bluuebunny/crossref_metadata_2025 huggingface dataset:
Determination of Nitrogen in Nitro and Oxime Compounds by the Iodic Acid Decomposition Method
Authors: Ohashi Shigeru
Published: July 2006

(1) The iodic acid decomposition method for the determination of nitrogen in organic compounds, which has been reported already by the author, was extended to analyses of nitro and oxime compounds.

(2) In a reaction vessel, a samplew as dissolved in acetone, reduced with a reducing agent to the corresponding amine, and then decomposed by heating with a mixture of iodic acid and strong phosphoric acid. The liberated nitrogen was determined by means of an azotometer.

(3) After testing many reducing agents it was concluded that a mixture of iron metal powder and diluted sulfuric acid was the best.

(4) For various nitro and oxime compounds satisfactory results were obtained by means of this modified method.

(5) The specific gravity and the chemical composition of strong phosphoric acid prepared in the various conditions have been described complementally.
The Structon Theory of Glasses and Solutions
Authors: Huggins Maurice L
Published: July 2006

In sodium silicate glasses and in many liquid solutions, curves representing the dependence of various properties on composition show distinct breaks. This behavior can be reasonably interpreted in terms of the types of environment around each atom or molecule or atomic group responsible for strong intermolecular interactions, together with the assumption that in these systems only the most stable environments are present in significant amounts. Only closest neighbors need be considered, hence the types of environment can conveniently be described in terms of “ structons,” each structon type being defined as a given kind of atom (or molecule or atomic group) surrounded by close neighbors in a given way.

The compositions at the breaks in the property curves limit, and in some cases determine uniquely, the types of structon present in and between the different composition ranges.

The structon theory has been applied to sodium silicate glasses and certain liquid solutions, in which there are strong hydrogen-bond interactions between molecules.
Polarographic Behavior of Nitroammonocarbonic Acids in Aqueous Media. I. Nitrourea
Authors: Namba Keiho , Suzuki Kyoichi
Published: July 2006

1) The relationship of pH–E1⁄2 (vs. S.C.E.) and of pH–il of nitrourea under the dropping mercury electrode was studied.

2) It is presumed from the experiment on the effect of the effective height of the mercury reservoir and of temperature upon ii that ii will follow the diffusion law in acidic solution.

3) The electron number consumed for reduction was calculated by assuming the diffusion coefficient.
Spectrochemical Study of Microscopic Crystals. IX. Absorption Spectra and Structure of Cobalt(II) Mercury(II) Tetrathiocyanate
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Polarized absorption spectra of CoHg(SCN)4 in the crystalline state have been determined by Tsuchida-Kobayashi’s microscopic method in the regions between 2400 and 7000 Å.

Absorption spectra of HgCo(NCS)4 shows the existence of the Co(NCS)4-group. Thus it has been concluded that the NCS-group is attached to a cobalt atom through a nitrogen atom, and to a mercury atom through a sulphur atom on the other end of the NCS-group.
Syntheses of Adenosinesulfuric Acids
Authors: Egami Fujio , Takahashi Noriko
Published: July 2006

Syntheses of adenosinesulfuric acids were achieved by sulfation of adenosine with chlorosulphonic acid.

The crude product was a mixture of AMS, ADS and ATS, and the proportion of each component varied according to the amount of chlorosulphonic acid used and to the reaction temperature.

Quantitative separation of AMS, ADS and ATS has been achieved successfully by ionexchange chromatography.

Barium adenosine-5′-monosulfate was obtained in crystalline form, and the ultraviolet absorption spectra were measured.
Surface Chemistry of Synthetic Protein Analogues. V. On the Effect of Salt on the Monolayers of the Copolypeptide of l-Lysine, l-Phenylalanine and l-Glutamic Acid
Authors: Hamaguchi Kozo , Isemura Toshizo
Published: July 2006

By studying the surface pressure-area and surface viscosity-area curves of the copolypeptide of l-lysine, l-phenylalanine and l-glutamic acid over a range of pH values and salt contents in the substrate, the following four distinct results were obtained:

(1) When the concentration of potassium chloride in the substrate was kept constant (0.07 m/litre), the (A)F-pH curve has a minimum area region between pH 5.6 and 8.0 which is parallel to the pH axis and this region corresponds to the isoelectric band of this copolypeptide at this salt concentration. The width of this band was the function of the salt concentration; when the salt content was increased this band became wider.

(2) When the pH’s of the substrates was kept constant (pH 2.2), the F-A curves were more expanded at low salt concentrations. This fact could be interpreted by the increment of surface pressure due to the free energy of the electrical double layer which is formed between the ionized groups of the monolayer (NH3+ ions) and the counter ions (Cl− ions). The values of surface potentials calculated from the F-A curves and from Gouy’s equation agreed with each other.

(3) The surface viscosities became higher when the salt concentrations in the substrate at constant pH’s were decreased and became maximum at its isoelectric point. The surface viscosity depends markedly on the number of inter- or intra-salt-linkages between -NH3+ and COO− ions and not on the shape of each polymer molecule.

