bluuebunny/crossref_metadata_2025 huggingface dataset:
ON ENANTIOTROPY AND MONOTROPY. II
Authors: Nagasako Noboru
Published: July 2006

1. The affinity of transition and the heat of transition from diamond to graphite and from white phosphorus to red phosphorus have been evaluated on the basis of the Nernst’s theorem and it has been made clear that they are monotropic under the atmospheric pressure. The former case will probably be enatiotropic under high pressure, whereas the latter case will remain monotropic even under high pressure.

2. An approximation formula for the estimation of the affinity of transition has been derived and by means of which the dimorphisms in ethyl ether, iodine monochloride, benzophenone, phthalide, bromonitrobenzene, acetamide, monochloracetic acid, nitro-p-toluide and erythrite have been estimated to be monotropic.
ON THE DEVIATION OF GASEOUS MIXTURES FROM DALTON’S LAW OF PARTIAL PRESSURES DUE TO CHEMICAL CAUSES. III. HYDROGEN CHLORIDE AND METHYL ALCOHOL
Authors: Shidei Jitaro
Published: July 2006

1. The gaseous pressures of methyl alcohol of several amounts have been measured at temperatures ranging from 70° to 130°C. It is shown that the pressures measured when plotted against the weights contained in a litre, to which the weights actually taken were converted, give a series of excellent straight lines which nearly pass through the origin of the co-ordinates.

2. The pressure of gaseous hydrogen chloride have been measured over the temperature range, 50° to 130°C. These are shown to be in good agreement with those which are calculated by van der Waals’ equation, changes of his constants with temperature being allowed for by van Laar’s equations.

3. Measurements have been carried out of the deviation from Dalton’s law at temperatures between 70° and 130°C. in mixtures of several proportions of hydrogen chloride and methyl alcohol. The deviation is discussed from the assumption of the existence of the two reactions:-

CH3OH+HCl \ightleftarrows CH3OH·HCl

CH3OH·HCl \ightleftarrows CH3Cl+H2O.
ELECTRODE POTENTIAL OF NICKEL. PART III. MECHANISM OF THE RE-ACTIVATION OF THE PASSIVE STATE OF NICKEL
Authors: Murata Kwanji
Published: July 2006

1. The re-activation by the action of the hydrogen of the nickel electrode, which has once been affected by oxygen, has been explained on the ground that nickel itself behaves as a catalyser, on the combination of oxygen and hydrogen.

2. It has been thermodynamically deduced that the equilibrium conditions in the nickel half-cells are expressed by pH2×aNi++×aOH−2=10−19.56 from which it has been calculated that when the activity-product (aNi++×aOH−2) attains the solubility product of nickel hydroxide, the corresponding partial pressure of hydrogen is 0.22 atm. This is the critical pressure above which only equilibrium can be established and if the partial pressure of hydrogen is less than this value the nickel will tend to go into solution accompanied by the precipitation. of nickel hydroxide until pH2 rises to the critical pressure.

3. On the above deduction, the changes with time in the electromotive force of the cells which were-prepared in the atmosphere of hydrogen or of nitrogen have been explained.

4. The abnormal behaviour of the nickel electrode observed by previous investigators has also been discussed on the same basis of proof.

5. The changes in free energy of various reactions have been calculated.
EQUILIBRIA IN THE SYSTEMS CONTAINING WATER AND CHLORIDES OF IRON, COBALT AND NICKEL AT 25.0°
Authors: Osaka Yukichi , Yaginuma Tokuzo
Published: July 2006

The equilibria in the following systems at 25.0° have been studied:

1. FeCl3–CoCl2–H2O,

2. FeCl3–NiCl2–H2O,

3. CoCl2–NiCl2–H2O,

4. FeCl3–CoCl2–NiCl2–H2O,

and the results have been given in tables and digrams.
ELECTRODE POTENTIAL OF NICKEL. PART I. MEASUREMENTS IN AN ATMOSPHERE OF HYDROGEN WITH REDUCED NICKEL POWDER
Authors: Murata Kwanji
Published: July 2006

1. A reproducible electrode, which gives a constant and reversible potential of active nickel was obtained by using powdered nickel reduced with hydrogen directly in the cell and also using an apparatus which allows the cell to be filled with the electrolyte entirely in the absence of air.

2. The potentials of the reduced nickel powder in 0.05 M and 0.005 M nickel sulphate solutions both at 25°C. and 18°C. were measured in an atmosphere of hydrogen.

3. The normal electrode potentials of nickel were calculated from these observed potentials on the ground of two different concepts of the strong electrolytes, one being that the ion concentrations calculated from the conductance viscosity ratios are involved in the expression of the electromotive force of a concentration cell and the other being that the ion activities are involved. The average values of these normal electrode potentials are −0.2496 volt (25°C.) and −0.2508 volt (18°C.) at one molal ion concentration, and −0.2480 volt (25°C.) and −0.2492 volt (18°C.) at one molal ion activity.

