bluuebunny/crossref_metadata_2025 huggingface dataset:
Dipole Moments of 2,3-Dihalogeno-2,3-dimethylbutanes
Authors: Morino Yonezo , Miyagawa Ichiro , Haga Toshio , Mizushima San-ichiro
Published: July 2006

The dipole moments of 2,3-dichloro- and 2,3-dibromo-dimethylbutane were measured in carbon tetrachloride solution in the temperature range from −25° to +55°C, and in benzene solutions at 25°C. The moment was found to increase with temperature in carbon tetrachloride solution. Much higher values of moment were observed in benzene solutions. It was concluded from these experimental results that there exist two rotational isomers, the trans isomer with vanishing or a small moment, and the gauche isomer with a finite moment. The experimental result could be explained satisfactorily by the rotational isomer theory, but not on the assumption of only one potential trough at the trans position.

By comparing the energy difference between the rotational isomers of these compounds with those of 1,2-dichloro- and 1,2-dibromoethane it was concluded that the electrostatic force plays an important role in the energy difference between the rotational isomers, whereas the potential barrier is mainly determined by steric repulsion.

An explanation was presented to reconcile the result of our dipole measurement with that of Raman and infrared measurement, the two results being in apparent contradiction with each other.
A Rapid Determination of Oxidation Values of Non-Volatile Organic Compounds by the Iodic Acid Decomposition Method
Authors: Ohashi Shigeru
Published: July 2006

A new method has been developed to permit accurate and rapid determination of oxidation values of organic compounds. The oxidation value of a compound can be readily obtained by determining the iodine produced from the reaction of the organic compound and potassium iodate in strong phosphoric acid. The iodine produced is absorbed into the sodium arsenite solution and the excess arsenite is titrated with the standard solution of iodine.

The apparatus and procedures for this method have been investigated. According to the data obtained on some pure nonvolatile organic compounds, utilizing sample weights of 10 to 80 mg., it is indicated that this method is very accurate and an analysis can be accomplished as rapidly as in twenty to thirty minutes.
Decrease of the Surface Area of Raney-type Catalysts in the Aluminium dissolution Process
Authors: Sato Masaki , Ohta Nobuto
Published: July 2006

Variations of the surface area in the dissolution process were investigated on a Raney copper catalyst “No. 16” (for dehydrogenation of cyclohexanol) and a Raney nickel catalyst.

It has been found that nascent bare atoms of copper or nickel formed at the initial step move rapidly, perhaps particularly in alkali solution, to reconfigurate the surface-structure to a more stable one.

That is to say, the surface area reaches a maximum at an initial step, where only a small quantity of aluminium is dissolved out, then rapidly decreases to a stable value in spite of successive dissolution of aluminium. The rate of decrease is much greater than that recognized on reserving the catalyst in its dried state or in water.

By calculating reliable “n” values, the number of adsorbed molecular layers on the surface area from the modified B.E.T. equation, it has been deduced that the average catalytic activity per unit area of the surface may be decreased in process of dissolution of aluminium.
Surface Chemistry of Synthetic Protein Analogues. VI. The Interaction of Urea and Salt with Non-electrolytic Polypeptides
Authors: Isemura Toshizo , Hamaguchi Kozo , Kawasato Hideyo
Published: July 2006

The interaction of urea and potassium chloride with non-electrolytic polypeptide monolayers was investigated. The film of polypeptide was expanded considerably in the presence of urea in the substrate. The number of molecules was, however, not changed by the interaction with urea. The molecular weights of polypeptides determined by surface pressure measurement on the substrates with or without urea were the same. Whereas the co-area of the molecule was increased by increase of urea concentration in the substrate. Urea might be bound to the peptide linkages in backbone by hydrogen bonding and the formation of aduct seems improbable.

Although potassium chloride affected the nature of electrolytic polypeptide film profoundly, it scarcely affected that of the nonelectrolytic polypeptide film. The interaction with urea was discussed in relation to the protein denaturation.
Studies on Dimethylglyoximato cobalt (III) Complexes. II Absorption Spectra of Bis-(dimethylglyoximato)- and Bis-(mono-O-methyl-dimethylglyoximato)-cobalt (III) Complexes
Authors: Nakahara Akitsugu
Published: July 2006

Two new compounds, [Co(NH3)2(DCH3)2]Cl and H[Co(DCH3)2(NO2)2] have been synthesized as the first examples of tervalent-cobalt complexes of dimethylglyoxime-mono-methylether. Absorption spectra of the compounds and several bis-(dimethylglyoximato)-cobalt (III)-complexes in solution have been measured.

The absorption curves of bis-(dimethylglyoximato)-cobalt (III)-complexes, generally, consist of three inflations and one maximum. The inflation in the visible region is the vestige of the first absorption band, and the two other inflations and one maximum in the ultraviolet region are the specific absorption bands which are due mainly to the dimethylglyoximate ions in coördination.

As for the first absortion bands, the results of the measurements can successfully be elucidated on the basis of the spectrochemical- and hyperchromic-series found by Tsuchida et al. For NH4[Co(DH)2(NO2)2], is also the specific band originated from the nitro-groups in coördination remarkable.

The isolated maxima on the curves of H[Co(DH)2Cl2] and H[Co(DH)2Br2] in the longer wave-length region are nothing but the first absorption bands which are shifted towards red owing to the bathochromic effect of the two halogenide ions.

In the dibromo-complex, the third absorption band is conspicuous. It has never been recognized clearly in the other complexes with dimethylglyoxime.

