bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies of the Electrolytic Conductance of a Dye Solution. I. Complex Formation in an Aqueous Solution of the Mixture of Chlorazol Sky Blue FF and Chrysophenine G
Authors: Shinzawa Kinko , Tanizaki Yoshié , Ando Noboru
Published: July 2006

The conductances of aqueous solutions of Chlorazol Sky Blue FF (Blue), Chrysophenine G (Yellow), Sodium Chloride and their binary mixtures at various constant ratios have been measures. The conductance observed with a mixture of Blue and yellow increased abnormally compared with that obtained by the sum of individual dye conductances; the difference between the observed and the sum values reached a maximum at about the same fraction of the equivalent concentration of component dyes. A similar relation of the conductance against the fraction of the conductance against the fraction of the equivalent concentration of components, obtained with mixture, in which component dye was substituted by sodium chloride. did not always show a coincidence between the observed value and the sum one. the difference, however was much smaller than that obtained with dye mixtures. Thus, the abnormal increase described above may be attributed to the formation of complexes of Blue and Yellow; a 1:1 complex and a 1:2 complex, consisting of Blue and yellow already known, were sufficiently reflected in the conductance curve, especially in the conductance curve, especially in a 1:2 complex.
Stability Order in Metal Chelate Compounds. I. 4-Carboxy -and 4-Sulfocatechol Complexes
Authors: Murakami Yukito , Nakamura Katsuyuki , Tokunaga Masasuke
Published: July 2006

The stability constants of 4-carboxy- and 4-sulfocatechol chelates with bivalent transition metals and alkaline earth metals have been evaluated in aqueous media at 30.0±0.1°C and 0.10 m of ionic strength. The stability orders, manganese<cobalt∼nickel<zinc<copper for transition metal chelates and strontium<calcium<magnesium for alkaline earth metal chelates, have been found to hold in these catechol chelate systems. A unique stability sequence, nickel<zinc, has been discussed in terms of the electron delocalization effect, in which metal d orbitals, lone pair orbitals of catechol oxygens and π orbitals of the benzene ring are involved. A reverse relationship for ligand basicity and chelate stability was observed for copper(II) and zinc(II) chelates, and the stability of metal chelates was found to increase in the sequence; catechol<4-carboxycatechol<catechol-4-sulfonate<Tiron. Substituent groups were considered to play an important role in this case.
Spectrochemical Study of Microscopic Crystals. XXIII. The Structure and Light Absorption of Red Cupric Complexes with Succinimide
Authors: Yamada Shoichiro , Miki Seiko
Published: July 2006

The dichroism in the visible and ultraviolet region has been determined by the microscopic method with single crystals of K2Cu(sucim)4·6H2O, Cu(deen)2(ClO4)2 and Cu(sucim)2 (iso-C3H7NH2)2. From a comparison of these spectra with the spectra of most cupric complexes, it has been concluded that these compounds contain square-planar complexes of copper(II), with the fifth and sixth co-ordination sites left empty. It has been concluded, in a similar way, that the compounds with a formula of Cu(sucim)2(amine)2, the amine being methyl, ethyl, n-propyl, isopropyl, n-butyl and n-amyl amines as well as ammonia, consist of quadri-co-ordinate, square-planar complexes in the crystalline state.

The absorption spectra of bis(succinimidato)-bis(alkylamine)-copper(II) complexes in chloroform, benzene and methylene chloride, in which the compounds are colored dark-blue, have been determined. The enormously large band shift toward a lower frequency, on going from the crystal to the solution, seems to indicate that the configuration in these solvents is not the square-planar or trans-bis-(chloroform) configuration, but deviates from the square-plane.
The Photoisomerization of cis-Azobenzene in the Presence of Iodine
Authors: Yamashita Shigeru , Cosgrave Desmond P , Ono Hiroshi , Toyama Osamu
Published: July 2006

