bluuebunny/crossref_metadata_2025 huggingface dataset:
Polarography of Bis(nitrophenyl)arsinic Acids
Authors: Maruyama Masao , Furuya Toshiko
Published: July 2006

1) Polarographic behavior of the six isomers of bis(nitrophenyl)arsinic acid was considered and the waves can roughly be divided into 1st and 2nd waves in acid range at the dropping mercury electrode.

2) The limiting current is controlled by the diffusion process and the Ilkovic equation is applicable.

3) The electrolytic reduction mechanisms of the 1st and 2nd waves are considered to be in the following manner, taking that of 4,4′-bis(nitropenyl)arsinic acid as an example: (see the figure of the preceding page).

4) By the utilization of the 1st wave, polarography can be used for the determination of bis(nitrophenyl)arsinic acids, especially those with the nitro group in 2-position.
Polarography of Bis(aminophenyl)arsinic Acids, Phenylarsonic Acid and Arsanilic Acids
Authors: Maruyama Masao , Furuya Toshiko
Published: July 2006

1) Polarographic behaviors of bis(aminophenyl)arsinic acids, phenylarsonic acid and arsanilic acids, were examined with dropping mercury electrode.

2) The reduction wave of bis(aminophenyl)arsinic acids appearing on the acid side is an irreversible three-electron reduction and this reduction mechanism is considered to be of the following type.

(Remark: Graphics omitted.)

3) An assumption was forwarded in the preceding paper that the 2nd wave shown by bis(nitrophenyl)arsinic acids on the acid side may contain a reduction wave owing to the reduction of arsenic and that it is more likely to be a three-electron rather than a 4-electron reduction. The foregoing results obtained with bis(aminophenyl)arsinic acids suggest that it would be more appropriate to consider an irreversible, three-electron reduction.

4) The reduction waves shown by phenylarsonic acid and arsanilic acids on the acid side are an irreversible, four-electron reduction and the reduction mechanism may be assumed as follows:

(Remark: Graphics omitted.)

5) Compounds like phenylarsinic acid (IX) do not exhibit a reduction wave at the dropping mercury electrode.

(Remark: Graphics omitted.)

6) Summarizing the foregoing facts, it may be concluded that these organic arsenic compounds which show a reduction wave at the dropping mercury electrode are quiquevalent arsenic compounds, the reduction wave is that of quinquevalent to tervalent, and that the compounds not possessing As=O are not reduced.

7) The limiting current of these compounds in the acid side is controlled by the diffusion process and is in proportiona.1 relationship with the concentration, so that it can be utilized for quantitative analysis.
Studies on the Mechanism of Eder’s Reaction. I. Inducing Photochemical Reaction of Manganese (II) -Oxalate System
Authors: Sakuraba Shukichi , Ikeya Shozo
Published: July 2006

Manganese(II)-oxalate is formed in the solution containing the manganese(II) and the oxalate ion and is activated by the ultraviolet absorption. The presence of this active manganese(II)-oxalate was supported by the reducing power towards mercury(II) ions and by the spectrophoto- metric measurement. This active manganese(II)-oxalate reacts with oxygen and hydrogen ion to form hydrogen peroxide and manganese(III) oxalate complex.

The photochemical catalytic action of the manganese(II) ion upon formation of hydrogen peroxide in an oxalic acid solution appears to be due to the activation of manganese(II)-oxalate molecule.
Studies on the Chemical Constitution of Agar-agar. XIX. Pyruvic Acid as a Constituent of Agar-agar (Part 1). Identification and Estimation of Pyruvic Acid in the Hydrolysate of Agar
Authors: Hirase Susumu
Published: July 2006

1. Pyruvic acid has been isolated as its 2,4-dinitrophenylhydrazone from the hydrolysate of agar for the first time.

2. Quantitative determination has indicated that the content of pyruvic acid is 1.06% of agar or one residue for every fifty one hexose residues.

3. It has been suggested that pyruvic acid would be an intrinsic constituent of agar.

4. Several polysaccharides other than agar have been examined, but none of them produced pyruvic acid on hydrolysis.
Oxidimetric and Reductometric Titrations in Neutral Solutions. (Application of Sodium Triphosphate as Masking Agent to Volumetric Analysis.)
Authors: Suzuki Susumu , Harimaya Kenji , Ueno Morio , Tsuji Nobuo , Yamaoka Noriko
Published: July 2006

Antimony(III), arsenic(III), chromium(II), iron(II), molybdenum(V), selenium(IV), thallium(I), titanium(III) and vanadium(IV) are titrated in neutral solutions with oxidizing standard solutions, chromate,bromate, hypobromite, permanganate, and vanadate solution, in the presence of triphosphate. A few of these elements, chromium(II), iron(II), titanium(III) and vanadium(IV) in their mixture are also determined.

On the other hand, cerium(IV), hypobromite, chromate, triiodide, permanganate, vanadate and hydrogen peroxide, are titrated with reducing standard solutions, chromium(II), iron(II), titanium(III), and vanadyl solution containing triphosphate. Some of them in mixtures are also determined.
Sedimentation and Diffusion Studies of Calf Thymus Histone
Authors: Ui Nobuo
Published: July 2006

Two fractions of calf thymus histone, histone I and histone II, were examined by sedimentation and diffusion. Histone I was ultracentrifugally homogeneous in the buffer solutions below pH 7, but showed the presence of an aggregate above pH 7. The sedimentation constant (at infinite dilution) of histone I was calculated to be 2.03 S in an acetate buffer of pH 5.0 at ionic strength of 0.2. The homogeneity of this sample was also confirmed by diffusion experiments in the same buffer, and 5.13×10−7cm2/sec., was obtained as the diffusion constant. Combining the values of sedimentation and diffusion constants as well as the value of partial specific volume, 0.74, the molecular weight was calculated to be 37,000.