(4) The (A)F-pH and (η)A-pH curves could be interpreted in terms of effective free charges and the number of salt-linkages.
Interaction between Surface Active Agents and Proteins. I. Precipitations formed by Mixing Sodium Alkyl Sulfates and Egg Albumin
Authors: Aoki Koichiro , Hori Joji
Published: July 2006

(1) Precipitation reactions between SDS and egg albumin, SOS and egg albumin, and SBS and egg albumin were studied. There was an instant precipitation when SDS and egg albumin solutions were mixed, and when SOS and egg albumin solutions were mixed, but not when SBS and egg albumin solutions were mixed. Comparing the precipitation curve of the SDS-egg albumin system and that of the SOS-egg albumin system, we can find that both detergents form a complex having the same formula AD40 (A : albumin, D: detergent) in the region of protein excess, and therefore we can conclude that there is no difference between the reactivities of SDS and SOS toward egg albumin. On the contrary, in the region where redissolution of precipitate occurs, the precipitation curves do not coincide. This means that the two detergents have different powers to dissolve precipitate. In addition, when the concentration of SOS differs, the power to dissolve precipitate differs.

(2) It was found electrophoretically that the complex is formed in turbid supernatants after centrifugation and also in transparent solutions the composition of which is in the region where no precipitation occurs.

(3) Observing the precipitation curves of the system horse serum albumin-SDS and the system egg albumin-SDS, we can see that there is a region where no precipitation occurs when a great excess of serum albumin is used; but there is not such a region when a great excess of egg albumin is used.

(4) We measured the lowering of the CMC of SDS and of SOS caused by the increase in the concentration of buffer solution. The lowering does not depend upon the kinds and pH’s of buffer solutions but upon the ionic strength of buffer solution which dissolves detergent.
The Effect of Temperature on Micelle Formation and Solubilization in Benzene
Authors: Kitahara Ayao
Published: July 2006

Van’t Hoff factors of fatty acid salts of higher aliphatic primary amines in benzene were determined cryoscopically and ebullioscopically. Slight or no micelle formation takes place at boiling temperature, though it does take place at melting temperature. Solubilization of water into benzene by these detergents was measured at 10°, 26° and 40°C. With rise of temperature the critical micelle concentration obtained from solubilization increases and the solubilizing power decreases, though the solubilizing power of propionate and butyrate shows an anomaly. Solubilization and micelle formation determined here change parallel to each other with varying temperature.
Cathodo-luminescence of Samarium as Applied to the Structural Studies of Alumina. IV. On Alumina yielded by Thermal Decomposition of Hydrated Crystals of Aluminium Salts
Authors: Iwase Eiichi , Nishiyama Seijiro
Published: July 2006

Hydrated crystals of some aluminium salts, namely nitrate, chloride, sulphate and ammonium alum were subjected to heat treatments in the presence of a small amount of samarium ions. Cathodo-luminescence spectra were investigeted on the samarium-bearing aluminas thus resulted. A conversion of the luminescence spectrum takes place, as the temperature of the heat treatment has been elevated, from the prototype I to the prototype II, which corresponds to the γ-α transformation of an alumina. It was, however, confirmed that there are some differences in the facility of this conversion according to the kinds of aluminium salts employed for the preparation of alumina.

Some alterations were, furthermore, perceived in the intensity of luminescence bands situating in the vicinity of 610 mμ, when the hydrated crystals of aluminium nitrate were submitted to the heat treatments of various elevated temperatures.

Hydrated crystals of these aluminium salts were heated previously at various temperatures between 180 and 1200°C. After the addition of samarium ions, they were roasted.

The resulting samarium-bearing aluminas give rise to cathodo-luminescence spectra, which reveal that a conversion to the genuine α-modification proceeds most readily in the case of aluminium nitrate, while it occurs with difficulty in the cases of hydrated aluminium sulphate and ammonium alum. It seems to be hard for samarium ions to enter into the configuration of alumina, when previous thermal treatments of aluminium salts have been carried out at much elevated temperatures.
Studies on the Cooking Mechanism of Wood. XIV. On the UV-Absorption Spectrum, Phenolic Hydroxyl Group and Carboxyl Group of Thiolignin
Authors: Mikawa Hiroshi , Sato Koichiro , Takasaki Chizuko , Ebisawa Kiyo
Published: July 2006

It was shown that the UV-absorption spectrum of thiolignin must be explained by assuming the existence of the carbonyl group, the double bond conjugated with the nucleus and the carboxyl group attached directly to the nucleus. The amount of the phenolic hydroxyl group and the carboxyl group of thiolignin were estimated by methylating with diazomethane and subsequently hydrolyzing the methylated lignin with alkali.
Magnetochemical Study of Hydroxyazobenzenes
Authors: Matsunaga Yoshio
Published: July 2006

The magnetic susceptibilities of azobenzene and its nine derivatives were measured by the Gouy method. The procedure to estimate the molar susceptibility from the values observed for constitutional fragments of the molecule was applied to these compounds, and the empirical constant for azo-group–0.4 was determined. Twenty hydroxyazobenzenes, mainly derivatives of phenol and p-cresol, were also measured, and their molar susceptibilities were compared with the calculated values for the azophenol form and the quinonehydrazone one. The author concluded that they are all in the azophenol form in the solid state.
Sterols and Other Unsaponifiable Substances in the Lipids of Shell Fishes, Crustacea and Echinoderms. XVII. Mono-unsaturated Sterol Components of the Starfish Asterina Pectinifera
Authors: Toyama Yoshiyuki , Takagi Toru
Published: July 2006

In a continuation of the study on sterol components of Asterina pectinifera, the present study is concerned with mono-unsaturated sterol components. The steryl acetate fraction recovered from the mother liquors of the recrystallizations, which were carried out for the separation of hitodesteryl (α-spinasteryl) acetate in a previous study, was subjected to fractional crystallizations by which two fractions, Δ7-spinastenyl acetate fraction and Δ7-cholestenyl acetate fraction, were eventually separated. Accordingly it has been found that the sterol mixture of Asterina pectinifera contains Δ7-spinastenol and Δ7-cholestenol besides hitodesterol.
Thixotropy of Alginate Gels
Authors: Sasaki Tunetaka , Miyamoto Shigeru , Morinaga Yasuko
Published: July 2006