The conversion of cis-azobenzene in a n-hexane solution to its trans-isomer in the presence of iodine has been studied by light irradiation. The experiments with wavelengths of 313 and 436 mμ at −78°C have shown that the excitation of the molecular complex formed between cis-azobenzene and iodine, by its charge-transfer transition or by the blue-shifted absorption of complexed iodine, yields trans-azobenzene with a quantum yield independent of the composition of the solution. By comparing this finding with the results previously obtained for the cis-trans photoiso-merization of free azobenzene in n-hexane, a probable mechanism has been presented: CI2 + hν → CI2*, CI2* → C* + I2 and C* → T, where C and T denote cis and trans-eizoben-zene respectively.

The results obtained at 0°C by irradiation at wavelengths of 546 and 577 mμ, which are solely absorbed by free iodine in the solution, are similar to those previously obtained for stilbene; they may, therefore, be explained in a similar way, i. e., by the photochemical dissociation of free iodine, followed by the iodine atom-catalyzed isomerization of cis-azobenzene.
Preparation of Radioactive Antimony-120 of a High Specific Activity by the Irradiation of Tin with Protons
Authors: Saito Kazuo , Suzuki Nobuo , Seto Kunio , Ikegami Hidetsugu
Published: July 2006

1) By irradiation of a tin target (antimony content, less than 8×10−4%) with 15 MeV. protons (120 μ amp. hr.), about 1 mc. of 120Sb was produced, with a specific activity more than 30 μc. per μg of antimony.

2) The radioactive antimony was either separated by extraction with amylacetate from more than 6 n hydrochloric acid containing tin(IV) or by cation exchange in a 0.4% tartaric acid solution of pH 0.6 to 1.6 containing tin-(II).

 3) 120Sb is electrolytically deposited on an evaporated film of silver or copper from a 1 to 3n hydrochloric acid solution containing 1% hydroxylamine hydrochloride with a yield of 70% within 3 hr.

4) Care should be taken to avoid hydro-lytic aging of antimony in diluted hydrochloric acid, which vitiates the extraction, the ion exchange, and the electrolysis.
Thermal and Radiation Oxidations of Benzene to Phenol in Aqueous Solutions Containing Metal Ions at Elevated Temperatures. II. The Effect of Iron Sulfate and Chloride on Phenol Yield
Authors: Hotta Hiroshi , Terakawa Akira , Shimada Kazuo , Suzuki Nobutake
Published: July 2006

In the ferric sulfate solution, benzene can be oxidized to phenol with a good yield above 170°C, when not irradiated, but at lower temperatures, when irradiated. In the ferrous sulfate solution, the yield of phenol is independent of irradiation, and somewhat larger than in the irradiated ferric sulfate solution. Such a high yield of phenol is due to the complexing of hydroxycyclohexadienyl peroxy radical, produced with OH radical and oxygen dissolved, with ferrous ions.
Synthetic Resins Catalyzing the Racemization of Amino Acids. I. The Preparation of the Resins
Authors: Toi Koji , Izumi Yoshiharu , Akabori Shiro
Published: July 2006

1) Four resinous catalysts (Resins A–D) for the racemization of amino acids were prepared. They had structures partially similar to that of salicylaldehyde or pyridoxal. Resins A and B were prepared by the chemical modification of o-cresol-phenol-formalin resin and salicylic acid-phenol-formalin resin respectively. Resins C and D were obtained by attaching chemically pyridoxal and salicylaldehyde residues respectively to a styrenedivinylbenzene lattice.

2) These resins catalyzed the racemization of amino acids in the presence of cupric ions at 100°C.
The Radiation-Induced Addition of Acetaldehyde to Isobutylene
Authors: Iizuka Shinji , Hatada Motoyoshi , Hirota Kozo
Published: July 2006

The radiation-induced addition of acetalde-hyde to isobutylene has been found to proceed at room temperature; the G(telomer)’s are smaller by one or two orders of magnitude than those when ethylene or propylene is adopted as the taxogen, and they increase markedly with the temperature, reaching a maximum at 110∼150°C.