Histone II was also found to be homogeneous by sedimentation and diffusion measurements in the acetate buffer of pH 5.0. Its sedimentation constant, diffusion constant, and molecular weight were calculated as 0.66 S, 7.30×10−7cm2/sec., and 8,400, respectively.
Electrophoretic Studies of Calf Thymus Histone
Authors: Ui Nobuo
Published: July 2006

Electrophoretic studies were made on histone I, the main fraction of calf thymus histone, at various ionic strengths, pH’s and temperatures. It was found that at least three components are present in this fraction.

Histone II, the other fraction, was electrophoretically not homogeneous either. One main and three minor components were found to exist, and their mobilities differed from that of any component of histone I.
Studies on Inorganic Constituents in Biological Materials.—On the Inorganic Constituents in Human Stones
Authors: Ohta Naoichi
Published: July 2006

Quantitative analyses of major constituents (calcium, magnesium, phosphorus, sodium and potassium) and heavy metal constituents (iron, copper, zinc, lead and manganese) were made on human stones (gallstone, urinary and pancreatic calculus) and their respective humours (blood, bile and urine). Then the distribution of these elements and the mutual relations present among them were discussed.

(1) According to the process of formation of gallstone (blood→bile→gallstone), the concentration of calcium, magnesium and phosphorus increases, while that of sodium and potassium decreases in case of major constituents, On the other hand, the concentration of heavy metal constituents, copper, zinc, lead and manganese increases. The concentration of iron decreases in the process of blood→bile and then increases again in the process of bile→a gallstone, whilst copper is extremely concentrated throughout these processes.

(2) In the process of urine→urinary calculus, each of major constituents increases; calcium, magnesium and phosphorus are extraordinarily concentrated, and heavy metal constituents also increase zinc is especially the most abundant of all. The correlation between lead and the calcification phenomenon in biological materials is observed, for lead indicates the highest concentration ratio in every case of gallstones (203 times that of bile) and urinary calculi (500 times that of urine).

(3) Pancreatic calculi differ greatly from the other stones, as their major constituents are calcium carbonate and they contain but little of the other constituents. Among heavy metals, zinc and lead are contained in a relatively high quantity; it seems that special connections exist between zinc and Insulin and between zinc and Carbonic anhydrase.

(4) The internal portion of a gallstone that is of layer structure contains a greater quantity of heavy metals than the external portion.
Oxidation of Chromia Supported on Alumina
Authors: Matsunaga Yoshio
Published: July 2006

Oxidation of chromia supported on gamma- and alpha-alumina at room temperature, 250, 350 and 450°C was examined by chemical and magnetic method. The mean oxidation number of chromium in the oxidized catalyst samples was determined as a function of the concentration of chromium. In the extreme case, infinite two-dimensional dilution of chromium, it was shown that chromia is oxidized completely to chromic anhydride. This chemical change is in sharp contrast to our knowledge of the thermal decomposition of chromic anhydride. The remarkable property of supported chromia to suffer oxidation was attributed to the relative importance of surface oxidation and explained nearly quantitatively by comparing it with the conclusion deduced from the susceptibility composition isotherm method developed by Selwood and his coworkers. Therefore, the study of oxidation of the chromia-alumina catalyst system by chemical analysis seems to be useful to the same degree as the magnetic method proposed by Selwood and more convenient for deducing the dispersed structure of supported chromia. Finally the condition of preparing the catalyst sample which has the greatest surface area of chromia per gram of catalyst was examined in reference to the above-mentioned conclusion.
Fundamental Studies on the Biogeochemical Prospecting for Manganese
Authors: Yamagata Noboru , Yamagata Toshiko
Published: July 2006

The possibility of practical application of foliar analyses for geochemical prospecting for manganese were examined. A positive correlation of manganese level between soil and plants was revealed by the experiments using water and soil culture.

For the practical application, a tree, Chamaecyparis obtusa was chosen to avoid small local variations, and the sampling variations due to age and position were determined.

The Mn/Fe ratio was found to be a more sensitive indicator than the manganese content itself and its average value in the mineralized district was 18.4; on the other hand, it was only 3.5 in non-mineralized district.
Further Studies on the Degradation of Yeast Ribonucleic Acid by Lanthanum Hydroxide
Authors: Miyazaki Masazumi
Published: July 2006

The degradation of yeast ribonucleic acid by lanthanum hydroxide was rein-vestigated. The results may be summarized as follows:

1) Most of the RNA seems to be degraded through mononucleotides to nucleo-sides and inorganic phosphate.

2) 2′- and 3′-purine nucleotides were detected as intermediate products. 2′-Nucleotides were produced in less amounts than the corresponding 3′-nucleotides.

3) On the whole, pyrimidine nucleo-sides were liberated faster than purine nucleosides.

4) Liberation of uridine was characteristic. It was preferencially liberated at the beginning and its liberation predominated again at the last stage of reaction.

5) “Lanthanum hydroxide resistant fraction (LaRF)” was dialysable, not precipitated with uranium reagent and had Rf value close to that of guanylic acid.
The Static Electrode Potential Behavior of Tantalum and its Behavior on Anodic Polarisation
Authors: Khairy E M , Hussein M Kamal
Published: July 2006

The electrode potential behavior of tantalum is investigated in buffer solutions initially free from the metal ions covering the pH range 1–12. A “W”-shaped EH/pH plot is obtained and the results reveal the existence of a natural passive pentoxide film overlayered with oxygen doublets. The electrode behaves within the pH range 3–7 as a metal-metal oxide electrode subject to an overvoltage of about one volt. From pH 7 to 12 the behavior is given by the system : Ta / TaO2+ yielding an equilibrium constant K=5.10−16.