4. The change in free energy of nickel electrode reaction per equivalent, that is, (Remark: Graphics omitted.) was calculated from the above electrode potentials.
A Thermistor Method for the Determination of Velocity Coefficients of Vinyl Polymerization. IV
Authors: Miyama Hajime
Published: July 2006

Concentration change of sensitizer during vinyl acetate polymerization photosensitized by 1, 1′-azo-biscyclohexanecarbon-itrile was measured with use of a spectro-photometer and the initiation velocity of polymerization was determined. Values of kp and kt at various degree of conversion were calculated from this value and the results of the previous paper. From this experiment, it was concluded that kp was nearly constant up to 40% conversion and as the conversion exceeded 40%, it decreased, while kt gradually decresed with the increase of the conversion.
Electron Diffraction Investigation on the Molecular Structures of Some Organosilicon Compounds. II
Authors: Yokoi Masatoki
Published: July 2006

The vapors of methyl or ethyl substituted silicon compounds containing Si–Cl, Si–Br, Si–O, Si–N and Si–S bonds were studied by electron diffraction method and their molecular structures were determined. Bond lengths obtained are summarized in Table IV. The Si-Br length in methylbromosi-lane series changes with the number of substitutions of Br, but the length is in accord with the data of corresponding bromosilanes. The valence angles of oxygen in linear and cyclic siloxanes were estimated to be about 140° and this value is nearly the same as that in α-quartz. The valence angles of silicon in cyclic compounds are almost tetrahedral and those of oxygen, nitrogen and sulfur vary with the size of the ring.
Structures of the Erdmann’s Salt, NH4[Co(NH3)2(NO2)4] and Some Other Related Nitro-ammine-cobalt (III) Complexes
Authors: Komiyama Yoshimichi
Published: July 2006

NH4[Co(NH3)2(NO2)4] belongs to the space group P212121, with four formula units per unit cell. All the atomic coordinates were determined by the method of two-dimensional Fourier series. The structure is found to be isotype to K[Co(NH3)2(NO2)4]. Two ammonia groups are co-ordinated to the central cobalt atom in the trans-positions.

General features of the structures of various nitro-ammine-cobalt(III) complexes were discussed. The absorption spectra of these complexes were reexamin-ed in their aqueous solutions. Results are briefly discussed in relation to their steric configurations.
The Molecular Structure of 1,2-Difluoro-1,1,2,2-tetrachloroethane
Authors: Iwasaki Machio , Nagase Shunji , Kojima Rimpei
Published: July 2006

The molecular structure of 1,2-difluorotetrachloroethane was studied by the electron diffraction method. The existence of the two isomeric forms, trans and gauche, was ascertained and the amount of the gauche form was found to be 55±10 per cent. This corresponds to the energy difference of 0−500 cal./mol. the trans form being more stable. The interatomic distances and the valency angles were determind as follows:

C—F=1.38±0.02 Å, C—Cl=1.76±0.01 Å, C—C=1.54±0.06 Å, <CCCl=112°±2°, <ClCCl=110°30′±1°, <FCCl=107°30′±1°30′, and the azimuthal angle of the gauche form=59°±4°.

The C—F bond distance in this molecule is greater than those distances of compounds having more than one fluorine atom bonded with a carbon atom. On the other hand, the C—Cl bond distance seems to be slightly shorter than those of chloro-alkanes having no substituted fluorine atom.
Benzylation of Acetylene. I. Formation of 3,4-Diphenyl-1-butyne and 3,4-Diphenyl-1,2-butadiene
Authors: Ando Teisuke , Tokura Niichiro
Published: July 2006

The reaction between benzyl chlorides and metal acetylides, prepared from metallic lithium and sodium in liquid ammonia resulted in the formation of new compounds, i. e. 3,4-diphenyl-1-butyne and 3,4-diphenyl-1,2-butadiene. The benzylation of acetylene did not stop at benzylacetylene but another benzyl group was introduced to form 3,4-diphenyl-1-butyne. 3,4-Di-phenyl-1,2-butadiene was formed by the isomerisation of the butyne. This isomeri-sation occurred not only by the action of hot ethanolic potash but also in liquid ammonia at the room temperature. 3,4-Diphenyl-1,2-butadiene was readily polymerized by heat.
Synthetic Studies on the Benzofuran Derivatives. II. Reactions of Aromatic o-Hydroxyaldehyde Derivatives and Ethyl Bromomalonate
Authors: Matsumoto Takashi , Fukui Kenji
Published: July 2006

2-Carbethoxy-4-hydroxy-5-carbomethoxycoumarone (V) and 2,2-dicarbethoxy-3-hydroxy-6-benzyloxycoumaran (XII) were synthesized respectively from 2,6-dihydroxy-3-carbomethoxybenzaldehyde (IV) or 4-benzyloxy-2-hydroxybenzaldehyde (X) and ethyl bromomalonate by the method of Tanaka for benzofuran synthesis. 2-Carbethoxy-4-hydroxy-5-carbomethoxycoumarone (V) was hydrolysed to 4-hydroxycoumarone-2,5-dicarboxylic acid (VI).

This dibasic acid VI was decarboxylated in quinoline with copper powder into a mixture of karanjol (VIII) and karanjic acid (IX).

2,2-Dicarbethoxy-3-hydroxy-6-benzyloxy-coumaran (XII) was hydrolysed to 6-benzyloxycoumarone-2-carboxylic acid (XIII).
Structure of Reineckate Complex Ion
Authors: Takéuchi Yoshio , Saito Yoshihiko
Published: July 2006

The crystal structure analyses of Reinecke’s salt, pyridine reineckate and choline reineckate established the configuration and bond characters of the reineckate complex ion, [Cr(NCS)4(NH3)2]−.

The bond character of the complex ion in Reinecke’s salt and pyridine reineckate corresponds to the structure N≡C–S−, while in choline reineckate the bond character is acounted for by the structure N−=C=S. This mutation of the bond character is discussed together with crystal structures of these reineckates.
Ultraviolet Spectrophotometric Determination of Iron(III) as Chloro-complex
Authors: Ishibashi Masayoshi , Shigematsu Tsunenobu , Yamamoto Yuuroku , Tabushi Masayuki , Kitagawa Toyokichi
Published: July 2006

The absorption spectra have been investigated for the solution of ferric perchlorate at various concentrations of hydrochloric acid. A method for spectrophotometric determination of iron has been studied using hydrochloric acid as reagent. Effects of temperature, acidity and diverse ions have been examined and the iron content of iron-base alloys has been determined by differential method.
A Simple Method of Sulfate Microdetermination
Authors: Egami Fujio , Takahashi Noriko
Published: July 2006

1) A simple method for sulfate microdetermination was established. Sulfate is precipitated as barium sulfate; then the excess of barium is precipitated as barium chromate. Finally the excess of chromate is estimated in alkaline solution with a spectophotometer at 375 mμ.