The absorption curves of bis-(mono-O-methyl-dimethylglyoximato)-complexes, as a whole, resemble those of corresponding dimethylglyoximato-complexes, but the bathochromic shift of the specific absorption bands from that of free ligand molecule amounts to a considerable degree in comparison with the cases of dimethylglyoximato-complexes. And this phenomenon is elucidated in connexion with the O-H-O hydrogen bonds.

From comparison of the reactions for preparing the bis-(mono-O-methyl-dimethylglyoximato)- and bis-(dimethylglyoximato)-complexes, the high stability of the latter was discussed.
Spectrochemical Study of Microscopic Crystals. VII. Absorption Spectra of Trans-dihalogeno-bis (ethylenediamine)-cobalt (III) Complexes
Authors: Yamada Shoichiro , Nakahara Akitsugu , Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

Dichroism of the crystals of trans-[Co(en)2Cl2]ClO4, [Co(en)2Cl2]Cl·HCl·2H2O and [Co(en)2Br2]Br·HBr·2H2O have been quantitatively determined by Tsuchida-Kobayashi’s microscopic method in the visible and ultraviolet regions.

As to the dichroism of the trans-dihalogeno-complexes, the following relations have been induced. The first band splits itself into two component absorptions. One at the longer wave-length is polarized in the X-Co-X direction, and the other at the shorter wave-length is polarized in the Co-en plane. For the third and specific bands, the X-Co-X-absorption is bathochromic to the Co-en-absorption.

On the basis of the above results, absorption spectra of several praseo-complexes in solution have been discussed.
Determination of thorium by Organic bases
Authors: Deshmukh G S , Xavier J
Published: July 2006

Quantitative estimation of thorium by precipitating it from aqueous thorium chloride (or nitrate) solution by o-tolidine, dianisidine, ρ-phenylenediamine, o-anisidine and o-phene-tidine has been studied. The precipitated complex is ignited to constant weight and determined gravimetrically as ThO2.
On the Electro-Osmotic Water Transport Through Cation—Exchange Resin Membranes
Authors: Oda Yoshio , Yawataya Tadashi
Published: July 2006

The water transference due to electroosmosis was studied for several cationexchange resin membranes of sulfonated phenol resin type, mainly in sodium chloride solution. It was shown that (1) the electroosmosis depended on the transport number of the membrane and the amount of water contained in the resin, and (2) the experimental results could be explained by introducing the idea of fixed water and mobile water in the membrane. The fixed water is supposed to be composed mainly of the hydration water attached to the polar groups of the resin.
Synthetic Studies on the Benzofuran Derivatives. Part I. A New Synthesis of Karanjin
Authors: Kawase Yoshiyuki , Matsumoto Takashi , Fukui Kenji
Published: July 2006

Starting from 7-hydroxy-3-methoxyflavone-8-aldehyde (II), 3-methoxyflavone-7,8-furan-α-carboxylic acid (IV) was synthesised in good yield by the method of Tanaka for benzofuran synthesis and was decarboxylated in quinoline with copper powder into karanjin (I).
Studies on A.C. Polarogroaphy. II. Fundamental Circuit and Some Experimental Results
Authors: Senda Mitsugi , Okuda Mitsuko , Tachi Isamu
Published: July 2006

Fundamental circuit for a.c. polarography, in which a.c. polarogram with varying as well as constant amplitude is automatically registered, was shown. And the close relation between reversibility of electrode reaction and a.c. polarographic behaviour of depolarizers was experimentally verified and another applicability of this method was pointed out.
Alkylalkoxypolysiloxanes. IV. Lower Members of Methoxy End-blocked Dimethylpolysiloxanes with One to Six Silicon Atoms
Authors: Tanaka Toshio , Okawara Rokuro
Published: July 2006

(1) Methoxy end-blocked dimethylpolysiloxanes have been prepared by the reaction of sodium bicarbonate with partially methanolyzed dimethyldichlorosilane.

(2) Distribution of the lower polymers was determined in regard to the composition of the partially methanolyzed dimethyldichloro-silane.

(3) Methoxy end-blocked dimethylpolysiloxanes from monomer (dimethyldimethoxysilane) to hexamer have been characterized.
Hyperconjugation. I. General Theory and Its Applications to Simple LCAO MO Calculations
Authors: I’haya Yasumasa
Published: July 2006

The theory of hyperconjugation has been extended and applied to computations of the electronic structures of methyl and ethylsubstituted acetylenes and benzenes using the empirical LCAO MO method not including the overlap integrals. The common empirical parameters introduced from experimental aspects were used consistently through the calculations. Charge distributions of the π-electrons, bond orders, resonance moments, relative shifts of near ultraviolet absorption spectra and oscillator strengths were calculated, and fairly satisfactory results, compared with the observed values, were obtained. Because of the lack of appropriate absorption data, the near ultraviolet absorption spectra of alkylbenzenes in normal hexane were obtained. The calculations show that when the methyl group is substituted for a hydrogen atom of the methyl group, the hyperconjugative effect is recognized as same as before.
Theoretical Analysis of Polarographic Waves. I. Reduction of Simple Metal Ions
Authors: Matsuda Hiroaki , Ayabe Yuzo
Published: July 2006

In the present paper, the general equation of the instantaneous diffusion current has been derived by taking into account the expansion of the mercury drop with the same accuracy as Ilkovic’s equation. Then, the general expression of the current-voltage curve for the reduction of simple metal ion has been given and its characteristics discussed upon being divided into three cases, i.e. reversible, irreversible and “quasi”-reversible. Reversible waves are given by electrode processes for which the value of ks is larger than 2×10−1 cm./sec., and on the other hand, irreversible waves are observed when the value of ks is smaller than 4×10−6cm./sec. In the irreversible case, it has been shown that the rate constant kj0 and the transfer coefficient α can be calculated from the observed values of the half-wave potential and the tangent of log-plot, respectively.