Anodic polarization experiments by the repetitive oscillographic method have been also utilised in buffer solutions and in other different media. The oscillograms are mostly characterised by sharp potential jumps associating the charging of the double layer, showing the decided resistivity of the surface film. The capacity of the double layer scarcely exceeds 1 μF / cm2, except in hydrofluoric acid solutions where it attains a maximum value of 30 μF / cm2.
Electrochemical Study of Ethylene Glycol-Acetic Acid System
Authors: Venkatesan V K , Suryanarayana C V
Published: July 2006

Equivalent conductivity, volume contraction, viscosity, dielectric constant and refractometric measurements of mixtures ethylene glycol and acetic acid at dif-ferentnt percentage compositions have been made. Probably a predominating dipole-dipole interaction occurs when ethylene glycol is added to anhydrous acetic acid up to about 60 mole per cent of the latter from where up to 30 mole per cent of acetic acid de-association seems to occur and from 30 mole per cent of acetic acid down-wards slight dissociation is evidenced. This system is dissimilar in behaviour to those of aqueous boric acid and some polyhydric alcohols.
Various Alky Amines and Ammonium Compounds as Accelerators for Grain Growth of Silver Chloride Suspensions in Aqueous Polyvinyl Alcohol Solution
Authors: Oh-yama Yasushi , Futaki Kiyoshi
Published: July 2006

Various alkyl amines and ammonium compounds (non-cyclic and cyclic) were tested as accelerators for the grain growth of silver chloride suspension in aqueous polyvinyl alcohol solution.

The relation previously found between the molecular weight and the grain growth acceleration activity (A) of various organic N-derivatives did not exactly hold for these series of compounds.

Instead, when the concept of the equivalent chain length is introduced, the data were able to be represented by:

logA=−logCg=(nE−β)⁄3.50, where Cg is the critical concentration for grain growth (in millimol), nE the equivalent chain length and β 8 or 12.

This equation quite resembles the relation between chain length and critical micelle concentration of many surface active compounds. The fact leads to the author’s assumption that the mechanism of grain growth of silver chloride would be intrinsically identical with that of micelle formation and this was discussed in another paper.

The equivalent chain lengths of some of these active substances were able to be derived empirically from the number of carbon atoms in the molecule.
Chemical Studies on Wood Hemicelluloses. II. On the Hemicellulose of Ganpi Bast Fibres. I
Authors: Machida Seishi , Nishikori Sadanori
Published: July 2006

The composition of the bast fibres of Ganpi plant (Wickstroemia sikokiana Franch. et Sav.) was investigated in the processes of the traditional paper-making of Japan. It was found that hemicelluloses of the bast fibres had significant bearings on the paper-making and the excellent character of Japanese paper.

The hemicellulose isolated from holocellulose of the Ganpi bast fibres by alkaline extraction were found to be composed of 13.6∼15.8% of d-glucuronic acid (which is partly present as 4-O-methyl-d-glucuronic acid), 58.1∼80.9% of d-xylose, and small amounts of d-mannose, d-galactose, l-arabinose, and l-rhamnose. It was shown that the degree of polymerisation of the hemicellulose calculated as a pentosan is about 160, and the molecule has basically a linear structure in which the uronic groups are present along the polymer chain at a ratio of one carboxyl group for each six or eight pentose sugar units.
Thermal Effects of Some Kaolin Minerals. I. Kaolinite and Kibuski-clay
Authors: Takahashi Hiroshi
Published: July 2006

The structural change of kaolinite and Kibushi-clay with heat-treatment in the relatively low temperature region has been studied. It has been found that there are generally three processes, and that the structural change depends on the degree of crystallinity of the original samples.
Separation of Radioactive Cesium in Biological Materials
Authors: Yamagata Noboru , Yamagata Toshiko
Published: July 2006

A simple and rapid separation method for cesium-137 in biological materials has been presented. It is composed of three steps, phosphate elimination, ammonium phosphomolybdate precipitation and chloroplatinate precipitation. The over-all yield of cesium is over 85% and the decontamination from other fission activities is more than 105 for cerium-144 and strontium-89. The contribution of the activities of rubidium-87 and potassium-40 is negligibly small in the determination of cesium-137 in biological materials by beta counting.
Studies on the Denaturation of Lysozyme. III. Comparative Study of Lysozyme Denaturation on Surface and in Solutions
Authors: Hamaguchi Kozo
Published: July 2006

In order to clarify the correlation between the denaturation of lysozyme on surface and that in solutions, the surface-, heat-, and urea-denaturation which were so far reported by the author were summarized.

The properties of lysozyme monolayers depend not only on the temperature of substrate but also on the state of lysozyme molecules in spreading solutions. The mechanism of the formation of the protein monolayer was clarified by the examination of the denaturation in solutions. Because of the very high content of disulfide bonds in lysozyme molecules, the role played by these bridges in the denaturation on surface and in solutions was also examined and its significance was made clear.
Hydrogen Bonding Effect on the Electronic Absorption Spectrum of p-Hydroxyazobenzene
Authors: Baba Hiroaki
Published: July 2006

The electronic absorption spectra of p-hydroxyazobenzene in iso-octane and also in the mixtures of iso-octane-ether and iso-octane-pyridine were measured. The spectral change observed when addition was made of a small amount of ether or pyridine to a solution of p-hydroxyazobenzene in pure iso-octane was satisfactorily interpreted as due to the formation of a hydrogen bond between the solute molecule and ether or pyridine. The equilibrium constants for the hydrogen bonds and the absorption curves of the hydrogen-bonded complexes were determined from the spectral data.