2) This method is able to be applied to sulfate solution containing sulfate sulfur in the range 10–300γ. (30–900γ as SO42−)

3) This method was successfully applied to the estimation of inorganic sulfate such as that in rain water and organic sulfate such as chondroitinsulfate, charoninsulfate, ethyl sulfate and p-nitro-phenyl sulfate.
The Stretching Vibration of N-H Link of 2-Aminopyridine
Authors: Soda Reisuke
Published: July 2006

The infrared absorption spectrum of 2-aminopyidine was abserved and compared with those of other compounds and the amino from of 2-aminopyridine was confirmed. The imino from was rejected and even if this tautomeric from exists its quantity is estimated to be negligibly small.
Absorption Spectra of Heteropolyanions. II The Heteropolytungstates Containing Co(II), Co (III) or Mn(IV) as Central Ions
Authors: Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

The visible and ultraviolet absorption spectra have been measured for some heteropolytungstates containing cobalt (II), cobalt (III) or manganese (IV) as central ions.

It has been shown that some cobalt (II) or cobalt (III) ions in the heteropolytungstates have tetrahedral co-ordination. This is the first case of the absorption spectra of [CoII(O=)4]- and [CoIII(O=)4]-complexes being measured.
Dielectric Investigation on Coals. I. Dielectric Properties of Japanese Coals
Authors: Miyasita Isao , Higasi Keniti
Published: July 2006

In a wide frequency range covering 300 c/s to 50 Mc/s dielectric constant and loss factor of ten Japanese coals were measured at room temperature. The result provides a view that Japanese coals are almost non-polar in effect and embrace no units of graphite structure of the sort proposed by Ellis.
Dielectric Studies on Colloidal Solutions. IV. The Dielectric Constant of the Solutions of Long-chain Amine Hydrochlorides
Authors: Shirai Micho , Tamamushi Bun-ichi
Published: July 2006

The dielectric constant and the equivalent conductivity of solutions of hexadecyl and octadecylamine hydrochloride have been measured at the frequencies of 2 Mc./ sec. and 30 Mc./sec. The dielectric constant of the solutions shows a considerable increase beyond the concentration for micelle formation.

The dielectric constant and the equivalent conductivity of the solutions of these amine salts in aqueous ethanol of various concentrations have been measured. The rise of the dielectric constant is diminished with increasing concentration of ethanol.

The effect of solubilization of benzene on the dielectric constant of the solutions has been investigated. The relative increase in the dielectric constant is reduced with increasing amount of solubilized benzene.

From these experimental results, it is concluded that the rise of the dielectric constant of the aqueous solutions is mainly due to Debye-Falkenhagen’s effect.
Studies on the Chemical Constitution of Agar-agar. XIX. Pyruvic Acid as a Constituent of Agar-agar (Part 2). Isolation of a Pyruvic Acid-linking Disaccharide Derivative from the Methanolysis Products of Agar
Authors: Hirase Susumu
Published: July 2006

1. Partial methanolysis of agar has led to isolation of a crystalline double barium salt, which is separable into its components, barium methylsulfate and a barium salt of an organic acid.

2. From the last salt above mentioned, there has been obtained a free acid having the formula C14H21O9(OCH3)2COOH as its crystalline monohydrates. Its methyl ester and amide have also been prepared in a crystalline condition.

3. The acid obtained, a new compound, has been proved to be a disaccharide derivative composed of 3,6-anhydro-l-galactose, d-galactose and pyruvic acid.

4. It has also been proved that the pyruvic acid residue is linked through its carbonyl group with the d-galactose residue.

5. The isolation of the pyruvic acidlinking disaccharide derivative substantiates the view that pyruvic acid is an intrinsic constituent of agar.
Synthesis of β- and γ-Thujaplicins
Authors: Katsura Shigeo , Moroe Tatsuo , Ikegami Norio
Published: July 2006

β- and γ-Thujaplicins were synthesized through 4-isopropylcycloheptanone from perillaldehyde and 4-isopropylcyclo-hexanone.
Hydrogen Bonding Effect on the Fluorescence of π-Electron System. III. Fluorescence Quenching of Some Nitrogen Heterocycles Caused by Hydrogen Bond Formation
Authors: Mataga Noboru , Tsuno Shizuyo
Published: July 2006

1. Hydrogen bonding effect on the fluorescence of acridine, 3,6-diaminoacridine and 3,6-bisdimethylaminoacridine was studied in non-polar solvent added with proton donors such as phenol, naphthols, aniline and pyrrole.

2. Their fluorescence yields are decreased when hydrogen bonded with these proton donors, in which the hydrogen bond is capable of conjugation with π-electron system, in contrast to the case of donors such as benzylalcohol and β-phenylethylalcohol in which the hydrogen bond is isolated by σ-bond from π-electron system, and hydrogen bonding with which leads to the enhancement of fluorescence yield.

3. No viscosity dependence of quenching has been observed. From this fact participation of diffussion controlled dynamical process in the non-radiative degradation of excited state is unlikely.

4. The cause of non-radiative degradation of excited state by hydrogen bonding was ascribed to the delocalization of π-electrons through the hydrogen bond, especially in the excited state.
Studies on the Mechanism of Eder’s Reaction. II. On the Properties of the Active Oxalic Acid in Manganese (III and VII)-Oxalate Reaction Systems
Authors: Sakuraba Shukichi , Ikeya Syozo
Published: July 2006

1) The active oxalic acid produced in the manganese (III or VII)-oxalate reaction system has the same properties with the activiated manganese oxalate formed by ultraviolet irradiation. These active intermediates are able to reduce mercury (II) chloride and, if oxygen is dissolved in the solution, react with oxygen to form hydrogen peroxide and the manganese (III) ion. These will probably be an ionic radical with a long life that has the same formula.