At last, the equation of the current-voltage curve due to the reduction of organic substance has been derived.

Addendum.—Recently J. Koutecky7) reported a theoretical treatment of the instantaneous and mean diffusion current for any point along the wave, in which the present diffusion problem was solved by an other method. The present work has been independently carried out.
Separation of RaD, RaE and RaF by Ion Exchange
Authors: Ishimori Tatsujiro
Published: July 2006

RaD, RaE and RaF may be satisfactorily separated from each other by means of an anion exchanger, Amberlite XE-98. Carriers are not necessary. The use of an anion exchanger and strong acidities of eluents helps to prevent the formation of radiocolloids. This separation technique seems to be highly suitable for the preparation of carrier-free RaE and RaF tracer. It is efficient in separation and easy to manipulate.
The Effect of Layered Water on the Color Reaction of Benzidine or Other Similar Compounds with Montmorillonite
Authors: Takahashi Hiroshi
Published: July 2006

The relationship between layered water and coloration of some complexes between montmorillonite and benzidine or other similar compounds has been discussed, and it is shown that they may be divided into types according to the structures of organic compounds. The shrinkage and swelling of the layer distance of the complex caused by its dehydration and hydration are observed.

The coloration of the monofunctional-complex is not so remarkable and that of the bifunctional-complex is remarkable. In the case of monofunctional-complex or the bifunctional-complex with benzidine, the amino-or hydroxyl-radical fixes on one side of the silicate layer, and then, when it is saturated with water, the water molecules get into the silicate layer. On the other hand, in the bifunctional-complex with paramine, as the amino- or hydroxyl-radical fixes on both sides of the silicate layers, the water molecules no longer get into it.
Lower Members of Diethoxycyclopolysiloxanes from Diethoxydichlorosilane
Authors: Okawara Rokuro , Hotta Saburo , Shimura Toshiro
Published: July 2006

(1) Diethoxydichlorosilane did not easily react with sodium bicarbonate.

(2) Diethoxycyclopolysiloxanes beginning with cyclotrimer could be obtained from the hydrolysis of diethoxydichlorosilane by using pyridine as an acid acceptor.

(3) The lower members of diethoxycyclopolysiloxanes having three to five silicon atoms have been characterized.

(4) The cyclotrimer was found to be formed only in the limited conditions of hydrolysis and it was decomsosed spontaneously in a sealed soft glass ampulla.
A Kinetic Study on the Vinylation of Alcohol
Authors: Tsuruta Teiji , Komatsubara Hiroyuki , Furukawa Junji
Published: July 2006

To elucidate the vinylation mechanism, a liquid phase reaction between phenylacetylene and benzyl alcohol was kinetically studied. The reaction was found to proceed along a second order mechanism between the acetylene and the alcoholate. A possible mechanism of the reaction was proposed.
Absorption Spectra of Co(III) Complexes. I. Curve Analyses of the First and Second Absorption Bands
Authors: Shimura Yoichi , Tsuchida Ryutaro
Published: July 2006

The measurements of the visible and ultraviolet absorption spectra of about fifteen Co(III) complex compounds have revealed that the first and second bands of these complexes are not symmetrical either on the scale of frequency or wave-length, and that these bands cannot be represented by the equation of Kuhn and Braun, nor of Lowry and Hudson.

To fit the unsymmetrical absorption bands, a new experimental absorption equation has been developed and its adequacy substantiated.

Some relationships between the first and the second bands of Co(III) complexes are also investigated.
The State of Metal Ion in Aqueous Solutions and its Surface Chemical Effects. III. Rheological Study for the Effect of Metal Ions on the Monolayer of Stearic Acid
Authors: Kimizuka Hideo
Published: July 2006

The effect of metallic ions on the monolayer of stearic acid was studied by the rheologi-cal method.

(1) It was shown that the development of visco-elastic property of the film is closely correlated with the formation of metal soap. Result obtained by the rheological measurement enables us to classify the metal ions into three groups; Li, Ca, Sr and Ba belong to the 1st, showing the formation of the condensed solid film and the rheological behavior of Voigt model; Th, Fe, Al, Co, Cu and Zn, the 2nd, exhibiting the formation of the expanded solid film and the rheological behavior of Maxwell model; Na, K, Rb and NH4, the 3rd, forming no solid film. These results were discussed in relation to the phenomena observed in the studies of the metal ion monolayer interaction, the adsorption of ion on the built-up film and the effect of ion on the wettability of a solid surface. These phenomena could be correlated with the formation of simple soap or complex metal ion-monolayer aggregate, the 1st and 3rd resulting in the former and the 2nd, in the latter.

(2) It was frequently observed for the interacted film with the ions of the 2nd group that the area of solidification is larger than the limiting area estimated from the surface pressure-area curve, while in the case of the film with the ions of 1st group the values of both area coincide with each other.

(3) It was shown that the monolayer of stearic acid, spread on the substrate containing ferric hydroxide sol, formed an expanded solid film.

(4) It was shown for Co and Sr ions that the strength of interacted film is a measure of film-bound ion.
Cathodo-luminescence of Samarium as Applied to the Structural Studies of Alumina. III. On Alumina derived from Boehmite and Bayerite through Thermal Decomposition
Authors: Iwase Eiichi , Nishiyama Seijiro , Isono Toshiaki
Published: July 2006

Investigations were carried out on cathodoluminescence spectra of samarium ions imbedded in alumina, which had been derived from bayerite and boehmite. The mode of thermal transformation of these alumina was concluded from the spectrographic results mentioned above.

