties and Crystal Structure of 1,1,1,2-Tetrachloro-2-methylpropane
Authors: Koide Tsutomu , Oda Tsutomu , Nitta Isamu
Published: July 2006

1,1,1,2-Tetrachloro-2-methylpropane is cubic at room temperatures. X-ray date may be interpreted on the basis of a body-centered packing of molecules in disorder, orientational or rotational. The cube edge of the unit containing two molecules is a=7.4Å. The crystal undergoes transition at about −62.2°C, when cooled, and at −39.7°C,when heated starting at a lower temperature.
Partial Methanolysis of the Mucilage of Chondrus Ocellatus Holmes
Authors: Araki Choji , Hirase Susumu
Published: July 2006

1. The mucilage of Chondrus ocellatus Holmes has been investigated by the partial methanolysis method.

2. A new disaccharide, the structure of which is shown to be 4-O-β-d-galactopyranosyl-3,6-anhydro-d-galactose, has been isolated in the form of its dimethylacetal and methyl β-glycoside in a good yield.

3. The disaccharide has been named carrabiose.

4. It has been suggested that 1→3′ linked carrabiose represents the repeating unit for the most part of the carbohydrate of the Chondrus mucilage.
Investigation on Mixed Complex. I. Spectrophotometric Study of Mixed Complexes Formed by Cupric Ion and Bidentate Ligands
Authors: Kida Sigeo
Published: July 2006

The dismutation constants of the three mixed complexes [Cu en ox], [Cu en aca]+ and [Cu dgH aca] were determined photometrically. The negative logarithms of their dismutation constants were found to be 1.10, 0.42 and \={1}.96 respectively.

By the use of determined, dismutation constants absorption spectra of these mixed complexes were found. The frequency of the absorption maximum was found to coincide with the mean value of the parent complexes. At the same time the absorption of the mixed complex is generally stronger than the mean absorption of the parent complexes.
A New Spectrophotometric Method for the Determination of Small Amounts of Chloride Using the Mercuric Thiocyanate Method
Authors: Iwasaki Iwaji , Utsumi Satori , Hagino Ken , Ozawa Takejiro
Published: July 2006

A new spectrophotometric method suitable for the determination of a small amount of chloride using iron alum solution in nitric acid solution, and mercuric thiocyanate solution in a mixture of dioxane and alcohol solution has been established.

The calibration curves conform to Beer’s law at concentrations up to 50 p. p. m. of chloride. The calibration curves are reproducible within ±1% for the range of 5-80 p. p. m. Cl− (Procedure A), and within ±0.05 p. p. m. for the range of 0.05-5 p. p. m. Cl− (Procedure B). As the calibration curves are affected by temperature, it is necessary to measure the absorbance always under the same conditions of temperature in order to achieve good accuracy.

The colored solution is stable. A very small volume of the sample solution such as 5 cc. or 2.5 cc. is good enough for the determination. Interfering substances are few, because this method is carried out in acid medium. Br−, I−, CN−, SCN−, S2−, S2O32−, BrO3−, [Fe(CN)6]4− and [Fe(CN)6]3− interfere, but usually they are not present in natural waters in concentrations that would give a serious error.

This simple method is suitable for rapid determinations, because it is unnecessary to control pH or filter the precipitate. It is suggested that this method can be widely applied to the determination of chloride in waters, rocks, etc.
Metal Chelate Compounds with Higher Rings. I The Preparations and Some Properties of Copper (II) Complexes of ω-Aminocarboxylic Acids
Authors: Nakahara Akitsugu , Hidaka Jinsai , Tsuchida Ryutaro
Published: July 2006

Three new compounds, bis-(γ-aminobutyrato)-copper(II), bis-(δ-aminovalerato)-copper (II), and tetrakis-(ε-carboxyamylamine)-coppe(II) perchlorate, have been prepared. The first and the second compound belong to the bis-(glycinato)-copper(II) type, having a 7-and 8-membered ring, respectively. The last compound has a structure of ammine-derivative complex. In all cases preparations were carried out in non-aqueous media such as ether and chloroform.

It has been concluded that the 8-membered ring is the highest ring for the formation of metal chelate compounds, so far as the copper(II) complexes of ω-aminocarboxylic acids are concerned.

Stability of higher chelate rings was considered as the functions of steric constraints and electronic influences which may be induced with the separation of the two functional groups.
SPECTROCHEMICAL STUDIES OF HYDROXYAZO-COMPOUNDS. PART VI
Authors: Uemura Taku , Tabei Shozo
Published: July 2006

1. The c-hydroxyl-group in hydroxyazo-compounds gives rise to two bands in their absorption carves.

2. The methyl-group shows perhaps no influence upon the shape of the absorption curves of hydroxyazo compounds.
ON THE OXIDATION OF STANNOUS HYDROXIDE IN SODIUM CARBONATE SOLUTION BY MEANS OF AIR
Authors: Miyamoto Susumu
Published: July 2006

1. The oxidation velocity of stannous hydroxide suspended in sodium carbonate solution of various concentrations by means of air was studied. The oxidation velocity was independent of the quantity of stannous hydroxide.