It is made clear that the effects of hydrogen bonding on the absorption bands are dependent upon the type of the electronic transitions from which the bands originate. The π→π* bands situated in the ultraviolet region are markedly displaced to the red, while the π→π* band in the visible region slightly to the blue. A theoretical explanation for the above phenomena is offered.
Studies on the Cobalt (III) Complexes Containing Only One Chelate Ring. I. Syntheses of [Co(NH3)4gly]X2 and [Co(NH3)4alan]X2
Authors: Shimura Yoichi
Published: July 2006

The three new complexes, [CoIII(NH3)4 gly]SO4·H2O, [CoIII(NH3)4 alan] SO4 and [CoIII(NH3)2 gly2]Cl, have been synthesized by the reaction of [Co(NH3)4(OH2)Cl]SO4 with the amino-acid radicals in the presence of ammonia and decolorizing charcoal.

The visible and the ultraviolet absorption spectra of the glycinato-ammine and alaninato-ammine series of cobalt (III) complexes have been measured and discussed in relation to the geometrical structures of the complex ions.
Heats of Dilution of Polystyrene Solutions. II
Authors: Amaya Kazuo , Fujishiro Ryoichi
Published: July 2006

The heats of dilution in the systems of polystyrene - benzene and polystyrene-cyclohexane were measured and the values of interaction parameters were derived. The heat of mixing of ethylbenzene, which may be regarded as the monomer unit of polystyrene, with the same solvents was also measured and it was found that the interaction of polymer solutions has the same sign as those of the corresponding monomer unit solutions.
Tricalcium Phosphate and its Variation
Authors: Ando Jumpei
Published: July 2006

Properties of tricalcium phosphate and effects of many other ingredients upon the structure and solubility of the phosphate were investigated. By the reaction of calcium salts with phosphates in aqueous solution, tricalcium phosphate hydrate with a definite structure is not formed but hydroxy apatite with an excess of phosphoric acid is formed, which varies to β-tricalcium phosphate by heating between 700–800°C. Contrary to many other reports, it was found that β-tricalcium phosphate was fairly soluble in citric acid. The solubility is reduced remarkably by a small amount of admixtures, especially of magnesia. Magnesia stabilizes the β modification and prevents β→α inversion of the phosphate. The effect of alumina and ferric oxide is similar but not so intense as magnesia. On the contrary, barium oxide stabilizes the α modification. Sodium oxide affects variously according to the ratio of substitution for lime. Constitution and solubility of phosphate fertilizers were discussed in relation to these results.
Ultraviolet Absorption Spectra of Three Isomeric Pyridinemethanols and Their N-Oxides
Authors: Hata Norisuke
Published: July 2006

The ultraviolet absorption spectra of three isomeric pyridinemethanols and their N-oxides were measured in various solvents, n–π* Absorption was observed as the shoulder absorption only in n-hexane solution of 3-pyridinemethanol, for which a qualitative discussion was made.

It was also found that the substituiton of a hydroxymethyl group in 4-position of pyridine or 2-position of pyridine N-oxide caused the blue shift. To explain this fact the presence of a weak intramolecular hydrogen bond in 2-pyridinemethanol N-oxide was assumed.
Polymerization of Olefins with Trialkylboron Catalysts. I. Polymerization of Vinylchloride and Acrylonitrile
Authors: Ashikari Nobuyuki
Published: July 2006

It was found that trialkylboron is an excellent catalyst for the polymerization to some olefins which have comparatively large polarities. Vinylchloride and acrylonitrile were polymerized with this catalyst at a comparatively low temperature, and white polymers were usually obtained.

Vinylchloride was polymerized in bulksolution- and emulsion-system, and the rate of polymerization or the relation between the yield and the concentration of catalyst was investigated. Generally, the molecular weight of the polyvinylchloride was small (less than 50,000).

The polymerization of acrylonitrile was studied chiefly in a solution system. Usually, the molecular weight of polyacrylonitrile was fairly large.
Ultraviolet Absorption Spectra of Three Isomeric Pyridine Monocarboxylic Acids and Their N-Oxides
Authors: Hata Norisuke
Published: July 2006

The ultraviolet absorption spectra of 2-, 3- and 4-pyridine monocarboxylic acid and their N-oxides were measured in various solvents. The absorption spectra of these compounds with the exception of picolinic acid show the blue shift with the change of the solvent from dioxane to ethanol and water.

The absorption band of picolinic acid occurs in the region of the shorter wavelength than that of isonicotinic acid; this fact may be caused by the formation of the intramolecular hydrogen bond, which prevents the resonance of this molecule. The absorption band of picolinic acid N-oxide occurs in the region of the shorter wevelength than that of nicotinic or isonicotinic acid N-oxide, for which the present author attributed the formation of the intramolecular hydrogen bond and the steric interaction in picolinic acid N-oxide. We also observed the n–π* absorption in picolinic acid N-oxide.
Partial Hydrogenation of 1,4-Butynediol. II. On the Role of Calcium Carbonate as a Carrier of the Palladium Catalyst
Authors: Fukuda Tosao
Published: July 2006

1. The role of calcium carbonate as carrier of the palladium catalyst was studied in the hydrogenation of 1,4-butynediol.