2) The inhibitory action of oxygen on the decomposition of the manganese (III) oxalate complex can be interpreted by the reproduction of the manganese (III) ion, and it is most remarkable at pH about 3.2.
Further Studies on the Preparation of Calf Thymus Histone
Authors: Ui Nobuo
Published: July 2006

Calf thymus histone was prepared as gently as possible without using acids, alkalis or organic solvents. It was clearly shown that two components with sedimentation coefficients of 2 S and 0.7 S are present.

Sedimentation, electrophoresis and solubility behaviors of these preparations were similar to those of the preparations obtained by the previously reported method using acid and ethanol, and it was confirmed that histone consists of two fractions, histones I and II. It was also ascertained that acid as well as ethanol causes no alteration of the proteins.
Spectrophotometric Method for the Determination of Small Amounts of Sulfate Ions
Authors: Iwasaki Iwaji , Utsumi Satori , Hagino Ken , Tarutani Toshikazu , Ozawa Takejiro
Published: July 2006

The authors have devised a new method for the determination of small amounts of sulfate. Sulfate is precipitated as barium sulfate using barium chromate suspension in an acid solution (0.5 M acetic, 0.01 M hydrochloric acid), and the excess of barium is almost completely precipitated as barium chromate by adding ammonia water (containing calcium ion) and ethanol. Finally the amount of chromate which is exchanged with sulfate is estimated.

The proposed method may be applicable to the determination of 0.3–100p. p.m. sulfate with satisfactory results.
Dye-sensitized Photopolymerization of Acrylonitrile-Vinyl Acetate Copolymers
Authors: Taniyama Masakazu , Oster Gerald
Published: July 2006

Copolymers of acrylonitrile and vinyl acetate have been produced using a dye-reducing agent combination as the photo sensitizer. Visible light was employed as the radiation source. Nitrogen analyses were performed on the polymers obtained. The copolymerization ratio were 3.88 and 0.009 for acrylonitrile and vinyl acetate, respectively. Below an initial monomer molar ratio of acrylonitrile of 0.3, the resultant copoly-mer dissolves in acetone.
Molecular Rotations of Glucides in Relation to their Structures. III. Optical Superposition in Pentoses
Authors: Yamana Shukichi
Published: July 2006

The method of calculation of optical rotatory power, devised by Kirkwood and improved by the author was applied to the pentose group, and it was concluded that the principle of optical superposition of Kirkwood’s idea exists in this group.
Molecular Rotations of Glucides in Relation to their Structures. IV. The Internal Conformation of C6–O Bond in d-Mannopyranose and d-Glucopyranose in their Aqueous Solutions
Authors: Yamana Shukichi
Published: July 2006

The internal conformation of C6–O bond in the molecules of d-mannopyranose and d-glucopyranose in aqueous solutions were presumed by a new method, and was concluded to take trans (mostly) and gauche II (only sometimes) forms.
Absorption Spectra and Chemical Behavior of the Hexahydroxylamine Cobalt (III) Complex
Authors: Yoneda Hayami
Published: July 2006

The absorption spectrum of hexahydroxylamine cobalt(III) complex was measured and compared with the hitherto obtained data of the other hexammine cobalt (III) complexes. The frequencies of the first and second absorption bands of this complex were 68.5×1013 and ca. 94×1013 sec.−1 respectively. These values are much greater than those found in other hexammine cobalt (III) complexes, and this fact may indicate the strong interaction between the central cobalt (III) ion and nitrogen atoms of the co-ordinating hydroxylamine. In addition to the study of absorption spectra, the rate of decomposition of this complex was measured. The rate of decomposition was proportional to the concentration of the hydroxyl ion, and the activation energy was 32.5 kcal. mole−1. In order to explain the above results, the following equilibrium, assuming the proton dissociation, was proposed;

[Co(NH_2OH)_6]^3++H_2O\ightleftarrows[Co(NH_2OH)_5NHOH]^2++H^3O^+
Heat of Mixing of Mono- and Di-propylene Glycol with Water
Authors: Amaya Kazuo , Fujishiro Ryoichi
Published: July 2006

The heat of mixing of propylene glycol and di-propylene glycol with water was measured. The results obtained for these systems were compared with each other and it was found that the oxygen atom in the ether bond of di-propylene glycol plays an important role for the acceptor of hydrogen bonding and makes a great contribution to the heat of mixing.
The Photochemical Degradation of 6 Nylon. I
Authors: Hashimoto Takeshi
Published: July 2006

1) The photochemical degradation of 6 nylon was investigated through the measurement of intrinsic viscosity and the amount of water-soluble material of 6 nylon taffeta irradiated for various periods of time in Fade-Ometer.

2) The intrinsic viscosity or the number-average degree of polymerization decreases rapidly at the initial stage, while the amount of water-soluble material increases approximately in proportion to the exposure time.

3) It is deduced from the relationship between the number-average degree of polymerization and the amount of water-soluble material that the molecular chain of 6 nylon is randomly split off by light. The relationship is well explained by the theory of random breaking of the polymer chain.
Spectrophotometric Determination of Iron in Serum
Authors: Umemoto Shunji , Yamamoto Yasuhisa
Published: July 2006

To improve the procedure of photometric determination of iron in human serum, Torii’s method recently proposed for the determination of iron was applied to serum. After the removal of protein from serum, the iron in serum is reduced, the pH of the solution is adjusted to 4.5, the color-developing reagent is added, and the excess of the reagent is removed by extraction with carbon tetrachloride. The green solution thus obtained is effective for spectrophotometric determination.