A conversion to anhydrous alumina different from α-modification, presumably to β- or ζ-modification, occurred owing to the effect of the contaminating alkali minutely present, when this alumina was derived from calcination of either boehmite or bayerite, each of which had been produced in a solution of sodium aluminate.

The bohemite and the bayerite, purified thoroughly from the alkali, as well as those prepared in the absence of the alkali are readily converted to α- through γ-modification of alumina by thermal treatments.

The heating of the bayerite obtained through rapid carbonation of a solution of sodium aluminate is not, however, likely to result in a simple γ-α transformation of alumina even when the alkali has been removed by careful washing.
Cathodo-luminescence of Samarium as Applied to the Structural Studies of Alumina. V. On Alumina Derived from Hydrargillite by Thermal Treatments
Authors: Iwase Eiichi , Nishiyama Seijiro
Published: July 2006

Results of investigations are summarised as follows on the cathodo-luminescence spectra of samarium ions imbedded in various samples of aluminas, which were thermally derived from hydrargillite.

The transformation from γ- to α-modification of alumina takes place according as the temperature for heat treatment of the hydrargillite is elevated, at whose dried state the samarium ions have been impregnated.

After the hydrargillite was subjected to a previous heat treatment at the temperature range between 250 and 900°C, impregnated with the samarium ions and then calcined over a blast flame of coal gas mixed with air, it gives a characteristic cathodo-luminescence spectrum, which was designated by one of the present authors as the prototype III. The configuration of the alumina giving rise to luminescence bands of this prototype under the excitation by the cathode-rays is when once formed, stable and persistent for heat treatments of much elevated temperatures.

The activated alumina standardised after Brockmann can give, after being impregnated with the samarium ions, the particular cathodo-luminescence spectrum of the prototype III owing to the above-said ions. The appearance of this luminescence spectrum in its pure form is of use for choosing a material as well as for finding an activation method in the preparation of the alumina suitable for the chromatographic purpose.

The dual transformation conception postulated recently by Day on the thermal decomposition of the hydrargillite was elucidated from a structural point of view. The luminescence prototype III of samarium ions seems to be due to the special configuration of alumina, such as χ- and κ-modifications, in which the aluminium ions occupy preferably the tetrahedral rather than the octahedral interstices of oxygen network ofcubic close packing.
Photonitrosation of Cycloalkanes with Nitrosyl Chloride. I. Synthesis of Cyclohexanone Oxime
Authors: Ito Yoshikazu
Published: July 2006

The photonitrosation of cyclohexane with nitrosyl chloride was investigated. It was established that cyclohexanone oxime may be easily produced in good yield (72%) under suitable conditions. The dilution of nitrosyl chloride with hydrogen chloride was most effective for preventing the side reactions, and the photonitrosation of cyclohexane was carried out successsfully at a temperature of 10°C.

The color of the reaction liquid played the role of indicator for a successful photonitrosation; the side reactions seemed not to occur practically so long as the color of the reaction liquid is yellow, and hence, the addition rate of nitrosyl chloride into cyclohexane should be controlled following the color change of reaction liquid.
Dependence of the Exchange Reaction Rate in Catalyst Bed upon the Rate of Feed Gases and the Length of the Bed
Authors: Sakata Sadahiro , Morita Noriyoshi
Published: July 2006

(1) Exchange reaction has the prominent feature that the rate does not change with the progress of the reaction and can be determined only by the mechanism of the reaction. Therefore we can immediately detect the effect of variation in any one of the reacting conditions by the observed conversion of the isotopic exchange reaction.

(2) The relation between exchange reaction and isotopic exchange reaction is considered and an equation which gives the exchange reaction rate (R) using the integral conversion of the isotopic exchange reaction (x) is introduced.

(3) The method is applied to the exchange reaction of oxygen atoms between gaseous oxygen and water vapor catalyzed by chromic oxide, and examination is made of the effect of the variation in the rate of feed gases and in the length of the catalyst bed.

(4) At feed rates higher than 32.0 cc. (S. C.)/sec. cm2 the value R remains almost constant, but by the lowering of the feed rate more than this and by the shortening of the bed length, R is decreased. This decrease accompanied decreases both in activation energy and in frequency factor.

(5) The results are explained by the effects of mass-transfer through the gas film, of eddy or diffusional mixing of the reacting gases and of other kinds of disturbances. Masstransfer resistance of the gas film is a small fraction of the retardation. Mixing of the reacting gases may contribute a higher percent.

(6) The results are compared with the rate of exchange between hydrogen and deuterium measured by Holm and Blue.
On the Lower Boiling Product of Silicon-methylchloride Reaction
Authors: Okawara Rokuro , Sakiyama Minoru
Published: July 2006

(1) Tetramethylsilane, dimethylchlorosilane and methyldichlorosilane and a small amounts of trichlorosilane and hydrocarbon by-product were found in the lower boiling product (b. p. 26°–40°C) of silicon methylchloride reaction.

(2) Dimethylethoxysilane and methyldiethoxysilane besides small amounts of dimethyldiethoxysilane and triethoxysilane were found in the ethanolysis product.

(3) Owing to the contamination of the hydrocarbon by-product, dimethylchlorosilane could not be isolated by repeated distillation. To characterize this substance, it was synthesized from dimethylethoxysilane and benzoylchloride.