Thixotropy was observed on the gels formed by the addition of the suitable amounts of cupric chloride, barium chloride, lead nitrate, calcium chloride, cadmium sulfate, zinc sulfate and nickel sulfate to the solutions of sodium alginate. The setting time of the thixotropic gels was observed to change with the amount of the electrolyte added, the ageing time of the gels, the degree of polymerization of sodium alginate used and pH of the system. The thixotropic behavior was observed to change also with the volume of the system. Furthermore, it was found that thixotropy was observed when about 25–54% of the total alginate ions combine with cupric ions, whereas the combination of more than half of the total alginate ion results in nonthixotropic gelation. The thixotropic gel could be formed also by the addition of sodium alginate to the once precipitated copper alginate.
Cyanoethylation of Trichlorosilane. I. β-Addition.
Authors: Nozakura Shunichi , Konotsune Shiro
Published: July 2006

1. Cyanoethylation of trichlorosilane was found to be catalysed by organic bases, benzoylperoxide, or platinized asbestos at about 160°C. The catalytic activities of organic bases increased in the order, dimethylaniline << quinoline < pyridine, piperidine < triethyl-amine. Pyridine hydrochloride and benzyltriethylammonium chloride has also catatytic effects.

2. The orientation of the addition reaction was found to be almost exclusively of the β-position.

3. An ionic mechanism was suggested for the organic base-catalysed addition reaction.
Heats of Dilution of Polyvinylalcohol Solution. I
Authors: Amaya Kazuo , Fujishiro Ryoichi
Published: July 2006

The heats of dilution of P. V. A. solutions were measured and the interaction parameter α between P. V. A. and water was found to be in the range of −2∼−4cal./cc. That these values are remarkably lower than that of ethanol solution suggests the presence of strong intersegmental hydrogen bonds of P. V. A.. The effect of pre-heating was also observed. It may be attributed to the increase of intersegmental associations by heating.
Spectrochemical Study of Microscopic Crystals. XI. The Structure and Polarized Absorption Spectra of Some Metallic Compounds with Remarkable Interaction between Metal Atoms through Anions
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Polarized absorption spectra of [Pd(NH3)2Cl2] [Pd(NH3)2Cl4], Pt(en)Cl3 and (NH4)3AgAuCl7in the crystalline state have been determined by Tsuchida-Kobayashi’s microscopic method in the regions betwen 2400 and 8000 Å.

The crystals of the above compounds which are supposed to involve infinite chains of a type, - - -X–Mm–X- - -Mn- - -X–Mm–X- - - -, have been found to display absorption at longer wave-length than any of the respective component complexes. This absorption at the longer wave-length has been shown to be completely polarized along the direction of the supposed chains in the crystals.

The above results show that in these crystals there would be rather strong interaction between the metal atoms through the anions along the infinite chains.
By-products of Acrylonitrile Synthesis from Acetylene and Hydrocyanic Acid. I. Neutral Constituents
Authors: Morimoto Shiro
Published: July 2006

By distilling the reaction products of the vapor phase acrylonitrile synthesis from acetylene and hydrocyanic acid an intermediate fraction was obtained between two main fractions, acrylonitrile and succinodinitrile. The neutral portion of the intermediate fraction was carefully distilled through an efficient column and separated into constant boiling fractions. From these fractions propionitrile, benzonitrile naphthalene were isolated and identified as the byproducts. On the basis of the boiling points and the infrared spectra of other fractions, the presence of unsaturated nitriles such as 1-cyanobuta-diene, 2-cyanobutadiene, 1-cyanohexatriene, 2-cyanohexatriene, 3-cyanohexatriene as the constituents of the neutral portion was suggested.

Heartfelt thanks are to be returned to Professors Shiro Akabori and Shunsuke Murahashi of Osaka University for their kind instruction and suggestions, to Kazuo Adachi, Masamichi Miura, Tadamichi Fukunaga, Tatsuo Takaya, Yasumasa Kiyokawa, Shinpei Hamada, Sumihiko Mori, Tohoru Okuda and Noriyuki Yamamoto for their helpful technical assistance, and to Yoshiki Matsui for taking infrared absorption spectra.
On the Thermal Dissociation of Organic Compounds. VIII. The Effects of the Substituents on the Thermal Dissociation of Tri-substituted Ureas
Authors: Mukaiyama Teruaki , Ozaki Shoichiro , Kobayashi Yasuhiro
Published: July 2006

The rate constants of the thermal dissociation of tri-substituted ureas in fatty acids and alcohols were determined. It was shown that tri-substituted ureas dissociate faster than 1, 3-dis-substituted ureas. In tri-substituted ureas, the rates in alcohols are faster than in fatty acids in contrast with 1, 3-disubstituted ureas.

Tetra-substituted ureas which are not formed by the addition reaction do not react under the same condition with tri-substituted ureas.

The bimolecular mechanism for the dissociation of ureas involving the direct attack of one solvent molecule on urea was denied.
On the Thermal Dissociation of Organic Compounds. IX. The Urea Linkage (1,3-Di-substituted Ureas in Alcohols)
Authors: Mukaiyama Teruaki , Fujita Yasuhiro
Published: July 2006

The rate constants of the thermal dissociation of 1,3-di-n-propylurea, 1,3-di-n-amylurea, 1,3-di-n-heptylurea, 1,3-diisopropylurea, 1,3-diisobutylurea, 1,3-dicyclohexylurea and 1,3-di-t-butylurea in benzyl alcohol, ethylene glycol and glycerol were determined.