It has been shown from the gas chromato-graphic and NMR analyses of the telomer produced that the radical chain mechanism proposed in former papers by the present authors is reasonable, although minor products seem to be formed in accordance to an ionic mechanism.

It has been found that the G values of all the telomers decrease in the presence of several solid materials, suggesting the catalytic decomposition of acetyl and other intermediate radicals.
The Structure of Bis(dithizonato)-zinc(II) and -Cadmium(II)
Authors: Yamamoto Yasuo , Yoshinaga Tetsuo , Yamada Shoichiro
Published: July 2006

Two forms of bis(dithizonato)cadmium(II) have newly been isolated. Upon recrystallization from pyridine, both the forms yielded the same dark red crystalline powder. A comparison of their infrared and ultraviolet spectra shows that the mode of coordination and the configuration of zinc(II) and cadmium(II) are the same as in the mercury(II) complex.
The Dehydrating Cyclization of S-Carboxymethyl-cysteine and N-Acetyl-S-carboxymethyl-cysteine
Authors: Ozawa Hitoshi
Published: July 2006

S-Carboxymethyl-cysteine (SCMC) cyclizes by dehydration to form 3-oxo-5-carboxy-per-hydro-1,4-thiazine (SCMC-lactam) when the aqueous solution was heated at 110∼180°C. SCMC-lactam was also obtained from N-acetyl-SCMC when the latter was treated with N,N′-dicyclohexylcarbodiimide and hydrolyzed subsequently at pH 9.0.
Studies in the Two Phases System Sodium Formate-Pyridine. Extraction of Nickel and Separation from Chromium
Authors: Deshmukh G S , Rao A L J
Published: July 2006

The distribution of nickel in the two phase system, sodium formate-pyridine is studied in detail. The effects of pH, volume of pyridine and molarity of formate are studied and the optimum conditions for the complete extraction are established. The possibility of using this extraction technique for the separation of nickel and chromium has also been worked out and a procedure for the analysis of a syn-thetic mixture of nickel and chromium is given.
The Hydration of Some Organic Compounds in an Aqueous Solution. I. Studies of Aliphatic Aldehydes by Raman-effect Observation
Authors: Matsushima Michiko
Published: July 2006

The Raman spectra of acetaldehyde, its aqueous solution and its heavy water solution have been recorded at various temperatures and in various concentrations in order to find the Raman frequencies characteristic of the hydrated species and in order to investigate the reversible hydration process. Almost all the lines have been assigned tentatively on the assumption that the hydrate molecule has Cs symmetry. The lines at 325, 480, 567, 1353, 1440, 1449, 2874, 2939 and 2996 cm−1 can be referred to as the lines characteristic of the hydrate. Supporting data have also been obtained for the related compounds for the sake of comparison. Moreover, through the intensity measurements, equilibrium constants, as well as the heat of hydration, have been evaluated as the basis for a discussion of the hydration process.
The Determination of the Water Content of the Low Polymers of Formaldehyde by the Karl Fischer Method. I. The Determination of the Adsorbed Water and Bound Water Formed by the Pyrolysis of the Polymer
Authors: Muroi Kaname , Ogawa Kunihiko
Published: July 2006

The adsorbed water of the low polymer of formaldehyde was determined by extraction with dry methanol and Karl Fischer titration. The sum of the adsorbed water and the water formed by the pyrolysis of the sample was determined by titration with the specially prepared Karl Fischer reagent SS, after the sample had been dissolved in propylene glycol by heating. The method of the separation and the determination of the two kinds of water was thus established. When the average numerical degree of polymerization of the polymers was calculated from the content of bound water determined by this method, satisfactory results were obtained. To verify the accuracy of the determination of water content, formaldehyde and methanol were determined independently; their sum was found to be almost 100%.
Ionic Hydration in an Aqueous Electrolyte Solution and Its Parameter
Authors: Tamura Kiyoshi , Sasaki Tsunetaka
Published: July 2006

Tait’s equation for water and Harned and Owen’s treatment of an electrolyte solution, together with sound velocity data, enabled the calculation of the molar volume of electrolytes in the solution state. The results agreed fairly well with the molar volume of the super-cooled molten electrolyte extrapolated to room temperature.