(4) By hydrolysis, linear copolymers M′Dn′M′ and M′DnM′ were found. Of these, copolymers M′Dn′M′ having two to eight silicon atoms and M′DM′ have been characterized.
Studies on the Cooking Mechanism of Wood. XIII. On the Phenolic Hydroxyl Group of Lignosulphonic Acid
Authors: Mikawa Hiroshi , Sato Koichiro , Takasaki Chizuko , Ebisawa Kiyo
Published: July 2006

The amount of the phenolic hydroxyl group of the lignin in situ was estimated to be about one per 5-6 methoxyl. Phenolic hydroxyl group of low sulphonated lignosulphonic acid is the same as that of the lignin in situ. There exist two types of phenolic hydroxyl groups (I) and (II) in lignin and lignosulphonic acid, the former being conductometrically titratable and the latter untitratable. With several lignosulphonic acid preparations, the ratios of these two types of phenolic hydroxyl groups were measured, the ratio being 1: 1 with lignin in wood, low sulphonated lignosulphonic acid, and birch α-lignosulphonic acid and about 3: 7 with α-acid of gymnosperm origin. The structures of these two types of phenolic hydroxyl groups were suggested.
Diphenylcarbazone as an Internal Indicator in Volumetric Analysis Determination of Molybdenum by Lead Nitrate
Authors: Deshmukh G S
Published: July 2006

The use of diphenylcarbazone as an internal indicator in the volumetric determination of molybdenum by standard lead nitrate solution is suggested. The end point is characterised by the sharp appearance of a permanent pink colour when molybdate is run into the lead solution and corresponds to the formation of Pb (MoO4). The colour change is completely reversible and errors due to overtitration are therefore eliminated.
Studies on Dimethylglyoximato-cobalt (III) Complexes. IV. Intramolecular O-H-O Hydrogen Bonds in Bis-(dimethylglyoximato)-cobalt (III)-complexes
Authors: Nakahara Akitsugu , Fujita Junnosuke , Tsuchida Ryutaro
Published: July 2006

Infrared absorption spectra of hydrogen dichloro-bis-(dimethylglyoximato)-cobaltate (III) prepared from both normal and deuterated dimethylglyoxime and of several other dimethylglyoximato-cobalt (III)-complexes were measured. It has been ascertained through the data of deuterated complexes that the absorption band at 1725 cm−1 of hydrogen dichloro-bis-(dimethylglyoximato)-cobaltate (III) is attributable to the O-H stretching frequency under the formation of intramolecular O-H-O hydrogen bonds.

All the bis-(dimethylglyoximato)-cobalt (III)-complexes show similar O-H stretching bands in the same region. It has been forecast that a series of examples of the very short and symmetric O-H-O hydrogen bond may be expected in the bis-(dimethylglyoximato)-cobalt (III)-complexes.
Reaction between Iron Pentacarbonyl and Ammonia under High Pressure of Carbon Monoxide
Authors: Uchida Hiroshi , Bando Kenichiro
Published: July 2006

Iron pentacarbonyl has been found to react with ammonia under high pressure of carbon monoxide at temperatures higher than 150°C, to result in a stable powder usually having the practical composition Fe2(CN)4(CO)(NH3)4. In a particular case of the reaction the composition tends to increase in (CO) but decrease in (NH3), till it attains the composition Fe2(CN)4(CO)2(NH3)3.

The crude powder is insoluble in most of solvents, and can not therefore be further purified by recrystallisation, while a potassium salt of the complex anion has been crytallized from its caustic potash solution, in yellow fine prismatic crystals, which have appeared to have the composition K2(Fe(CN)4(CO)(NH3))·1.5H2O. considering this composition in conjunction with that of the crude powder, the powder seems to consist of a complex anion (Fe(CN)4(CO)(NH3))2− and a complex cation (Fe(NH3)3)2+.

Besides this compound having a different chemical composition from those found by J. A. Müller and thereafter by W. Hieber et al., its manufacturing procedure is characterized by the use of iron pentacarbonyl and ammonia as the starting materials.

The product obtained by the reaction of iron pentacarbonyl and ammonia under high pressure of carbon monoxide has been found to accelerate markedly the formation of form-amide from carbon monoxide and ammonia. The product comprises powder and brown liquor, and further the liquor consists of formamide, ammonium carbamate, urea and a minute quantity of an iron salt, among which urea seems most effective for the acceleration.
On the Dielectric Constant of Polar Liquid
Authors: Yasumi Masasi , Komooka Hitoshi
Published: July 2006

An equation for the dielectric constant of polar fluids is obtained from the point of view of the classical theory of electricity in the continuous medium.

The obtained equation has a close relationship to the empirical equation of Wyman.

The comparison with the experimental data are represented.
Synthetic Studies on Oxirane Compounds. I. Ammonolysis of 2,3-Epoxyl-3-pheny-1-propanol
Authors: Suami Tetsuo , Uchida Ichiro , Umezawa Sumio
Published: July 2006

1-Phenyl-1-amino-2, 3-propanediol, m. p. 90–91°, was obtained by ammonolysis of 2,3-epoxy-3-phenyl-1-propanol. Several derivatives of this compound were described.