2. The hydrogenation velocity on Pd-CaCO3 catalyst was not the highest among various palladium catalysts. And the partial hydrogenation of 1,4-butynediol might also be achieved by using the Pd-BaCO3 catalyst poisoned by both lead acetate and quinoline. On the poisoned Pd-CaCO3catalyst, however, the 1,4-butynediol polymerization, a side reaction of the hydrogenation, was suppressed largely.

3. Consequently, it seems that the role of calcium carbonate as a carrier is to decrease the polymerization as a side reaction of the hydrogenation, but not to increase the activity for the hydrogenation, nor to give the selectivity for the hydrogenation.
A New Viscosity Relationship in a Wide Concentration Range of Aqueous Solutions of Potassium Chloride
Authors: Suryanarayana C V , Venkatesan V K
Published: July 2006

A systematic investigation of viscosity from 1.00 m. to saturation of aqueous solutions of potassium chloride at temperatures of 30, 35, 40, 45, 50 and 55°C has been made. New concepts of concentration and viscosity have been defined. At a given molal concentration the ratio of the mole-fraction at that concentration to that at saturation at the same temperature has been called concentration potential Cp. The newly denned viscosity term ηp is the ratio of the viscosity at a given concentration to that at saturation at the same temperature. Using these two quantities the variation of viscosity with concentration could be expressed for potassium chloride solutions by a simple exponential equation:

η_p=A e^BC_p

where A and B are constants.
Electronic Structure and Spectra of s-Tetrazine
Authors: Mataga Noboru
Published: July 2006

(1) π-Electronic structure and the nature of the electronic transitions in the s-tetrazine molecule has been elucidated using the semiempirical LCAO SCF MO method.

(2) There is satisfactory agreement between the calculated and the observed values of the excitation energy for the transition to the lowest excited state.

(3) Tsubomura’s qualitive argument concerning the influence of configuration interaction on the lowest energy transition of nitrogen heterocycles has been confirmed by the quantitative calculation.

(4) The cause of the intensification of 1Lb band compared with the parent hydrocarbon has been analysed by the same method employed previously, and it has been confirmed that, also in the case of s-tetrazine the perturbation on MO by hetero-replacement has only a small influence on the oscillator strength.

(5) The spectral simirarity of nitrogen heterocycles with the parent hydrocarbon has been ascribed to the fact that their MO’s correspond closely each other, and it has been pointed out that the configuration interaction plays a very important role in the determination of spectra, which is also a cause for the spectral similarity.
Electronic Spectra of Quinoline and Isoquinoline and the Mechanism of Fluorescence Quenching in These Molecules
Authors: Mataga Noboru
Published: July 2006

1. A pertubation theory based on the Hartree-Fock SCF theory including a limited number of configuration interactions was applied to quinoline and isoquinoline.

2. The theory satisfactorily interprets the excitation energies and oscillator strengths of 1Lb bands of these nitrogen heterocycles.

3. The previous assumption concerning the effect of π-electronic state on the fluorescence quenching in nitrogen heterocycles due to the near-by existence of a halogen atom, was confirmed for the case of quinoline, on the basis of the theoretical calculation.
Analysis of the Hardening Reaction of Furfurylalcohol Resin
Authors: Yamada Shigehiko , Hayashi Shigeo
Published: July 2006

Decreasing tendency of resistance in the system consisting of furfurylalcohol resin, graphite filler and accelerator was observed and analysed, and this observation gave an activation energy of the final cure, together with that of the apparent cure calculated from the saturation time of adhesion power. Besides, activation of sulfonylchloride accelerator was investigated taking account of the adhesion power increase and resistance decrease.

These considerations may be full of suggestions for the practical use of such a cement system.
Formation and Aging of Precipitates. VII. Habit of Crystals in Vanadium Pentoxide Sols by Electron Microdiffraction Method
Authors: Takiyama Kazuyoshi
Published: July 2006

The crystals in Biltz-, Müller-, and ion-exchange sols were all identified with vanadium pentoxide by the electron diffraction method.

The crystals in aged Biltz sol were fiber-like. The specimen prepared ordinarily gave rise to the Debye-Scherrer pattern and that of the tactoid corresponded to the fiber pattern. The fiber axis of the fibrous crystal was decided to be the b-axis.
Molecular Rotations of Glucides in Relation to their Structures. VI. Optical Superposition in Methyl Pentoses. Presumption of Two Unknown [M]D20(W)
Authors: Yamana Shukichi
Published: July 2006

It was concluded by PM-method that the principle of optical superposition of Kirkwood’s idea exists in methyl pentoses, and two [M]D20(W), formerly unknown, were presumed.
Ion Exchange in Concentrated Solutions. II. Beryllium Chloride-Hydrochloric Acid System
Authors: Ohtaki Hitoshi , Yamasaki Kazuo
Published: July 2006

The ion exchange equilibrium was studied in the concentrated solutions of beryllium chloride and hydrochloric acid.The amount of water in the resin was calculated from the difference of hydrogen ion concentration before and after the ion exchange equilibrium. A cationic complex containing beryllium was found to be formed in the solution. The expenses of the present study were defrayed by Grant-in-Aid for Fundamental Scientific Resiarch from the Ministry of Education.
The Separation of Sulfate, Sulfite, Thiosulfate and Sulfide Ions with Anion-Exchange Resins
Authors: Iguchi Akira
Published: July 2006

1. The distribution coefficients of sulfate, thiosulfate, sulfite and sulfide in the nitrate solution were measured.

2. By the addition of ethanol or acetone to the neutral eluant solution, the adsorb-ability of sulfate, sulfite, thiosulfate and sulfide was increased, while that of sulfite in alkaline acetone solution showed a marked decrease.