The concentration coefficient of electrostrictive pressure, L=Pe/C1C2, the volume contraction due to the dissolution of one mole of solute, ΔV, and the volume of hydration water per mole of solute, Vh, as an incompressible part of water have been evaluated. We have found a common variable, [h], for L, ΔV and Vh, and it has been proposed that this variable can be used as a parameter of hydration expressing the mole number of hydration water per mole of electrolyte. A conventional hydration number, [h*], was also proposed.
Influence of Substituent Groups on Nuclear Reactivity in the Formation of Substituted Biphenyls by Reaction of Aromatic Diazo and Related Compounds with Aromatic Liquids. VI. p-Chlorophenylation
Authors: Migita Toshihiko , Morikawa Naotake , Simamura Osamu
Published: July 2006

N-Nitroso-p-chloro(36Cl)acetanilide has been decomposed in mixtures of benzene and mono-substituted benzene C6H5X (X=NO2, Cl, OCH3, and CH3), and the reaction products have been analyzed for 4-chlorobiphenyl and isomeric 4-ClC6H4C6H4X by the isotope dilution method. On the basis of these results, the partial rate factors for the p-chlorophenylation have been calculated to be, for nitrobenzene: o, 4.35; m, 0.61; p, 6.18; for chlorobenzene: o, 2.70; m, 0.87; p, 1.33; for anisole: o, 3.93; m, 0.94; p, 1.54 and for toluene: o, 2.97; m, 1.07; p, 1.32.

The values of the partial rate factor for the meta position give a satisfactory Hammett plot with a slope of −0.27. This fact demonstrates that the p-chlorophenyl radical shows a measure of electrophilic character in the homolytic aromatic substitution.
Influence of Substituent Groups on Nuclear Reactivity in the Formation of Substituted Biphenyls by Reaction of Aromatic Diazo and Related Compounds with Aromatic Liquids. VII. p-Nitrophenylation and p-Methoxyphenylation
Authors: Itô Ryôichi , Migita Toshihiko , Morikawa Naotake , \={O}kuni Morihiko , Simamura Osamu
Published: July 2006

N-Nitroso-p-nitroacet(anilide-14C) and N-nitroso-p-methoxyacet(anilide-14C) have been decomposed at 20.0°C in mixtures of benzene and monosubstituted benzenes C6H5X (X=NO2, Cl, OCH3, and CH3), and the reaction products have been analyzed for 4-nitro-and 4-methoxybiphenyl and isomeric 4-NO2C6H4C6H4X and 4-CH3OC6H4C6H4X by the isotope dilution method.

From the results of these competitive experiments, the partial rate factors for the p-nitrophenylation and p-methoxyphenylation have been calculated (Tables I and II).

The values of the partial rate factor for the meta position give a satisfactory Hammett plot with a slope of −0.81 for the p-nitrophenylation and one with a slope of +0.09 for the p-methoxyphenylation, showing that the p-nitrophenyl radical has a pronounced electrophilic character while the p-methoxyphenyl radical has little, if any, nucleophilic character.
The Stability of Fused Rings in Metal Chelates. II. Copper(II) Complexes of Schiff Bases Derived from Pyruvic Acid and Amino Acids or Diamines
Authors: Nakahara Akitsugu , Yamamoto Haruyo , Matsumoto Hironobu
Published: July 2006

The preparation and some properties of four new copper(II) chelates of Schiff bases produced from pyruvic acid and amino acids or diamines have been reported.

The relative stability of these compounds as well as of other rather popular copper(II) chelates has been discussed on the basis of spectroscopic and polarographic investigations.