A part of the cost of the present research has been defrayed from the Scientific Research Encouragement Grant from the Ministry of Education, to which the authors’ thanks are due.
Diphenylcarbazone as an Internal Indicator in Volumetric Analysis. III. Volumetric Determination of Thorium by Ammonium Molybdate
Authors: Deshmukh G S , Bokil Indumati
Published: July 2006

A simple volumetric method for the quantitative estimation of thorium as molybdate is described. This is based on the titration of aqueous thorium nitrate (or chloride) solution against standard ammonium molybdate in presence of ethanol by using diphenyl-carbazone as the internal indicator. Under specified operative conditions, normal thorium molybdate is precipitated. The indicator behaves reversibly and the accuracy of the method is comparable with those obtained by classical procedures.
Studies on Serine Peptides. I. Optical Resolution of O-Benzyl-Dl-serine and Synthesis of Dl-Serine Peptides
Authors: Okawa Kenzi
Published: July 2006

The optically active O-Benzyl-l-serine was prepared in 78% yield by the enzymatic resolution of the N-acetyl derivative with Takadiastase.

Dl-Seryl-glycine was prepared by the N. C. A. method of Bailey and Dl-seryl-l-leucine was synthesized by the Fischer’s acid chloride method respectively.

As was expected, it was found that O-benzyl-serine can be utilized as the starting material in the peptide syntheses.
Hydrazinolysis of Peptides and Proteins. II. Fundamental Studies on the Determination of the Carboxyl-ends of Proteins
Authors: Akabori Shiro , Ohno Ko , Ikenaka Tokuji , Okada Yoshimi , Hanafusa Hidesaburo , Haruna Ichiro , Tsugita Akira , Sugae Kin-ichi , Matsushima Taijiro
Published: July 2006

1. Fundamental experiments on the hydrazinolysis method, a method for characterization of C-terminal amino acids of proteins, were carried out.

2. Amino acids were found to decompose to various extents by heating with anhydrous hydrazine.

3. Amino acid hydrazides were hydrolysed about 1% or less by heating with anhydrous hydrazine (ca. 99%) for ten hours. Hydrolyses of them in neutral and slightly acidic solutions at room temperature are negligible, but in alkaline solution the extent of hydrolyses are somewhat greater though less than 0.2% in five hours in 1% bicarbonate solution.

4. Procedures for separating free amino acids from amino acid hydrazides as DNP-derivatives with or without treatment of iso-valeraldehyde prior to dinitrophenylation were reinvestigated thoroughly.

5. Some experiments on the hydrazino-lyses of peptides were done.

6. Fundamental investigations of the characterization of the mode of linkage of monoaminodicarboxylic acids in peptide chains by the hydrazinolysis method indicate its availability.

7. Standard methods for quantitative estimation of C-terminal amino acids or proteins are established based upon the results obtained by the present investigation.

8. Brief consideration on the mechanism of the hydrazinolysis was described and the scope of this method was discussed in conection with that of the carboxypeptidase method
Methylhydropolysiloxanes from Cohydrolysis of Methylhydrochlorosilanes and Methylchlorosilanes
Authors: Okawara Rokuro , Sakiyama Minoru
Published: July 2006

1) The low boiling fraction of siliconmethylchloride reaction was cohydrolyzed with the three kinds of methylchlorosilane and the methylhydropolysiloxanes, MM′, M′-D′DM′, M′D2M′3T and M′2TD′M′, have been prepared and characterized.

2) A complete series of linear methylhydropolysiloxanes, MD′nM having three to eight silicon atoms have been prepared and characterized from the cohydrolyzate of methyldichlorosilane and trimethylchlorosilane.
Ultraviolet Spectrophotometric Determination of Iron
Authors: Ishibashi Masayoshi , Shigematsu Tsunenobu , Yamamoto Yuroku , Tabushi Masayuki , Kitagawa Toyokichi
Published: July 2006

Absorption has been investigated for the solution of ferric perchlorate at various acidities in ultraviolet region and the existence confirmed of two isosbestic points at 223 mμ and 271 mμ. A method of spectrophotometric determination for iron has been proposed which involves the measurement of absorbance at the isosbestic point. Effects of temperature, acidity and diverse ions have been examined and the purity of iron base alloys has been determined by differential method.
Study on Zinc Oxide-Chromium Oxide Catalyst. II. Variation of Catalytic Activity for Methanol Decomposition with Addition of Chromia and Structural Dependence of Activity
Authors: Uchida Hiroshi , Ogino Yoshisada
Published: July 2006

From the results on the rates of methanol decomposition by the catalysts of different zinc oxide-chromium oxide compositions the rate (ν) of evolution of carbon monoxide per unit surface area of catalyst has appeared to be represented by the following equation

v=ae^αE·e^-E/kT

where a and α are constants applicable throughout the two series of catalysts produced by different methods. The activation energy (E) of the methanol decomposition attains to a minimum value when the catalyst has a certain chromia content. It is directly related with the activation energy of electrical conductivity of the catalyst in hydrogen at high temperature but neither with the concentration of n-type conductivity centres nor with that of p-type conductivity centres. At such temperatures, the adsorption of hydrogen on the oxygen atoms in the surface was considered to participate in the electrical conductivity.

Moreover, the results on determinations of the surface area and the excess oxygen content, together with the information about the structure obtained from diffraction patterns, reveal that there is a similarity in tendency between the increase of concentration of zinc chromite spinels in the catalyst surface and the decrease of activation energy of the decomposition. This relation can be explained from the view of E. Cremer on the compensation effect. The quantity of chromia added in excess of the proper amount for combination with zinc oxide causes both the surface area and the activation energy to increase towards those of chromia alone.

The addition of chromia has therefore a considerable influence upon the activation energy of methanol decomposition, which is quite contrary to what G. Natta described on the methanol synthesis.
Synthetic Amphoteric Polypeptide. II. Synthesis and Some Properties of a Reversibly Contractile Amphoteric Polypeptide
Authors: Yuki Heimei , Sakakibara Shumpei , Taki Toshio , Tani Hisaya
Published: July 2006

1. A reversibly contractile amphoteric polypeptide, copoly-26 : 26 : 1-(l-glutamic acid, l-lysine, Dl-cystine), was synthesised.