The interference of copper is avoided by the addition of thiosulfate, and the substances other than copper remaining after the removal of protein from serum do not give any appreciable interference.
Synthesis of 2-Alkyl-4H,1,3-benzoxazine-4-ones
Authors: Hanada Takeyosi
Published: July 2006

2-Alkyl-4H,1,3-benzoxazine-4-ones (Ia, Ib, and Ic) were synthesized from the corresponding O-acylsalicylamides (II), and some of the properties of I were studied.
Electron Diffraction Investigation on the Molecular Structure of 1,1,2,2-Tetrafluoro-1,2-dichloroethane
Authors: Iwasaki Machio
Published: July 2006

The molecular structure of 1,1,2,2-tetrafluoro-1,2-dichloroethane was investigated by means of the sector-microphotometer method of electron diffraction. The existence of two isomeric forms, i. e., trans and gauche, was confirmed, and the amount of the gauche form was found to be 48±5 per cent. at 10°C. This corresponds to the energy difference of 440±110 cal./mol., the trans form being more stable than the gauche form. The interatomic distances and the bond angles were determined as follows: & C–F=1.33_0±0.01_5Å ∠CCF=108°±1°30’

& C–C=1.54±0.04Å ∠CCCl=112°±1°30’

& C–Cl=1.74_5±0.01_5Å ∠FCCl=110°±1° \oindentand the azimuthal angle of the gauche form=62.5°±3°.
Mutual Solubilities of Some Hydrocarbon Oils and Liquid Ammonia. II. Application of the Solubility Parameter Theory
Authors: Ishida Kiyoharu
Published: July 2006

The result of the comparison of experimental data for the critical compositions and the logarithms of activity coefficients at infinite dilution for binary systems of some hydrocarbon oils and liquid ammonia with those expected from the solubility parameter theory, is that the solubility relations may be more satisfactorily interpreted by the theory by assuming that ammonia is associated nearly to dimerized from in the liquid state.
Isotopic Exchange Reaction between Cyclohexane and Deuterium on Evaporated Molybdenum Films
Authors: Hayakawa Teruo , Sugiura Toshio
Published: July 2006

Isotopic exchange reaction between cyclohexane and deuterium over evaporated molybdenum films has been studied mass-spectrometrically at the temperature range 56-111°C. The present results were compared either with Anderson and Kem-ball’s or Burwell and Tuxworth’s, and summarized as follows;

1) Since the deuterium content in our experiments was considerably low the production of considerable amounts of highly deuterated products requires a process of multiple exchange.

2) The present results clearly indicate that one can observe no discontinuities which separate the concentrations of C6H6D6 and C6H5D7.

3) The pressure-dependence was studied for this exchange and the initial rate (k) was found to be expressed as k∞p (C6H12)1.0·p (deuterated hydrogen)−0.6.

4) According to the present kinetic evidence, the rate-determining step of this exchange is probably the desorption of the cyclohexyl radicals.

5) So far as the present experiments were concerned, it seems reasonable to consider that the deuterium isotope effect gives no significant influence upon the present exchange reaction.
Isotopic Exchange Reaction between Cyclohexane and Deuterium on Evaporated Tungsten Films
Authors: Hayakawa Teruo , Sugiura Toshio
Published: July 2006

Isotopic exchange reaction between cyclohexane and deuterium over evaporated tungsten films has been studied mass-spectrometrically at the temperature range 79∼111°C. The present results are summarized as follows;

1) The production of highly deuterated products in the initial stage of this exchange requires a process of multiple exchange.

2) Evaporated tungsten films showed, however, little tendency for multiple exchange, while evaporated molybdenum films promoted multiple exchange to a large extent.

3) One can observe no discontinuities which separate the concentrations of C6H6D6 and C6H5D7.

4) It seems reasonable to consider that marked discontinuities between C6H6D6 and C6H5D7 observed by Anderson and Kemball for evaporated films of rhodium and palladium must not be attributed to the characteristic chair conformation of the cyclohexane molecule.

5) The deuterium isotope effect gives no significant influence upon the overall reaction of this exchange.
The Mechanism of the Isotopic Exchange Reaction between Cyclohexane and Deuterium on Evaporated Metal Films
Authors: Hayakawa Teruo , Sugiura Toshio
Published: July 2006

The theoretical treatments of the isotopic exchange reaction between cyclohexane and deuterium over evaporated metal films have been studied. The present results of the theoretical calculations were compared with the experimental results already obtained by the present authors for evaporated films of molybdenum and tungsten. The present results are summarized as follows:

1) The agreements between the theoretical and the experimental values of the initial product distributions for these metal films are well maintained.

2) The initial rate of tripping of the adsorbed radicals on evaporated films of molybdenum or tungsten at each temperature is considerably greater than that of desorption (or chemisorption) of cyclohexane. This coincides well with the experimental fact that the rate-determining step of this exchange reaction may be attributed to desorption of the adsorbed radicals.

3) The differences between the activation energy of tripping of the adsorbed radicals and that of desorption for evaporated films of molybdenum and tungsten amount to 6.8 and 9.7 kcal./mol. respectively.
Alkylalkoxypolysiloxanes. VII. Lower Members of tert-Butoxy End-blocked Dimethylpolysiloxanes with One to Four Silicon Atoms
Authors: Okawara Rokuro , Imaeda Sh\={o}hei
Published: July 2006

1) tert-Butoxy end-blocked dimethylpolysiloxanes were prepared from dimethyldichlorosilane, tert-butanol and water by the use of pyridine as an acid acceptor.