It has been demonstrated that any stress on any individual ring in metal polydentatechelates does not generally tend to be deposited in the same ring, but rather spreads to some extent over the whole fused-ring system,, sometimes strengthened and at other times weakened or even completely cancelled by another stress on another ring in the system. Therefore, the stability of fused rings should not be discussed on the basis of a simple summation of the stability of individual rings contained in the fused-ring system. It has been concluded that the stability of metal polydentate chelates increases with a decrease in stress over the whole fused-ring system.
Studies of the Transient Intermediates in the Photoreduction of Methylene Blue
Authors: Kato Shunji , Morita Masaharu , Koizumi Masao
Published: July 2006

The intermediate species which are produced in the course of the photoreduction of methylene blue have been investigated by flash photolysis in plain aqueous, borate and phosphate buffer solutions with and without reducing agents. In an acidic solution, an absorption band with the lifetime of 30μsec. appears at 375 mμ, while in neutral and basic solutions, two bands appear, at 415 and 520 mμ, with lifetimes of 70∼90 μsec. The bands at 375 and 415 mμ are considered to be due, respectively, to the acidic and basic forms of the triplet state, since the transient spectra change with pH, making an isosbestic point.

The band at 415 mμ is overlapped by another one with a lifetime longer by several hundred microseconds; this is presumed to be semiquinone. The intensity of the band at 520 mμ decreases upon the addition of reducing agents and increases upon the introduction of oxygen.

Hence, this band may be due to the halfoxidized form of the dye. These results support the reaction scheme that the excited state of the dye reacts with the ground state, which has been proposed in the investigation of steady light photobleaching.
The Preparation of 2, 5-Thiophenedicarboxaldehyde
Authors: Sone Tyo
Published: July 2006

The application of Kröhnke’s method to 2,5-bis(chloromethyl)thiophene has afforded 2,5-thiophenedicarboxaldehyde, from which some condensation products with amines and active methylene compounds have then been derived. 2-Methyl-5-acetyl-3-thiophenecarboxaldehyde and 2-methyl-3,5-thiophenecarboxaldehyde have also been prepared, from 2-methyl-3-chloromethyl-5-acetylthiophene and 2-methyl-3-chloromethyl-5-thiophenecarboxaldehyde respectively, by the Sommelet procedure.
Entropy and Molecular Motion in the Condensed Phases of Tetrahedral Molecules
Authors: Chihara Hideaki , Shinoda Takako
Published: July 2006

By a comparison of the entropies of sublimation at the triple points of carbon tetrafluoride, carbon tetrachloride and neopentane with those of inert gas solids, it has been shown that these molecules are in the state of hindered rotation rather than of reorientation in the solid at the respective triple points, with heights of the potential barrier of 1.0, 2.4 and 1.3 kcal./mol. respectively. The hindering potential has been shown to be proportional to the transition temperatures of these solids.

A simple model for the structure of liquid carbon tetrachloride has been presented to account for its entropy of vaporization; the model consists in assuming nearest neighbor crystallite embryos in the liquid.
The Synthesis of Methylacetylene by the Pyrolysis of Propylene. II. The Mechanism of the Pyrolysis
Authors: Sakakibara Yasumasa
Published: July 2006

A study has been made of the mechanism of the pyrolysis of propylene at high temperatures (800∼1400°C). Of the gaseous products, hydrogen, methane, ethylene, allene, and 1-butene, obtained in the yields of 25, 43, 40, 27, and 9 mol. per 100 mol. of propylene pyrolyzed (3% conversion) respectively, have been found to be the primary products, while methylacetylene, acetylene, and butadiene, obtained in the yields of 9, 4, and 2 mol. respectively, have been found to be the secondary products. In view of the results of the pyrolysis of allene itself, even at a low conversion of 3%, allene appears to undergo considerable secondary reactions, such as isomerization to methylacetylene, addition to propylene and allyl radicals, and decomposition, for example, to acetylene and methane via methylacetylene. On the basis of the observed results, free-radical mechanisms have been proposed for the primary reactions and main secondary reactions. The mechanism for the primary decomposition reaction is a chain process in which the chain is initiated by the reaction C3H6→C3H5· (allyl radical) + H, and is, via the chain-propagating step, terminated by two types of reactions, C3H5·+H→ C3H6 and C3H5· + CH3·→1-C4H8. The formation of allene-methylacetylene has been satisfactorily explained by considering secondary reactions.
Nature of the π-Electronic Spectra of Aromatic Compounds I. Aromatic Hydrocarbons and Their Hydroxyl Derivatives
Authors: Nishimoto Kichisuke , Fujishiro Ryoichi
Published: July 2006