The effects of the substituents on the thermal dissociation of 1,3-di-substituted ureas was discussed and the effects of the solvents on the reaction was also discussed in comparison with those in fatty acids.
Colloid Chemical Studies on Starching Materials. I. Structural Viscosity of Poly-Vinyl Alcohol Solution
Authors: Nakagaki Masayuki , Shimazaki Ayako
Published: July 2006

The structural viscosity is measured for the aqueous solutions of poly-vinyl alcohol-The relative viscosity, (η/ηw), shows linear relationship to the reciprocal of the rate of flow, Q:

η=η_N+2.57×10^-5×P_0/Q

where ηN and P0 are constants. P0 corresponds to the pressure to destroy a net-work structure in the solution, or an apparent yield value, and ηN corresponds to the viscosity coefficient of the destroyed structure, which is assumed to flow as Newtonian. As for the Newtonian viscosity ηN of polyvinyl alcohol solutions, [ηN] defined by

[η_N]=1n(η_N/η_w)/C

is independent on concentration, as far as measured. Comparing the intrinsic viscosities of specimens of the same polymerization, degree, the completely saponified specimen shows smaller value than partly saponified one. This may be explained by the decrease of molecular extension due to the strong intramolecular interaction of OH groups. The apparent yield values P0 is 0.5∼3.5 cm. H2O and is highly dependent on the history of the solution. The completely saponified specimen shows greater P0 value. It will also be explained by the strong intermolecular interaction of OH groups to form net-work structure.
Studies on the Oxy-acid Phosphors. V. Stannate Phosphors (Part I)
Authors: Kotera Yoshihide , Sekine Tadao , Yonemura Michiko
Published: July 2006

Various stannate phosphors were prepared and some of their emissions were determined. Stannate phosphors emit green, blue or yellowish white light when activated by manganese, blue, violet or red by bismuth, orange, green or blue by lead, while those activated by cerium show blue or red emission. It is expected that the activation by tin also occurs in some cases. This is supported by the fact that the emission of magnesium stannate activated by titanium changes by the variation of flux. For different specimens of calcium stannate activated by titanium or cerium, emission spectra under excitation of cathode rays were measured.
The Oxygen Equilibrium of Denatured Hemoglobin and the Mechanism of Denaturation
Authors: Kubo Masaji
Published: July 2006

The oxygen equilibrium curve of a slightly denatured preparation of hemoglobin solution was determined by the spectrophotometric method. The plot of Y, the degree of partial saturation with oxygen, against log p, the logarithm of the partial pressure of oxygen, was not symmetric across the point at 50% saturation. The trend of asymmetry was such that if the lower left portion of the curve was rotated through 180° about the point at Y=l/2, it lay below the upper right portion of the original curve. The condition of this trend of asymmetry was derived from the theory of chemical equilibrium. This condition was tested with various conceivable changes in k the equilibrium constant of oxygenation of a single heme, as well as in α the constant of interaction stabilizing the combination of each of two adjacent hemes with an oxygen molecule. It was found that the deviation from the equivalence of α, of whetever kind and degree, can never satisfy the required condition, provided that the k’s of the four hemes remain equivalent to each other. A number of other conceivable cases were subjected to critical examination. The condition of asymmetry was so severe that it could rule out almost all except the case in which one of the four hemes increases its affinity towards an oxygen molecule compared with the other three. This conclusion is in conformity with the results on hemoglobin dissociated in a dilute solution or split in a urea solution.
Synthetic Amphoteric Polypeptide. I. Syntheses and Some Properties of Linear Amphoteric Polypeptides
Authors: Yuki Heimei , Sakakibara Shumpei , Tani Hisaya
Published: July 2006

1. Two linear highmolecular amphoteric polypeptides were synthesized.

2. The pH-dependences of viscosity and optical rotation were measured. Some of these properties resembled that of vinyl polyampholytes and some proteins.
The Reaction between Diphenylalkanes and Maleic Anhydride by the Friedel and Crafts Method
Authors: Koga Wataru
Published: July 2006

(1) By the reaction of diphenylmethane and diphenylethane with maleic anhydride in the presence of aluminium chloride, diphenyl-methane-4, 4′-di-γ-oxocrotonic acid and biben-zyl-4,4′-di-γ-oxocrotonic acid were produced, respectively. And cis and trans isomers of dimethyl esters of these acids were prepared.

(2) By the reduction of the above two acids by zinc and acetic acid, diphenyl-methane-4, 4′-di-γ-oxobutyric acid and biben-zyl-4, 4′-di-γ-oxobutyric acid were prepared.

(3) These saturated keto acids were reduced by amalgamated zinc in the mixture of ethanol and hydrochloric acid to diphenyl-methane-4,4′-dibutyric acid and diphenyl-ethane-4, 4′-dibutyric acid.
Studies on the Synthesis of Metal Complexes. I. Synthesis of an Ammine-carbonato Series of Cobalt (III) Complexes
Authors: Mori Motoshichi , Shibata Muraji , Kyuno Eishin , Adachi Tomohiko
Published: July 2006

A green compound is isolated from the concentrated solution obtained by the action of hydrogen peroxide on cobalt (II) ions in the presence of potassium bicarbonate, and the formula K3[Co(CO3)3]·3H2O is assigned to it on the basis of the analysis of the solid and of the absorption spectrum of the solution.