2) The lower members of those polysiloxanes having one to four silicon atoms were characterized.
The Ignition of Methane-Oxygen Mixture by Shock Wave
Authors: Suzuki Momotaro , Miyama Hajime , Fujimoto Shiro
Published: July 2006

Using the shock tube, the authors measured the minimum ignition pressure P1 of the reservoir for the methane-oxygen mixture of various pressure P0 and various compositions, and obtained the following results.

1) The higher the value of P0, the easier the ignition.

2) The concentration range of methane in the gaseous mixture for shock ignition is 3—42%, and the minimum value of P1/P0 or the ignition temperature, was found at a gaseous mixture of about 20—25% methane.

3) The ignition easier is by the use of the shock tube with conical end rather than with the plane end.

4) Shock ignition temperatures estimated indirectly were found to be remarkably lower than the thermal ignition temperature.
Studies on Micelle Formation in Non-polar Solvent by Thermistor
Authors: Kitahara Ayao
Published: July 2006

The apparent mean aggregation number (Z) of dodecylammonium carboxylate in cyclohexane was obtained from the vapor pressure depression measurement by the use of a pair of thermistors. The monomer concentration (C1) was calculated from Kreuzer’s equations. The C1 was nearly independent of the concentration. The true aggregation number (λ) was obtained, assuming that the micelle is monodisperse. The cmc extraploated from C1 agreed approximately with those by other methods.

The change of the heat content associated with micelle formation was calculated from the change of the cmc with the temperature and from the temperature dependence of the equilibrium constant for the λ-mer aggregation. Both agreed roughly with each other.
Studies on the Cobalt(III) Complexes Containing Only One Chelate Ring. III. Rotatory Dispersion of Tetrammine-I-leucinato-cobalt(III) Perchlorate, [Co (NH3)4(I-leuc)](ClO4)2
Authors: Shimura Yoichi
Published: July 2006

A new complex compound, [CoIII(NH3)4(l-leuc)](ClO4)2, has been prepared, in which the asymmetric center is only on a carbon atom of the ligand leucinate ion. From the measurements of the visible and the ultraviolet rotatory dispersion of this compound, it has been concluded that the so-called “vicinal effect” exists between the cobalt atom and the asymmetric carbon atom.

The rotatory dispersion measurements have also been made for d-[Co en2 (l-leuc)]Cl2, d-[Co en2 (NH3)Cl(2)(1)]Br2 and d-[Co en3]Br3·2H2O. On the basis of these data the relation of the splitting of the first absorption band with the so-called anomalous rotatory dispersion has been discussed. Thus it has been shown that the anomalous rotatory dispersion of [Co(NH3)4(l-leuc)]2+ or of [Co en2 (NH3) Cl]2+ is explicable by assuming the overlap of the two inversive dispersions, Ia and Ib, which correspond to the component bands, Ia and Ib, of the split first absorption band.

In agreement with the observations by several previous authors, it has been shown that all the complexes studied scarecely show the anomalous rotatory dispersion in the vicinity of their second absorption bands.
Formation and Aging of Precipitates. VI. Morphology of Crystals in Various Vanadium Pentoxide Sols by Electron Microscopy
Authors: Takiyama Kazuyoshi
Published: July 2006

Vanadium pentoxide sols were prepared by Biltz’, Müller’s and ion exchange method, and the crystals in the sols were observed with an electron microscope. The crystals in Biltz sol were small fibrils at first, but they grew into long fibrous crystals upon aging. The crystals in Müller and ion exchange sols were fibrils and needles respectively and hardly grew at all. The growth of the fibrous crystals in Biltz sol is likely to be due to the recrystallization of the fibrils.
Partial Hydrogenation of 1,4-Butynediol
Authors: Fukuda Tosao , Kusama Tokishige
Published: July 2006

1. The effect of lead acetate and the poisons on the Pd-CaCO3 catalyst was studied with the hydrogenation of 1,4-butynediol.

2. The hydrogenation of 1,4-butynediol with the Pd-CaCO3 catalyst at room temperatures takes place in two distinct steps; the first step is the hydrogenation to 1,4-butenediol, and the second is its hydrogenation to 1,4-butanediol.

3. When Pd-CaCO3 catalyst is poisoned by increasing amount of lead acetate, the activity for the hydrogenation of 1,4-butynediol increases at first, and then gradually decreases as the poisoning proceeds. On the other hand, that for the hydrogenation of 1,4-butenediol simply decreases with increasing amount of lead acetate.

4. The hydrogenation of 1,4-butynediol with Pd-CaCO3 catalyst is slightly retarded by quinoline, but not by pyridine or piperidine. On the other hand, the hydrogenation of 1,4-butenediol is retarded to some extent by pyridine, more markedly by piperidine, and stopped almost completely by quinoline. The effect of these bases is almost the same when they are applied to the Pd-CaCO3 catalyst poisoned by lead acetate.

5. The partial hydrogenation of 1,4-butynediol can be achieved by using quinoline, but not by using pyridine or piperidine.

6. The selective hydrogenation may result from the strong adsorption of 1,4-butynediol on the catalyst surface. When the catalyst adsorbs the poisons, the properties of the catalyst surface may be changed. As a result, the selectivity of the catalyst may become very characteristic. Consequently, the selective hydrogenation may take place as observed.
Polarographic Investigations of Vitamin C. II. On the Reduction Waves of Some Conjugated Tricarbonyl Compounds as Related Compounds of Dehydro-l-ascorbic Acid
Authors: Ono Sozaburo , Takagi Masanosuke , Wasa Tamotsu
Published: July 2006

Alloxan, dehydro-reductic acid and mesoxalaldehyde show reduction waves which are similar to that of dehydro-l-ascorbic acid. The half-wave potentials of alloxan, dehydro-reductic acid, dehydro-l-ascorbic acid and mesoxalaldehyde in pH 3.5 are −0.05, −0.27, −0.42 and −0.35 V. (vs. N.C.E.), respectively.