The π-electronic spectra of a number of aromatic hydrocarbons and their hydroxyl derivatives have been theoretically studied by the ASMO-CI method within the framework of a limited LCMO approximation. The calculated singlet frequencies are in satisfactory agreement with the experimental findings. The experimental Clar relation is obtained theoretically. The present theory suggests that the substitution of a hydroxyl group at the α-position of the parent hydrocarbon has effects of a substantial red shift in the 1La band and a rather small shift in the 1Lb band, but the band characteristics are practically the same as those of the parent hydrocarbon. On the other hand, the substitution at the β-position has the effect of mixing the 1La species with the 1Lb species to a considerable extent, so that the band characteristics of the parent hydrocarbon should be considerably modified by this type of substitution. In the light of the present theory, it is better to regard the spectra of phenanthrene and pyrene as modified biphenyl spectra. A plot of the calculated frequency against the corresponding Hückel energy gives a rather good correlation.
Studies of the Hydration and the Structure of Water and Their Roles in Protein Structure. I. The Effective Volumes of 1-1 Electrolytes in Aqueous Solutions and the Electrostriction of Water
Authors: Goto Sachio
Published: July 2006

The effective volumes, the apparent volumes and the magnitudes of electrostriction for various 1-1 electrolytes in aqueous solutions have been determined from an analysis of the densities of solutions at various concentrations. The molar values thus obtained are stoichiometrically additive. The state of water molecules around ions and particularly the existence of clathrates around various univalent ions, such as lithium, rubidium, cesium, bromide and iodide, and the numbers of hydration water have also been discussed.
Studies of Ammonium Dioxovanadium(V) Bisoxalate Dihydrate
Authors: Sathyanarayana D N , Patel C C
Published: July 2006

A simple method for the preparation of the yellow diamagnetic complex, (NH4)3[VO2·(C2O4)2]·2H2O, is described. Around 200°C, the complex suffers decomposition, giving a bluish-grey paramagnetic compound (NH4)2·[(VO)2(C2O4)3]. The infrared spectrum of the yellow complex shows a covalent bonding between vanadium and the oxalate groups.

The absorption in the ultraviolet region is due to the electron transfer within the VO2 group. An octahedral structure, with the two linearly-arranged oxide oxygens at unequal lengths from vanadium(V), is suggested for the complex anion.
Characterization of the Alumina-Boria Catalyst
Authors: Izumi Y\={u}suke , Shiba Tadao
Published: July 2006

This study has aimed to secure an optimum means for the preparation of an alumina-boria catalyst by a systematic examination of the relationship between the physical characteristics of the catalyst and its activity, and to clarify the mechanism of the development of activity on the basis of the experimental evidence about the chemical interaction of alumina with boric acid and about the chemical structure of the catalyst. The applicability of the catalyst has been studied kinetically for some specific reactions relating to the transalkylation of aromatic compounds. It has been found that alumina-boria shows a higher activity for these reactions than does silica-alumina.

The results and conclusion may be summarized as follows:

I) Boric acid is dehydrated to produce metaboric acid as a probable intermediate and reacts with an active alumina at about 130°C with little disturbance of the crystal structure of alumina, and effective acidic centers are produced. Most of the acid centers are of the Brönsted type. Alumina-boria does not show any definite chemical structure characteristic of aluminum borates, such as 9Al2O3·B2O3, 2Al2O3·B2O3 or Al2O3·B2O3. It is suggested that such a bond as Al-O-B-O-Al may be formed between surfaces of the crystal structure of alumina and may result in acidic centers.