A series of ammine-carbonatocobalt (III) complexes, K3[Co(CO3)3]·3H2O, blue (perhaps, cis) and violet(perhaps, trans)-K[Co(NH3)2(CO3)2]·H2O, [Co(NH3)4CO3]Cl and [Co(NH3)6]Cl3, are synthesized from the abovementioned green solution by means of successive substitution of carbonate ions by ammonia groups. Hexamminecobalt (III) tricarbonatocobaltate, [Co(NH3)6] [Co(CO3)3], is also obtained by adding a hexamminecobalt (III) salt to the green solution of tricarbonato-complex. Three complexes, K3[Co(CO3)3]·3H2O and blue- and violet-K[Co(NH3)2(CO3)2]·H2O, are probably to be regarded as new complexes and may be identified by their absorption spectra.
By-products of Acrylonitrile Synthesis from Acetylene and Hydrocyanic Acid. II. Amines Obtained by Hydrogenation of Nitriles
Authors: Morimoto Shiro
Published: July 2006

The basic substances were obtained from the hydrogenation products of the neutral by-products of acrylonitrile synthesis from acetylene and hydrocyanic acid. They were fractionated by distillation through a Stedmantype column. n-Butylamine and n-amylamine were isolated and identified as derivatives of phenylthiourea. On the basis of chromatograms, i.e., the paperchromatograms of hydrochlorides of amines and chromatograms of N-2, 4-dinitrophenyl-derivatives on the column of cation exchanger, the presence of seven amines, i.e., n-propyl-, n-butyl-, 2-methylbutyl-, n-amyl-, di-n-propyl-, n-heptyl-and benzyl-amines was confirmed and that of two primary heptylamines other than n-heptylamine, i.e., 2-methylhexyl- and 2-ethylamyl-amines, was suggested.
Hydroformylation and Hydrogenation of Methylacrylate in Presence of Dicobalt Octacarbonyl or Iron Pentacarbonyl. Dependence of Reaction Rate on Partial Pressures of Carbon Monoxide and Hydrogen
Authors: Uchida Hiroshi , Bando Kenichiro
Published: July 2006

Hydroformylation of methylacrylate in the presence of dicobalt octacarbonyl was investigated by paying a special attention to the effect of varying ratios of carbon monoxide to hydrogen on the rate. The rate attains the maximum value at a certain partial pressure of carbon monoxide, and increases with the increasing partial pressure of hydrogen. The tendencies agree with the results obtained by G. Natta on the hydroformylation of cyclohexene. The rate equation proposed by A. R. Martin with respect to the rate of hydroformylation of di-isobutene can represent the tendencies observed in the present results.

In the presence of iron pentacarbonyl, methylacrylate has been found to be reduced to methylpropionate under high pressure of hydrogen containing carbon monoxide. The reduction becomes more difficult with the increasing partial pressure of carbon monoxide, but was made catalytically neither by an iron catalyst reduced from iron oxide nor by the one produced by the thermal decomposition of iron pentacarbonyl.
Magnetochemical Study of Nitroso Compounds
Authors: Matsunaga Yoshio
Published: July 2006

The magnetic susceptibility of nine nitroso compounds, as solids and as solutes, were measured by the Gouy method. The constant for the nitroso group attached to a carbon atom was found to be paramagnetic of the order of 10 units. The author suggested that the second term in Van Vleck’s equation for the diamagnetism of a molecule is dominant in this case. Some quinones and their monoximes were also measured, and it appeared that the ability of the oxime group to localize aromatic electrons is less than that of the carbonyl group. In addition, the structure of nitrosodialkylaniline hydrochloride was discussed from the magnetic standpoint.
STUDIES ON AMINO-ACID ANHYDRIDES, I. MOLECULAR COMPOUNDS OF DIKETOPIPERAZINE WITH COPPER HALIDES
Authors: Asahina Tei-ichi , D\={o}no Tsurumatsu
Published: July 2006

1. Molecular compounds of diketopiperazine with copper chloride and bromide were prepared.

2. The formation of such compounds in aqueous solution with formulae other than those obtained in solid state was ascertained.

3. The meaning of these molecular compounds for the chemistry of protein was discussed.
A MICROANALYTICAL.DETERMINATION OF SULPHUR IN ORGANIC COMPOUNDS BY TITRATION
Authors: Kubota Bennosuke , Hanai Sadahiko
Published: July 2006

A microanalytical determination of sulphur in organic compounds is carried out by decomposing cautiously the material to be analysed in the hydrogen atmosphere on reduced nickel, which absorbs the sulphur completely and changes itself into sulphide, and by determining iodometrically the hydrogen sulphide which is evolved from the reduced nickel when it is dissolved in hydrochloric acid. It was found thus that the nickel catalyst is able to be applied to the organic microanalysis of sulphur.
PERMEABILITIES OF COLLOIDAL SUBSTANCES TO GASES
Authors: Kanata Kazuo
Published: July 2006

1. Permeabilities of rubber, gelatine and celluloid for oxygen, hydrogen,, carbon dioxide, sulphur dioxide, and ammonia were determined.

2. By ascertaining the permeabilities of celluloid and gelatine, it became clear that the sorptions of these substances are not adsorption phenomena.

3. Something about the mechanism of permeability and absorption was discussed and the author reached the conclusion that the permeability and hence the absorption is caused by the dissolution of gas in the colloidal, substance.
ELECTRICAL CONDUCTANCE OF NICKEL SULPHATE SOLUTION AND IONIC CONDUCTANCE OF NICKEL
Authors: Murata Kwanji
Published: July 2006

1. The conductances of aqueous solutions of nickel sulphate at concentrations 0.0001 to 1 equivalent per liter at 25°C. and 18°C. were measured and the equivalent conductances at infinite dilution were found.