Of these four substances, the lower the height of the reduction wave, the greater both the shift of the half-wave potential of the anodic wave of the corresponding reduced form from the standard oxidation-reduction potential of the system and the temperature coefficient of the height of the reduction wave.

Inactive forms of these substances at the electrode reaction may be the hydrated ones as proposed in the case of dehydro-l-ascorbic acid.

Alloxan has been proved to be polarographically reversible by the controlled potential electrolysis and the half-wave potential of the reduction wave coincides with that of the oxidation wave of dialuric acid, while no such observations have been made with the other three.
Fractionation of Ribonuclease-resistant Fraction on ECTEOLA-cellulose
Authors: Tanaka Kentaro
Published: July 2006

RNase-resistant material obtained from yeast RNA was fractionated on an ECTEOLA-cellulose column. The elution was performed with sodium chloride-neutral phosphate buffer as solvent, the concentration of sodium chloride being increased by either gradient or stepwise procedure. Separation of oligonucleotides seemed to be affected by their molecular size. The products of larger molecular weight present in pancreatic-RNase digests of yeast RNA were very rich in guanylic acid.
Phase Relationship in the System 3CaO·P2O5–MgO·SiO2–SiO2
Authors: Sata Toshiyuki
Published: July 2006

The phase relationship in the system 3CaO·P2O5–MgO·SiO2–SiO2 was investigated by the usual quenching method. In the partial system 3CaO·-P2O5–SiO2, the existence of solid solution and the change of the transition temperature of α–β tricalcium phosphate were not found by X-ray examinations.

The partial system 3CaO·P2O5–MgO·SiO2 is pseudo-binary, whose eutectic is at 1246°C and 40% 3CaO·P2O5. In this system, β-3CaO·P2O5, always appeared in quenched samples, has a maximum solid solubility of 7±2% MgO·SiO2.

The system 3CaO·P2O5–MgO-SiO2–SiO2 has two quintuple points, the one an alteration point and the other a ternary eutectic at 50.5% 3CaO·P2O5, 15.0% MgO, 34.5% SiO2 that melts at 1230±4°C.

This system is of great importance to the manufacture of the fused phosphatic fertilizer and the bone ash magnesia porcelain. For instance, in this system, the lower liquidus groove lies at higher silica side along 3CaO·P2O5–MgO-SiO2, in accord with the results of cone fusion and melting point measurements already obtained by Kiyoura and Sata.
Ion Exchange in Concentrated Solutions. III. Magnesium Chloride-Hydrochloric Acid and Aluminum Chloride-Hydrochloric Acid Systems
Authors: Ohtaki Hitoshi , Yamasaki Kazuo
Published: July 2006

Ion-exchange equilibria in the concentrated solutions of magnesium chloride-hydrochloric acid and aluminum chloride-hydrochloric acid system were studied. Amounts of the water present in the resin at equilibrium were estimated for these systems. In the magnesium chloride-hydrochloric acid system a large part of magnesium in the resin exists as MgCl+ at equilibrium when the concentration of hydrochloric acid is high. Selectivity coefficients of magnesium chloride-hydrochloric acid and of aluminum chloride-hydrochloric acid systems were calculated.
Rate of Methanol Synthesis
Authors: Uchida Hiroshi , Ogino Yoshisada
Published: July 2006

Over a wide range of the total pressure and the ratio of hydrogen to carbon monoxide measurements on the methanol synthesis have been made at different temperatures at different space velocities. Relations of the total pressure to the methanol concentration and the conversion efficiency, and the dependence of the methanol concentration and the conversion efficiency on the ratio of hydrogen to carbon monoxide are presented.

Based on the assumption of the logarithmic adsorption isotherm and of the methanol desorption as the rate determining step, the rate equation for the methanol synthesis has been derived, which follows:

r=k_d{(P_COP^2_H2)^0.7-P_CH3OH·(P_COP^2_H2)^-0.3/K}

The equation has proved capable of representing our experimental results satisfactorily over relatively wide ranges of the pressures, the ratio of hydrogen to carbon monoxide and the space velocity.
Electronic Spectra of Acridine and Phenazine
Authors: Mataga Noboru
Published: July 2006

The electronic spectra of three-ring nitrogen heterocycles have been calculated by the perturbation method based on the Hartree-Fock self-consistent field theory. There is a satisfactory agreement in general between the calculated the and observed excitation energies and oscillator strengths, and the mechanism of the electronic transitions in these molecules has been discussed in detail.
A Study on the Micellar Solutions of Sodium Oleate and Elaidate
Authors: Tamamushi Bun-ichi , Shirai Michio , Tamaki Kunio
Published: July 2006

The electrical conductivity, the interaction with pinacyanol iodide, the degree of hydrolysis, and solubilization power for benzene have been measured for sodium oleate and elaidate.

The conductivity behavior of these salts is consistent with the experimental result for hydrolysis and the latter result is also consistent with that of solubilization measurement. The result of dielectric polarization is also compatible with other results.