3. By the use of these results a mutual separation of sulfate, thiosulfate, sulfite and sulfide was effected by the anion-exchange chromatography.
Studies on Organic Peroxides. IV. Polymerization of Vinyl Acetate in Benzoyl Peroxide-Fe (II)-Benzoin Redox System
Authors: Hasegawa Shigeo , Hirai Nishio , Nishimura Norio , Kawano Tsugio
Published: July 2006

Polymerization of vinyl acetate in the benzoyl peroxide-iron-(II)-benzoin redox-system was studied in ethanol. From the extent of decrease in volume, the rate of conversion was calculated. It was found that the square of the initial rate of conversion was proportional to the initial concentration of ferrous ion and that the extent of conversion at the time when the polymerization was finished, decreased with increasing amount of ferrous ion which was added.

The initial rate of conversion in this redox system was found to depend also on the mole ratio of the monomer to ethanol. The reason might be ascribed to the change in the rate constant.
Effect of Substitution on Dipole Moments of Molecules
Authors: Yoneda Hayami
Published: July 2006

As a result of the examination of dipole moments of hydrides of various elements and their alkyl derivatives the following regularity was found. Hydrides of elements below the third period in the periodic table show the normal variation of dipole moments with successive alkyl substitution. That is, the dipole moment increases with successive alkyl substitution, which is expected from the consideration of the inductive effect of substituents. On the other hand, hydrides of elements in the second period in the periodic table show the abnormal variation of dipole moments with successive alkyl substitution, which apparently seems to contradict the existence of the inductive effect. That is, the dipole moment decreases with successive alkyl substitution. This fact was connected with the concept of s-p hybridization of non-bonding electrons, and the following rule was drawn. The more –I active a substituent is, the more the degree of s-p hybridization of non-bonding electrons decreases, and hence the more the contribution of the atom dipole moment to the whole dipole moment decreases. Some applications of this rule to the chemistry of coordination compounds were also presented.
The Infrared Spectra of Methoxy-, Methylmethoxy- and Methoxy Endblocked Dimethyl-polysiloxanes
Authors: Tanaka Toshio
Published: July 2006

1) The infrared spectra of the lower members of methoxy-, methylmethoxy and methoxy endblocked dimethyl-polysiloxanes have been discussed by comparing them with that of dimethylether, dimethylpolysiloxanes, and so on.

2) The characteristic absorption band of Si—OCH3 group has appeared near 1190 cm−1.

3) Except in the case of the first members of these alkoxysiloxanes, a spectral sequence corresponding to the structural unit sequence of SiO4, SiO3C and SiO2C2 has been observed in the region of 1000∼1100 cm−1.
Synthesis of α-Substituted Glutarimides via Michael Condensation
Authors: Kametani Tetsuji , Taub William , Ginsburg David
Published: July 2006

A method for the synthesis of α-monosubstituted and α, α-disubstituted glutarimides by Michael addition of active methylene and methine compounds to acrylonitrile or acrylamide, is described.
Synthesis of Histidyl Peptides
Authors: Sakiyama Fumio , Okawa Kenji , Yamakawa Tsuneo , Akabori Shiro
Published: July 2006

N-α,N-Im-Dicarbobenzyloxyhistidine was prepared in good yield using sodium carbonate, and some histidyl peptide derivatives were synthesized by Sheehan’s method using the compound as a starting material.

Grateful acknowledgement is due to Ajinomoto Company for supplying materials of amino acids.
Kinetics of the Caro’s Acid Oxidation of Dimethylanilines
Authors: Ogata Yoshiro , Tabushi Iwao
Published: July 2006

The rates of the Caro’s acid oxidation of dimethylaniline and p-substituted dimethylanilines were measured in aqueous solutions of various pH’s and temperatures. The rates were found to be proportional to the product of the concentrations of both reactants. The effects of pH and p-substituents on the rate constant were estimated. The rate constant in acid media increased with increasing electron-withdrawing power of the p-substituent of dimethylaniline, while the constant in alkaline media increased with decreasing pH or increasing electron-releasing power of the substituent. A probable mechanism involving a rate-determining attack of neutral Caro’s acid molecule on free amine was proposed and discussed.
The Reaction of 1,8-Cineole with Acid Solutions
Authors: Matsuura Tamon , Komae Hisashi , Sait\={o} K\={o}z\={o}
Published: July 2006

The reaction of 1,8-cineole with 60% acetic acid at 70°C for 10 hours under stirring gave dl-α-terpineol (0.12%) and trans terpin (0.03%). By the action of 21% sulfuric acid at 70°C for 3 hours, cineole yielded dl-α-terpineol (4.6%), terpin hydrate (0.20%), trans-terpin (0.12%) and monocyclic hydrocarbons (a small amount). On the other hand, the reaxtion of cineole with 0.6% sulfuric acid solution at 70°C for 10 hours gave dl-α-terpineol and trans-terpin in poor yields. In this case the reaction products are the same as in the case of 60% acetic acid.

Next, terpin hydrate was treated with 64% acetic acid at 70°C for 10 hours. The reaction products were dl-α-terpineol (2.7%) and trans-terpin (trace). By the action of 21% sulfuric acid at 70°C, terpin hydrate was attacked easily, and after 15 minutes it was converted to dl-α-terpineol (17.8%), trans-terpin (0.20%), 1,8-cineole and monocyclic hydrocarbons (11%). The monocyclic hydrocarbons consisted of α-terpinene, dipentene, Δ2,4(8)-p-menthadiene and p-cymene. trans-Terpin was, also, treated with 60% acetic acid at 70°C for 10 hours, the reaction product being dl-α-tepineol (1.8%).