2. The ionic conductances of nickel also were calculated.

3. The relative viscosity and the degree of ionization of 1/20 mol nickel sulphate were calculated.
Correlation between Two Molecular Orbital Theories on Organic Reactions. I. Ionic Substitutions
Authors: Baba Hiroaki
Published: July 2006

A mathematical proof is given that under a certain condition the static and localization theories become completely equivalent to each other in predicting the reactivities in ionic substitutions of the positions in a given even alternant hydrocarbon. The said condition is concerned with the coefficients of the powers in the expansions of the secular determinants for the residual molecules. It is shown by numerical calculations that the condition is fulfilled by almost all positions in 12 molecules treated. The change in total energy of π-electrons is given as a function of a coulomb integral, and a new quantity called partial polarization energy is introduced which is defined as a function of the π-electron density at a given position. Both are useful for relating the static quantity to the dynamic one. The latter is a new measure of a general nature for the reactivity of the position towards the ionic reagents.
Magnetochemical Study of Sydnones
Authors: Matsunaga Yoshio
Published: July 2006

The molar susceptibilities of eight N-arylsydnones were measured by the Gouy method. Assuming that the influence of the conjugation between aryl and sydnonyl groups on diamagnetism is practically negligible, the molar susceptibility of unsubstituted sydnone was estimated as 38.7. Its isotropic part 24.57 was evaluated from the values for five of the contributing ionic forms calculated by the Gray-Cruick-shank’s method. From the magnitude of the exaltation of molar susceptibility which is equal to one third of an anisotropic part, the author suggested that the aromatic character of a sydnone ring is in the same order with those of furan and pyrrole rings. Four derivatives of N-phenylsydnone which have a substituent in meso-ionic ring were also measured, and the agreements between the observed and the calculated molar susceptibilities were found to be good within the limit of the latter’s estimation.
The Adsorption of Non-Polar Gases on Alkali Halide Crystals. II. Calculations of The Adsorption Behaviour of Non-Polar Gases on Cubic Sodium Chloride
Authors: Hayakawa Teruo
Published: July 2006

The potential energy of each isolated atom or non-polar molecule (argon, nitrogen, or carbon dioxide) adsorbed on the (100) plane of cubic sodium chloride has been theoretically calculated at four different positions on the crystal surface. In the present calculations, the repulsive constants of the modified BuckinghamCorner (6-exp) intermolecular potential for these non-polar gases have been used. The quadrupole interaction of the nitrogen or carbon dioxide molecule with a crystal has been taken into consideration. The good agreement between the theoretical and experimental values of the initial heat of adsorption for each adsorbate has been obtained.

The present theoretical calculations suggest that the surface heterogeneity caused by the lattice imperfection or crystal defects is of minor importance compared with other types of surface heterogeneity due to the distribution of sites grouped in patches. The present results also suggest that the adsorbed argon atoms or nitrogen molecules easily migrate two-dimensionally along the surface in the low coverage region. These results on the surface migration are in good agreement with the entropy curves of adsorbed argon and nitrogen experimentally determined.

The approximate calculation of the heat curve for argon on the (100) plane of cubic sodium chloride has been carried out following a similar method used by Young. The discordance between the experimental and approximately calculated heat curves is considerable, and this is attributed to the fact that the unreliable model (i. e. the uniform surface and the localized adsorption) has been assumed in these approximate calculations.
Irreversible Photobleaching of the Solutions of Fluorescent Dyes. IV. Photoreactions in Methanol, Isopropanol and Ketones, and the General Conclusion for the Photobleaching of Eosine
Authors: Imamura Masashi
Published: July 2006

Studies on the photoreaction of eosine in the water-alcohols and -ketones have been made both in the presence and in the absence of oxygen. The corrected rate equations, giving the satisfactory explanation for the data obtained, have been presented. Analysis of the experimental results so far obtained, on the basis of these rate equations, has led to the conclusion unambigously that the primary process of the aerobic photobleaching of eosine in the aqueous solution is the attack of oxygen on the triplet state of dye.
Studies on the Chemical Constitution of Agar-agar. XX. Isolation of a Tetrasaccharide by Enzymatic Hydrolysis of Agar-agar
Authors: Araki Choji , Arai Kiyoshi
Published: July 2006

1. A tetrasaccharide, forming a crystalline tetrahydrate, has been isolated from the products of enzymatic hydrolysis of agar. Its fully acetylated and methylated derivatives have also been obtained as crystals.

2. Identification of both monosaccharide and disacharide constituents has led to the assignment of the structure, O-3,6-anhydro-α-l-galactopyranosly-(1→3)-O-β-d-galactopyranosyl-(1→4)-O-3,6-anhydro-α-l-galactopyranosyl-(1→3)-d-garactose, to the tetrasaccharide isolated. The structure has been supported also by methylation data.

3. The tetrasaccharide has been termed neoagarotetraose, based on the general nomenclature suggested for oligosaccharides derived from agarose and a similar polysaccharide.

4. A probable course has been assumed for the enzymatic degradation of agarose.
Dielectric Studies on Colloidal Solutions. III. The Mobilities of Micelles of Long-chain Amine Hydrohalides
Authors: Shirai Michio , Tamamushi Bun-ichi
Published: July 2006

The electrophoretic mobilities of dode-cylamine hydrochloride, hydrobromide and hydroiodide, as well as tetradecyl-amine and hexadecylamine hydrochlorides have been measured. They decrease with increasing concentration as is expected from the electrostatic point-of-view of the micelle structure.