2. The effect of the concentration of sodium carbonate on the reaction velocity was small.

3. It was ascertained that sodium stannite is oxidized rapidly, while stannous hydroxide is oxidized very slowly by means of air.

4. The effect of temperature on the reaction was small.
ON ENANTIOTROPY AND MONOTROPY. I
Authors: Nagasako Noboru
Published: July 2006

It is a well known fact that there are two distinct behaviours of dimorphism in which transitions are of reversible and irreversible natures. O. Lehmann was the first in classifying it by the two categories, enantiotropy and monotropy. Later it was interpreted by Ostwald and others on the basis of the phase theory. However, clear definitions have not been made so far, which are consistent with all the experimental cases in the wide range of pT-diagram. To make it more complete and concrete, some definitions are given for the terms enantiotropy and monotropy. These terms not only serve to express the absolute stability but also to express the mutual stability of the two modifications in one component. The thermodynamic relations connected to them are also described. The cases of pseudequilibrium are also spoken of. As the result of these considerations, various theories on enantiotropy and monotropy are brought into one conformity.
ON THE DISSOLUTION VELOCITY OF OXYGEN INTO SODIUM HYDROXIDE, SODIUM CARBONATE AND HYDROCHLORIC ACID SOLUTION
Authors: Miyamoto Susumu
Published: July 2006

1. The dissolution velocity of oxygen when air was passed into sodium hydroxide, sodium carbonate and hydrochloric acid solution under some conditions was calculated from the oxidation velocities of sodium sulphite, stannous hydroxide and stannous chloride.

2. The mechanism of some negative induced reactions was discussed.
Studies on the Organic Phosphorescence. II. A Revision of Lewis’ Mechanism for the Phosphorescence
Authors: Kato Shunji , Koizumi Masao
Published: July 2006

Decay curves of the trypaflavine-silica gel phosphor were measured accurately by means of an oscillograph and a marked deviation from linearity was found at the initial stage. From the spectroscopic studies of fluorescence and phosphorescence, and the effect of light intensity on the shape of the decay curve, it was concluded that Lewis’ scheme must be modified in such a way that another state with a life time of the same order as that of T state directly couples with T state.
Action of Emulsifier upon Compositions of Emulsion Copolymers of Acrylonitrile and Water-insoluble Monomers
Authors: Uchida Moriya , Nagao Hideo
Published: July 2006

The following are the facts found from the monomer-polymer composition curves of aqueous copolymerization of the water soluble monomer as acrylonitrile and the water insoluble monomers as vinylidene chloride and styrene using the water soluble catalyst.

(1) The emulsifier-free aqueous copolymers contained consistently much more combined acrylonitrile than the corresponding bulk and emulsion copolymer.

(2) The emulsion copolymer contained less acrylonitrile as the amount of used emulsifier increased.

(3) The monomer-polymer composition curves of emulsion copolymerizations were identical with that of bulk copolymerization, only when critical micell concentration of emulsifier was in use.
Studies on Micelles. III. A Check of the New Conclusion from the Spectral Experiments with the Well-known Experimental Facts of Other Authors
Authors: Sasaki Hiroji
Published: July 2006

The conclusion, which is obtained by the spectral experiments on aqueous surfactant solutions, that the micellar concentration in aqueous surfactant solution is constant irrespective of surfactant concentration in the range which is from a little above the CMC to a considerably high surfactant concentration, coincides well with many other experimental results such as solubilization of dye, conductivity, self diffusion, X-Ray diffraction, density, viscosity and osmotic coefficient or cryoscopic behavior.
Sorption of Monobasic Dye-acid by Nylon-6 Fibre
Authors: Nishio Minoru
Published: July 2006

The equilibrium uptake of two typical monobasic dye-acids by nylon-6 (polycapramide) fibre has been measured for varying concentrations and additional evidence was given to confirm the mechanism of dye attachment to nylon as consisting of (1) combination with basic amine ends at normal dye bath pH and (2) combination mainly with the weakly basic nonterminal amide groups of the polymer chain at lower pH values. The Langmuir equation can well be applied to both regions of adsorption.

It is well known that the thermodynamic affinity of a dye for the fibre represents a fundamental characteristics of the dyeing process. The anion affinities of dye-acids for nylon-6, calculated from data on the equilibrium distribution of dye-acid between bath and fibre in terms of the change in standard chemical potential of the dye sorption process using the equation for wool developed by Gilbert and Rideal, were in good agreement with values for nylon-66 obtained by other workers.

Thus, the fundamental energetics of dyeing process and the mode of dye attachment are the same on these two fibres and some slight differences in dyeing behaviour must arise solely from differences in their physical structure due to the production process.