2. The foil of this polypeptide contracted at its isoelectric region and extended in both acidic and basic media. This extension and contraction was pH-dependent and fully reversible.

3. The load-elongation relation of the strip of this foil was measured in aqueous media using the load up to about 2,000 times the dry weight per 1 cm. of length of the strip. This relation was linear in this range.

4. The temperature-elongation relation was measured in aqueous media at 20–50°C. From the data it was concluded that, at a given temperature, the internal energy and entropy increased with the elongation of the strip.

5. The change of length of the strip in aqueous media, containing hydrochloric acid, sodium hydroxide, sodium chloride and some other neutral salts individually or in pairs, was measured. Some peculiar and interesting phenomena were observed.
Determination of Nitrate Nitrogen by the Strong Phosphoric Acid-Iodic Acid Decomposition Method
Authors: Ohashi Shigeru , Makishima Hiroshi
Published: July 2006

(1) The strong phosphoric acid-iodic acid decomposition method for the determination of nitrogen in organic compounds, which was already reported, has been extended to the analysis of nitrate nitrogen.

(2) In a reaction vessel salicylic acid was nitrated by heating with the sample and concentrated sulfuric acid and the product was reduced by heating with sodium thiosulfate. The resulting mixture was decomposed by heating with a mixture of strong phosphoric acid and potassium iodate. The liberated Kiba for his interest and encouragement, nitrogen was measured gas-volumetrically.

(3) In the presence of nitrate, ammonium defrayed from a grant given by the Ministry salt, and urea, the total nitrogen and the nitrogen except nitrate could be determined are due. by the strong phosphoric acid-iodic acid decomposition method, respectively.
The Adsorption of Water Vapor by Gelatin-Detergent Complexes
Authors: Tamaki Kunio , Tamamushi Bun-ichi
Published: July 2006

1. The adsorption of water vapor by gelatin-dodecyl sulfate ion complexes and gelatin-dodecyl ammonium ion complexes has been measured.

2. The adsorption of water vapor by both those kinds of complexes has been found to be less than that by pure gelatin.

3. The amount of adsorption on the gelatin-dodecyl sulfate ion complexes is always smaller than on the gelatin-dodecyl ammonium ion complexes, and this fact indicates that the former complexes are more hydrophobic than the latter.

4. The adsorption isotherms have been interpreted by the B.E.T. theory and the amount of the first monolayer adsorption has been calculated.

5. In both types of complexes, there is a certain parallel correlation but no stoichiometric relationship between the reduction in the amount of the first monolayer adsorption and the amount of combined detergent.
Heats of Dilution of Polyvinylalcohol Solutions. II
Authors: Amaya Kazuo , Fujishiro Ryoichi
Published: July 2006

Heats of mixing of 1,4- and 1,3-butandiols with water and heats of dilution of polyvinylalcohol of different acetyl contents were measured.

The results obtained for the two butanediols and water system were compared with the results for ethylalcohol-water system and for polyvinylalcohol-water system (reported in the previous paper) and it was found that the apparent interaction parameter of these substances with water decreases and becomes more normal as the degree of polymerization becomes larger. The interaction parameter for polyvinylalcohol of different acetyl content with water first increases and then (through max.) decreases as the content of acetyl radical increases.

All these results are consistently explained from the standpoint of intra-molecular or inter-segmental association.
Measurement of Solubilities of Sparingly Soluble Liquids in Water and Aqueous Detergent Solution Using Non-ionic Surfactant
Authors: Hayashi Makoto , Sasaki Tsunetaka
Published: July 2006

1. The solubility of iso-amyl alcohol, n-butyl alcohol and benzene were determined by the titration using the surfactant, Tween 80.

2. In the case of iso-amyl alcohol and n-butyl alcohol, the relation between the turbidity and the quantity of solute in surfactant solution is linear, and the solubilitylimits are both lower than the solubilities in pure water in the dilute region of the surfactant. This makes the determination of their solubility easy and accurate both in pure water and aqueous solution of the detergent.

3. The above method cannot be applied directly for the determination of the solubility of benzene. Ethyl alcohol-Tween 80 mixture is used instead of Tween 80 to overcome this difficulty.

4. The solubilities obtained by this method are accurate enough compared with other methods, in the case of iso-amyl alcohol and n-butyl alcohol, possible error being estimated to be 0.4%. In benzene, the error is somewhat larger, but is in good agreement with the values of the literature.
Spectrochemical Study of Microscopic Crystals. XIII. The Structure of Wolffram’s Red Salt, Pt(NH2·C2H5)4Cl3·2H3O and a Related Compound
Authors: Yamada Shoichiro , Tsuchida Ryutaro
Published: July 2006

Polarized absorption spectra of Wolffram’s red salt, Pt(EA)4Cl3·2H2O, and a related compound, Pt(EA)4Br3·2H2O, EA being ethylamine, have been determined by Tsuchida-Kobayashi’s microscopic method in the regions covering from 2400 to 7500 Å.

Both the compounds, which are supposed to be formulated by [Pt(EA)4][Pt(EA)4X2]X4·4H2O, have been found to show an absorption band that has not been observed with either of the components alone. Moreover, this band is strongly polarized along the needle axis. These relationships may be understood on the assumption that the crystals of these compounds involve infinite chains of ---X—PtIV—X---PtII---X—PtIV—X--- along the needle axis, X being chlorine or bromine.