On the basis of the above experiments a reaction mechanism for the action of acid solutions on 1,8-cineole was proposed.
Polymerization of Olefins with Trialkylboron Catalyst. III. Copolymerization of Butadiene, Isobutylene and 1-Phenylbutadiene
Authors: Ashikari Nobuyuki
Published: July 2006

The relative reactivities in the copolymerization of some monomers which do not polymerize alone with alkylboron catalyst, with those which polymerize alone, were obtained. The copolymerization rate of 1-phenylbutadiene with another monomer was so small that the relative reactivity could not be obtained. But, from the studies on the reaction product of 1-phenylbutadiene and methyl methacrylate, it was considered that the former copolymerized with the latter.
Recombination of Hydrogen, Nitrogen and Oxygen Atoms on Copper and Silver Single Crystal Surfaces
Authors: Nakada Kazuo
Published: July 2006

Recombination of hydrogen atoms, nitrogen atoms and oxygen atoms was carried out on single crystal surfaces of copper and silver subjected to various surface pre-treatments.

With both the recombination of hydrogen atoms and that of nitrogen atoms, copper surfaces electrolytically polished have always higher activity than those chemically polished. The Cu(100) surface chemically etched by ammonium persulfate was more active than that etched by nitric acid for both hydrogen atoms and nitrogen atoms, whereas with the Cu(110) the opposite order of activity was obtained. For both silver and copper, no evidence was found to show the different order of activity between the recombination of hydrogen atoms and that of nitrogen atoms. Concerning the recombination of oxygen atoms on single crystal surfaces of silver, the (110) face was found to be more active than the (100) face in accord with the result of our earlier work about the recombination of hydrogen atoms on single crystal surfaces of copper.
Polymerization of Methyl Methacrylate Initiated by the System of p-Toluenesulfinic Acid, Dimethylaniline and Oxygen
Authors: Uehara Ryoichi
Published: July 2006

Initiation of the polymerization of methyl methacrylate with the initiating system, p-toluenesulfinc acid-oxygen-dimethylaniline, has been investigated from the standpoint of chemical kinetics. The initial rate of polymerization of methyl methacrylate was linearly proportional to the square roots of the concentrations of each component of the initiating system, and methyl methacrylate. The polymerization initiating action of the initiating system is lost by changing the sulfinic acid to its anhydride or esters. The formation of a salt from the sulfinic acid and dimethylaniline was suggested as the first step of the initiation of the polymerization.
Synthesis of Polyanhydride. I. Mixed Anhydride of Aromatic and Aliphatic Dibasic Acids
Authors: Yoda Naoya , Miyake Akihisa
Published: July 2006

Copolymerization reactions of mixed anhydrides of aliphatic and aromatic dibasic acids have been investigated. It has been shown that a polyanhydride of regular structure was obtained from diacid chlorides and dibasic acids in organic medium, and that polyanhydrides of random structure were obtained from the mixed aromatic and aliphatic dibasic acids. A polyanhydride having its melting point at 225°C was prepared for terephthalic acid and adipic acid copolymer of regularly linked structure and that having its melting point at 215°C for terephthalic acid and sebacic acid copolymer. It was found that the stability of copolymer towards hydrolytic and thermal degradations was greater for those with regularly linked structure than for a polyanhydride of random structure. The mixed polyanhydrides of random structure were prepared and the diagram of composition versus melting point was obtained. The mole fractions of the two acid components were found to be 35∼40 mol. % of terephthalic acid and 60∼65 mol. % of aliphatic dibasic acid for copolymers melting at 220 to 240°C. It has further been shown that aliphatic and aromatic dibasic acids furnish a series of copolymers in which the solubility decreases and the melting point and the degree of crystallinity increase as the proportion of aromatic dibasic acid is increased.
Self-diffusion of Iodide Ion and Strontium Ion in Strontium Iodide Solutions
Authors: Matuura Ryohei , Koga Yasushi
Published: July 2006

The self-diffusion coefficient of iodide ion and strontium ion in aqueous strontium iodide solutions has been measured by a capillary method. It has been found that the Onsager’s limiting equation can be applied to the self-diffusion of both ions. The Dη⁄η0 vs. \sqrtc relation for iodide ion has been represented by two straight lines, while that for strontium ion has been shown by a much more complicated curve. The latter has been represented successfully by an empirical equation for strongly hydrated ions presented by Matuura and Shimozawa.
The Crystal Structure of Bis(adiponitrilo)copper(I) Nitrate
Authors: Kinoshita Yukio , Matsubara Ikuo , Higuchi Taiichi , Saito Yoshihiko
Published: July 2006

The crystal structure of bis(adiponitrilo)-copper(I) nitrate has been determined by the two-dimensional Fourier method. It is orthorhombic Pnnn with two formula units in a cell of dimensions: a=9.41±0.02 Å, b=13.73±0.02Å and c=5.85±0.01 Å.

The crystal consists of infinite three-dimensional networks of complex ion [Cu(NC–CH2–CH2–CH2–CH2–CN)2]nn+ and nitrate ions. A copper atom is tetrahedrally surrounded by four nitrogen atoms at a distance of 1.98 Å. Each adiponitrile molecule is coordinated to two different copper atoms with nitrogen atoms of both ends, forming a planar zigzag configuration of methylene groups. Thus the copper atoms and the ligand molecules form a complicated threedimensional 4-connected network. The nitrate ions lie perpendicularly to the a-axis. The trigonal nitrate ion seems to have statistical azimuthal orientations in the crystal and its apparent symmetry becomes 222.