All these experimental results show that sodium elaidate has a slightly greater tendency towards micelle formation than sodium oleate.
Fluorescence Quenching due to the Interactions between π-Electron Systems in the Excited State and Acid-Base Relation: Nitrogen Heterocycles, Naphthylamine and Naphthol in Aqueous and Alcoholic Solutions
Authors: Mataga Noboru
Published: July 2006

The acid-base relation in the fluorescence quenching in aqueous and alcoholic solutions, due to the interaction between π-electron systems in the excited state, has been pointed out. Roughly speaking, this is parallel with the fluorescence quenching due to hydrogen bonding between the π-electronic fluorescer and quencher in non-polar solvent. Remarkable solvent effects on the quenching efficiency have been found and some important roles of hydrogen bonding in this phenomenon have been suggested.
Colorimetric Determination of Bivalent Copper Using Sodium Alizarin-3-Sulfonate as a Reagent
Authors: Mukherji Anil K , Dey Arun K
Published: July 2006

The formation of a 1:1 copper chelate with sodium alizarin-3-sulfonate, having λmax at 500 mμ has been reported. The color formation has been applied to the colorimetric determination of copper on a micro-scale. The color has been found to be stable between pH 3.20 and 7.50, at temperatures 20∼30°C. The sensitivity of the reagent is 6.4 p.p.m. of the copper ion. The interference by a large number of cations and anions has been studied and the tolerance limits are quantitatively determined spectrophotometrically. It has been recommended that the reagent is suitable for the colorimetric determination of copper(II) on a micro-scale and the conditions have been prescribed.
Further Notes on the Ideal Mixture Law for Viscosity
Authors: Ishikawa Tetsuya
Published: July 2006

In the previous paper on the same subject the author made an erroneous explanation on the result of Na–K system.

Comparison of Ishikawa’s formula with Drucker and Kassel’s formula leads to the new relation, K=\varphi2M2a2⁄\varphi1M1a1, from which the association degrees of 27 kinds of liquid have been evaluated.

By the use of this relation, the abnormally high value of K of Na–K system has been proved to be normal.

Two systems of different crystal forms, Pb–Sn and Pb–Bi, and six systems composed of isomorphic compounds, benzyl-aniline, benzalaniline, dibenzyl, azobenzene, and stilbene are added for elucidating the degradation of atomic or molecular complexity with rise of temperature.
On the Nature of the Red Adduct of Styrene with Sodium
Authors: Hirota Kozo , Kuwata Keiji , Morigaki Kazuo
Published: July 2006

Paramagnetic resonance absorption could be observed on the solution of the pure red adduct, which was prepared according to the method reported by the present writers. The adduct, therefore, produces a radical anion consisting of odd electrons by dissociation. The proposition on the structure of the red adduct in the previous report was thus confirmed.
Dispersed Structure of Chromia-Zinc Oxide Catalyst System
Authors: Matsunaga Yoshio
Published: July 2006

Chromia-zinc oxide catalysts have been prepared by the impregnation method using non-sintered and sintered zinc oxide as carriers. Measurements of magnetic susceptibility have been made for these two series of catalysts of varying composition. The values of gram susceptibility and the mean oxidation number of chromium in the samples oxidized with air at room temperature are nearly independent of the content of chromium. After oxygen-treatment at 250° or 450°C has been carried out, however, the surface oxidation becomes appreciable in the samples of low content of chromium, and the variations in the susceptibility and the mean oxidation number suggest that the dispersed structure of chromia depends on the composition of the catalyst. It appears that chromic ions are distributed in the two compounds, namely the thin layers of chromia on the catalyst surface and the relatively large crystallites of zinc chromite and, as the chromium content is decreased, the former becomes more important. By comparison between the two series examined in the present work, it is suggested that the form of the magnetic susceptibility-composition isotherm is governed by the reactivity of the carrier and the cause of the discrepancy between the results obtained by Shida et al and by us may be due to the difference between the kinds of chemical behavior of the zinc oxides employed as carrier.
The Separation of Polythionates with Anion-Exchange Resins
Authors: Iguchi Akira
Published: July 2006

1) The distribution coefficient of di-, tri-, tetra-, and penta-thionates between anion-exchange resins and hydrochloric acid solution was measured. The adsorb-ability of the polythionates increases with the number of sulfur atoms in the ion, i. e. pentathionate>tetrathionate>trithionate>dithionate.

2) The separation of polythionates was accomplished by the anion-exchange chromatography by the use of hydrochloric acid in various concentrations as the eluant.

3) The application of anion-exchange chromatography to the analysis of Wackenroder’s liquid was studied.
On the Determination of Fine Structure of Cellulosic Fibers
Authors: K\={o}shiro Taketoshi , Yagami Kazuo , Shiratsuchi Eiichiro , Fujimura Toshikazu
Published: July 2006

In order to clarify the fine structure of rayon staple, it may be necessary to estimate not only the total crystallinity but also the distribution of crystalline size and quality. For this purpose, various methods which seemed to remove the amorphous region without recrystalliza-tion, were studied.

Methanolysis is affected by water content in the mixture and its residue may still contain an amorphous region because of its high accessibility. The recrystalli-zation may be possible during not only hydrolysis but also methanolysis.

The hydrolysis after pretreatment is not very effective to prevent recrystallization and may destroy crystalline region. Moreover, its procedure is troublesome.

The oxidizing-hydrolysis, which shifts the crystalline length distribution toward slightly higher DP region diminishing the shoulder on higher DP side and gives the lowest levelling-off accessibility, holds out considerable promise for the elucidation of the original crystalline structure. But its high solubility in alkaline solution may be derived from a carboxyl group formed during oxidation or from the cracks in a hydrogen-bond train of crystallites. Therefore, problems to study still remain.

The crystalline region of viscose rayon staple seems to have the chain-length distribution, which extends to a DP of ca. 40 and shows one maximum between the DP of 6 and 10.
A Theoretical Consideration of Simple Catalytic Reactions. Decomposition of Gaseous Hydrides
Authors: Tamaru Kenzi
Published: July 2006

The decomposition of arsine, stibine, tin hydride, methane, germane, hydrogen selenide and nickel carbonyl on the surface of the corresponding elements have been discussed from the statistical mechanical view-point. As these decompositions are catalytic reactions of the simplest type, several reasonable assumptions enable us to calculate the rates of each elementary step of each reaction and hence to decide the rate-determining step in a semi a priori fashion. It is shown that the calculations impose definite limitations to the possible mode of decompositions of this kind.