The new absorption at the longer wavelength may be considered as a charge transfer band along the infinite chains as assumed above.
Partition Equilibrium of Cumene Hydroperoxide between Water and Cumene
Authors: Yamada Shigehiko , Kat\={o} Tokio
Published: July 2006

The partition equilibrium was investigated in relation to the steam-blowing and stripping, during and after the hydroperoxidation of cumene, and the following results were obtained.

1. Equilibrium constant K does not depend on the concentration of CHP within the limit of experimental error, but it depends on the temperature.

2. The partition constant, K approximately satisfies the following formula,

K=1.3_4×10^-4e^1580/T.

3. The heat of transference of 1 mol. of cumene hydroperoxide from cumene solution into water under the equilibrium condition, was determined as 3.16 k cal./mol.
Some Optical Properties of Zinc Sulfide Phosphors Doubly Activated with Copper and Manganese
Authors: Shionoya Shigeo
Published: July 2006

Optical properties of ZnS: (Cu+Mn) phosphors have been extensively studies with the purpose to investigate the phenomena of sensitized luminescence in photoconductive phosphors. Spectra of emission, absorption and axcitation, thermoluminescence and photo-conductivity were measured. It was confirmed from the measurement of excitation spectra that the manganese emission is really sensitized by coper behaving as a sensitizer. Some interesting phenomena ascribe to this sensitization were found in the measurements of thermoluminescence and photoconductivity. The mechanism of the sensitization was discussed exhaustively. It appears reasonable to conclude tentatively in the present situation that the resonance transfer rather than the photoelectron transfer is the predominant mechanism.
Tie Line Correlation for Ternary Liquid Equilibria
Authors: Ishida Kiyoharu
Published: July 2006

The various methods for obtaining straight lines were examined for the tie-line data investigated at several temperatures near the critical solution temperature for binary mixtures of the solute and the solvent, and the following results were obtained.

1. The Hand plot and the Othmer and Tobias plot which are useful for the systems containing one partially miscible pair are unsatisfactory for the systems containing two partially miscible pairs.

2. The method proposed by Brown and the method by Conway and Philip which have been said to be applicable for the systems containing the formation of two pairs of partially miscible liquids do not give good results for the systems at temperatures near the critical solution temperature for binary mixtures of the solute and the solvent.

3. If a plot is made of the logarithm of the ratio of the concentration of the diluent in the diluent phase to the concentration of the solvent in the solvent phase against the logarithm of the concentration of the diluent in the diluent phase, a straight line will be obtained not only for systems containing two partially miscible pairs, but also for systems containing one partially miscible pair.
Constituents of the Mucilage of Gloiopeltis Furcata
Authors: Hirase Susumu , Araki Choji , It\={o} Toshiya
Published: July 2006

1. The mucilage of Gloiopeltis furcata has been investigated by the complete methanolysis method.

2. 3,6-Anhydro-l-galactose dimethylacetal and methyl d-galactoside have been isolated from the methanolysate. In addition, l-galactose has also been isolated in the form of the crystalline Dl-galactose diethylmercaptal.

3. The yields of the isolates have indicated that the mucilage used contains 3, 6-anhydro-l-galactose, d-galactose and l-galactose in the approximate molar ratio of 8:12:1.
Studies on Azeotropic Mixtures. I. General Considerations
Authors: Yoshimoto Toshio , Mashiko Yo-ichiro
Published: July 2006

The general expression for the azeotropeforming power of binary solution has been derived and the conditions for azeotrope existence presented. The quasi-crystalline model has been adopted for the solution, which is assumed to be a strictly regular solution at an azetropic point and an explicit representation for interaction energy of component molecules introduced.

Azeotropic mixtures have been grouped into four classes according to the type of molecular interaction and the azeotrope-forming power (molecular interchange energy) has been calculated and discussed.
THE CRYSTAL STRUCTURE OF THIOUREA
Authors: Demény László , Nitta Isamu
Published: July 2006

Using the Laue photographic and X-ray spectrometric methods the crystal structure of thiourea was investigated. The unit of structure built upon the simple orthorhombic translation group Γ0, is of the dimensions a=5.47, b=7.64 and c=8.54 A., and contains four chemical molecules of CSN2H4. Thus the density is 1.408. The plausible space group being Vh16, a possible atomic arrangement, neglecting H atoms, was found to be as follows:

(Remark: Graphics omitted.) with x=0.300, y=0.164 and z=0.144. The molecule has the symmetry of Cs, i.e. it has one plane of symmetry in it. In such a model, the distance. C–S is 1.81 Å., and that C–N is 1.39 Å. Discussion was also made upon its crystalline and molecular structures in comparison with those of urea.
MICRO-IDENTIFICATION OF ISOMERS AND HOMOLOGUES IN THEIR MIXTURE. I. THREE ISOMERIC XYLENES
Authors: Migita Masao
Published: July 2006

Methods to detect and identify the three isomeric xylenes in their mixture, especially in limited quantity, are given.

1. m-Xylene and p-xylene, even in minute quantity, can be successfully identified as their trinitro-derivatives, by their colour-reactions in alcoholic or acetone solution toward alkali, or by the optical properties of their crystals. These two methods leave little to be desired.

2. o-Xylene is identified microscopically as sodium sulphonate, but in case of a mixture very poor in o-xylene, we can not expect a result of high sensitivity by this method.

3. The technical method to separate p-xylene from its isomers, based on its insolubility in ordinary conc sulphuric acid, is tested and shown to be of little value.