All the atoms in the group Cu–N–C–C lie approximately on a straight line. This fact and the observed carbon-nitrogen distance of 1.13 Å suggest that the bond character in the carbon-nitrogen group may essentially be expressed as C≡N.

On the basis of the structures of this and the other related complexes, some remarks have been made on the mechanism of cuprous ion dyeing of polyacrylonitrile fibers.
Studies on the State of Formic Acid Adsorbed on Silica and Alumina by a Combined Method of Nuclear Magnetic Resonance and Infrared Absorption
Authors: Hirota Kozo , Fueki Kenji , Shindo Kotaro , Nakai Yasuo
Published: July 2006

The state of formic acid adsorbed on silica and alumina has been studied by a combined method of nuclear magnetic resonance and infrared absorption. The adsorbed formic acid in a monomolecular layer has been found not to be dissociated in the case of silica, but to be dissociated in the case of alumina.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. I. Biphenyl
Authors: Suzuki Hiroshi
Published: July 2006

1) The ultraviolet absorption spectra of biphenyl in the crystalline state, in the solution state, and in the vapor state have been discussed in detail.

2) The relation between the position of conjugation band in the spectra of biphenyl and the spatial configuration of the molecule has been clarified by calculations based on the simple LCAO molecular orbital method.

3) By using the results of the calculations, it has been inferred from the analysis of the absorption spectra that the angles between the planes of the two benzene rings in the most probable conformations of biphenyl in the solution state and in the vapor state are about 20°C and about 40∼43°C, respectively. These values coincide fairly well with the values estimated by other workers on different grounds.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. II. o-Alkyl-and o,o′-Dialkylbiphenyls
Authors: Suzuki Hiroshi
Published: July 2006

The method described in the preceding part of this series has been applied with allowance for the electronic bathochromic effect of the substituents to o-alkyl- and o,o′-dialkylbiphenyls, and the relation between the ultraviolet absorption spectra and the most probable spatial configurations of these compounds has been clarified, resulting in the conclusion that the interplanar angle in o-methylbiphenyl as well as its analogues is about 60°C and that o,o′-dimethylbiphenyl as well as its analogues has the cis-configuration in which the interplanar angle is about 70°C.

On the basis of the result, the interpretation by Braude and Forbes of the spectra of o-methyl- and o,o′-dimethylbiphenyl has been criticized.

In addition, the inferred spatial configurations of these biphenyl derivatives have been correlated with some physical and chemical properties of these and some related compounds.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. III. o,o′-Bridged Biphenyls
Authors: Suzuki Hiroshi
Published: July 2006

The ultraviolet absorption spectra of some o,o′-bridged biphenyls and their relations to the spatial configurations have been discussed. The method developed in the earlier parts of this series has been applied to these compounds, especially o,o′-three-atom-bridged (o,o′-7-memberedring-bridged) and o,o′-four-atom-bridged (o,o′-8-membered-ring-bridged) biphenyls, and the interplanar angles have been calculated to be about 44.5∼47.3° (average, 46°) for the former compounds and about 58.0∼61.5° (average, 59.8°) for the latter.
Effect of Dry Grinding on Gibbsite
Authors: Yamaguchi Goro , Sakamoto Kenichi
Published: July 2006

The effect of dry grinding on gibbsite was examined by X-ray diffraction, X-ray small angle diffraction and differential thermal analysis. It has been found that there are two sorts of structural change in the process of dry grinding. One, which occurs early in this process, is the slip of layers. In this stage (002) reflection retains its intensity. The other, which takes place after grinding of about 10 hr., is the three-dimensional disintegration of the crystal structure and the intensities of all diffractions become weak. Since only two reflections (002) and (110) are observed after 40 hr., it can be known that the direction of the slipping of layers is [110].

DTA-curve of gibbsite exhibits three endothermic peaks in the beginning of grinding but comes to exhibit only one peak which indicates the decomposition of gibbsite to alumina. This means that ground gibbsite decomposes directly to χ-alumina as fine gibbsite and boehmite is not produced in this process.
The Kinetics of Substitution Reactions Involving Metal Complexes. II. Effect of Acetate Ions on the Reaction between Copper(II) and Lead-Ethylenediaminetetraacetate Complexes
Authors: Tanaka Nobuyuki , Kato Kiyoko
Published: July 2006

The effect of acetate ions on the rate of the substitution reaction of copper(II) and lead-EDTA complexes is explained quantitatively on the basis of the formation of acetato complexes of copper (II) and lead(II) in acetate media and on the assumption that the substitution reaction proceeds only through the hydrated metal ions. The rate constants, the heats of activation and the entropies of activation for three elementary reactions are recalculated with the experimental results obtained previously.
Studies on the Graphitization II. Sub-structure and Crystallite Growth of Carbon Black
Authors: Kuroda Haruo , Akamatu Hideo
Published: July 2006

The sub-structures of carbon black and its change with heat-treatment have been investigated by means of X-ray small-angle scattering and electron microscopy.

With heat-treatment, the X-ray small-angle scattering intensity increases in the higher angle region, indicating the development of heterogeneous sub-structures to minute crystallites. Above 2000°C, the crystallite growth is rapidly accelerated, and at an extreme, a carbon black particle disintegrated to smaller crystalline units. Electron microscopic observations, especially for Thermax which has a large particle size, revealed that the crystallites, are in alignment with their c-axes being in the direction of normal to the particle surface. This alignment leads to the polyhedral shape of the heat-treated particles. From these observations, the substructures and the mechanism of crystallite growth in carbon black particles have been discussed.