The fractions of counter ions bound to micelles are computed from the electrophoretic mobilities obtained.These values are found consistent with the result obtained by the transference number measurement.

The ζ-potentials of micelle ions are calculated from the electrophoretic mobilities by Henry’s formula. They must be, however, less than the real values, if we take into account the expected highfrequency effects.
Microcolorimetric Determination of Sulfate by Reduction to Hydrogen Sulfide with Tin(II)—Strong Phosphoric Acid
Authors: Kiba Toshiyasu , Kishi Ikuko
Published: July 2006

A new reagent, “Tin(II)-strong phosphoric acid” has been prepared to permit a rapid and simple determination of sulfate sulfur by reduction to hydrogen sulfide. The procedure for the determination of semi-micro quantities of sulfate sulfur, previously devised by the authors, has been extended to the microgram scale by adopting the sensitive methylene blue colorimetric method. The rapidity and simplicity of the original method are still retained in this new colorimetric method, by which 1 to 35 micrograms of sulfate sulfur can be estimated. The apparatus is very simple, a test-tube of fused silica being employed as the reaction vessel. The standard calibration curve for colori-metric determination of sulfate sulfur by this method coincides well with that drawn for sodium sulfide by direct coloration with p-amino dimethyl aniline and ferric chloride. Interference of other anions can be kept out of consideration, because the sulfate ion is easily separated by addition of barium chloride solution and coprecipit-ation with ferric hydroxide. Large amounts of ferric hydroxide do not affect the method. Some examples of the determination of sulfate sulfur in ferric chloride reagent and Japanese acid clay are described.
Surface Chemistry of High Polymers. VII Polyacids and Some Vinyl Polymers
Authors: Hotta Hiroshi , Isemura Toshizo
Published: July 2006

The films of polyacids (poly-l-glutamic acid and the copolymer of maleic acid and vinyl acetate) and some related compounds were studied in order to know the behaviour of carboxyl groups in the linear polymer at the interface. The principal results obtained are as follows.

The orientation of carboxyl group is affected considerably by other accompanying groups in polymer. Hence, the surface moment of carboxylic compounds is various according to the surface orientation of respective groups in the polymer. Accordingly, the surface moment of copolymer cannot be explained by the simple additivity of the moment of constituent polar groups.

The surface moment of polyacids abruptly decreases nearly at the pH of aqueous phase equal to the pK of corresponding structural unit.
Effect of the Addition of Some Carbohydrates on the Decomposition Rate of Sodium Aluminate Solutions with Seeding
Authors: Sato Taichi
Published: July 2006

In order to study the influence of the presence of the organic matter in a sodium aluminate solution the decomposition rate was investigated by the addition of some carbohydrates as first step of study. Three kinds of carbohydrate, i. e. glucose, sugar and starch (white potato) were chosen and added to a sodium aluminate solution in verious amounts. These solutions were decomposed with seeding of hydrargillite, and these decomposition rates were compared in each case. Consequently it had been observed that the addition of glucose or sugar acts to retard the decomposition, and that the increase of an added amount of starch promotes the decomposition. But the retarding action of glucose is larger than that of sugar. On the other hand, the relation between the added amount of seed and the addition of carbohydrate was investigated. It had been seen that the presence of seed is stronger than that of glucose or sugar in the action of decomposition, and that this relation is different upon the presence of starch. Further the viscosity of sodium aluminate solution mixed with carbohydrate was measured. It has been observed from this measurement that the viscosity of sodium aluminate solution is almost unchanged with the addition of glucose or sugar, and that its viscosity is improved with the addition of starch. Then these results have been compared with the decomposition rate. From this result, it is concluded that the viscosity of solution does not always act on the decomposition as the factor of first order. Hence the action mechanism of these carbohydrates on the decomposition are discussed, and it is clearly concluded that there is a very large difference among the actions of each carbohydrate on the decomposition. In these results one must obtain some informations upon the action mechanism on the decomposition of sodium aluminate solution in the presence of organic matter.
Photometric Determination of Thallium with Rhodamine B
Authors: Onishi Hiroshi
Published: July 2006

Procedure is given for the spectrophotometric determination of 1–10μg. of thallium with rhodamine B. Ammonium persulfate was also found to be as effective as bromine in oxidizing thallium preparatory to rhodamine B—benzene extraction. For the separation of thallium from other elements, univalent thallium is extracted with dithizone in chloroform from a basic solution containing cyanide and then transferred to an aqueous solution by shaking the chloroform with dilute nitric acid. The procedure provides for the presence of antimony, gallium, gold, iron and tungsten.
Relation between Foaming Properties and the Structure of Surface Active Substances. I. Foaming Properties of Aqueous Soap and Sodium Dodecyl Sulfate
Authors: Kashiwagi Maresuke
Published: July 2006

1) The foaming power measurement by Ross-Miles method was found to be useful for the study of surface active substances.

2) A general rule for the foaming power would be that it increases with concentration up to cmc., and above it, becomes nearly constant or somewhat decreases. The foaming power is also inversely proportional to the surface tension.

3) The cmc. and other physical constants can be determined by the foaming power measurement.

4) Ion rather than micelle is presumed to be predominant with respect to foaming properties.

5) Effect of inorganic ions on foaming is slightly in the order of lyotropic series, namely Li+>Na+>K+>Rb+, just before salting out.
Crystallinity Studies of Polychlorotrifluoroethylene by Infrared Method. I. Measurement of the Degree of Crystallinity
Authors: Matsuo Hiroshi
Published: July 2006

The crystalline-amorphous ratio, and consequently the degree of crystallinity of polychlorotrifluoroethylene was measured by use of the ratio of observed absorbance of crystalline band at 440 cm.−1 to that of amorphous band at 760 cm.−1. The crystallinity as a function of temperature was measured by this method, and it was in good agreements with that obtained by specific heat methd. Furthermore, a linear relationship between the degree of crystallinity and the specific volume was found, and it leads to extrapolated values of film and 0.4901 and 0.4575 for the specific volumes of completely amorphous and crystalline meterials, respectively.
A Simplified Method for the Preparation of N-Acetylphenylalanines
Authors: Okuda Tôru , Fujii Yasuo
Published: July 2006

A simple and practical procedure is described of preparing N-acetylphenylalanines by hydrogenation of the corresponding unsaturated azlactones in an aqueous sodium hydroxide solution with Raney nickel under pressure. By this method N-acetyl derivatives of phenylalanine, p-methylphenylalanine, p-methoxyphenylalanine and 3,4-methylenedioxyphenylalanine were synthesized in good yield.
Studies on Organic Reagents for Inorganic Analysis. II. Spectrophotometric Study on Phenylfluorone Chelates of the Fourth Group Metal Elements
Authors: Sano Hirotoshi
Published: July 2006

The absorption spectra of phenylfluorone and its chelates with the fourth group metal elements, titanium, germanium, zirconium and tin were studied. It was found that in acidic solutions the absorption maxima of these metal chelates shift towards a longer wavelength with increasing ionicity of the bond between the metal and the terminal oxygen atom of the ligand phenylfluorone. These absorption spectra were examined by the aid of free electron gas model method. Kuhn’s theory was applied to the calculation of the value V0 from the absorption maximum observed in each metal chelate. It was shown that there was a certain relationship between the value of V0 obtained and the ionicity of the chelating bond which is estimated from the difference of electronegativity between the metal and the terminal oxygen atom. The relation can be expressed as follows: V_0=k(1-I)^n (4’) where, n is a parameter depending on the method used for the estimation of the ionicity, k a parameter characteristic of the chelating dye used and equal to the value of V0 for the polyene having the same number of the conjugated double bond. These results were applied to explain the “ red shift” observed in acidic solutions of organic dyes in the colorimetric determinations of metals. A more detailed investigation concerning the nature of the chelating bond will be reported later.
Studies on Crystals of Metallic Tris-ethylenediamine Complexes. III. The Determination of the Absolute Configuration of Optically Active Complex Ion, [Co en3]3+, by Means of X-rays
Authors: Saito Yoshihiko , Nakatsu Kazumi , Shiro Motoo , Kuroya Hisao
Published: July 2006

The absolute configuration of an optically active complex ion [Co en3]3+ has been determined by means of X-ray absorption edge technique. Cu Kα radiation was used to excite the cobalt atoms in the crystals of d- and l-2[Co en3]Cl3·NaCl·6H2O. The effects of the anomalous dispersion were observed by single crystal oscillation photographs as well as Laue photographs. A brief description of the principle of the method and the experimental procedure is included.
Fluorometric Determination of Thallium with Rhodamine B
Authors: Onishi Hiroshi
Published: July 2006

A method is presented for the fluorometric determination of traces of thallium. Except for the step of fluorometry, the procedure is essentially the same as previously described for the absorptiometry. A synthetic mafic rock was analyzed for thallium by the method which involves hydrofluoric acid decomposition of the sample, dithizone extraction, rhodamine B-benzene extraction, and the measurement of fluorescence intensity on the benzene extract.
The Leakage Method and the Sandwich Type Zisman Method for Measurements of Contact Potential Differences between two Metals Immersed in Poorly Conductive Dielectric Liquids
Authors: Tanaka Akira
Published: July 2006

For the purpose of measuring the C.P.D.between two metals immersed in poorly conductive dielectric liquids, two methods were presented in this report. One is the leakage method, which appears to resemble the ionization method but is different in one point; because in this leakage method we make use of the small electrical conductivity inherent in the liquid. It is another merit of this method that the measurement can be carried out without vibrating the electrode. When the liquid and the electrodes are properly chosen this leakage method may be applied to various purposes. The other is the sandwich type Zisman method, which is an excellent device of improvement of the vibrating electrode method in dielectric liquids. On the comparison of the measured values by the two methods, satisfactory agreements were obtained.

Of course, there is only limited knowledge at the present time on the nature of the electrical potentials observed in these dielectric liquids, yet the author ventures to say that the use of the term, “contact potential difference”, is most suitable in the case of these experiments.
Stoichiometric Investigations of the Liquid State. V. Vaporization Phenomenon of Associated Liquids
Authors: Tyuzyo Kiyoshi
Published: July 2006

1) Energy of vaporization of n-paraffin is discussed. It is shown that relation between ΔEvap at the boiling point and Evis is different from that of Eyring et al..

2) A new method for calculating the degree of association of the first kind from energy of vaporization is proposed. The degree of association calculated by this method is quite consistent with the　result of the previous paper and the value from literature.

3) A new method for calculating the energy of hydrogen bond is proposed. Energy of hydrogen bond obtained by this method is fairly consistent with the value from literature.

4) Considering all results, it can be concluded that the associated body of the first kind shows analogous behavior to n-paraffin.