II) The catalytic activity of toluene disproportionation shows a good correlation with the Bronsted acidity. This is well compatible with the likely theory that the reaction proceeds via a carbonium ion mechanism.

III) The activity of the disproportionation is considerably affected by the structure of the alumina used as the catalyst base as well as by the boria content of the catalyst. The catalyst prepared from η-alumina shows a higher activity than that from χ-alumina, while α-alumina does not give an active catalyst because of its poor reactivity with boric acid. A rise in the crystallinity of alumina lowers the reactivity. Excessive boria reduces the catalytic activity. An effective catalyst for the transalkylation of aromatic compounds can be obtained when alumina-boria is calcined above 400°C.

IV) The results of such reactions as the disproportionation of toluene, the isomerization of xylene and the transethylation between benzene and diethylbenzene can be well interpreted kinetically by assuming that the rates of these reactions are controlled by surface reactions between adsorbed molecules of the reactants.

V) In the disproportionation of toluene, a decrease in the activity of the catalyst with the length of the run was observed. This phenomenon can be explained analytically by taking into account the fact that some contaminant such as the carbonaceous material, which is produced by side reactions (cracking of toluene and xylene), covers effective sites of the catalyst.

VI) It seems to be due essentially to the higher concentration of active sites in alumina-boria that its activity of the transalkylation of aromatic compounds is higher than that of silica-alumina.
Physical Properties and Structure of Polyacetonitrile
Authors: Oikawa Eizo , Kambara Shu
Published: July 2006

The fact that a polymer containing C=N double bonds is formed from saturated nitrile complexes with metal chlorides is supported by the infrared absorption at about 1600 cm−1 and the characteristic addition of silver nitrate. The polyacetonitrile has an electric conductivity from 10−10 to 10−5Ω−1 cm−1 and an energy gap from 0.4 to 1.2 eV., indicating that the polymer is an organic semiconductor.

The electric conductivity increases and the energy gap decreases with increases in the heating time and temperature, suggesting a more extensive formation of a conjugated system, including also C=C double bonds among polymer chains at a higher temperature. This theory is supported by the evolution of ammonia, resulting in simultaneous decreases of the H and N contents of the polymer, the appearance of the absorption at 840 cm−1, by oxidation by potassium permanganate, by analyses of ESR line shapes, and by viscometric measurements. This structual change may bring about a noncrystalline pattern in X-ray diffraction. Therefore, it is indicated that polyacetonitrile does not have a complete C=N conjugated sequence because of some pyrolysis, accompanied by the extension of a conjugated sustem such as cross-linking at a higher temperature and a longer heating.
The Electrical Conductivity of Heterocyclic Compounds. Fluoridine and Triphenodioxazine
Authors: Inoue Hiroo , Noda Kazuo , Imoto Eiji
Published: July 2006

The electrical conductivities of fluoridine and triphenodioxazine have been measured, and it has been confirmed that (1) the ρ0 of three compounds decreased in the following order: triphenodioxazine > fluoridine in the surface-type cell and fluoridine > triphenodioxazine > pentacene in the sandwich-type cell; (2) Δε depended on the 1E1 of the absorption spectrum; (3) in the presence of oxygen, the dark- and photo-current of fluoridine increased, while those of triphenodioxazine decreased; (4) the photo-current of fluoridine was less than that of triphenodioxazine, and (5) the generation of the charge carrier in both fluoridine and triphenodioxazine was bimolecular in the absence of oxygen.
The Kinetics of the Reaction of Formaldehyde with Ammonia
Authors: Ogata Yoshiro , Kawasaki Atsushi
Published: July 2006

The kinetics of the reaction of formaldehyde with ammonia to form hexamethylenetetramine has been investigated in dilute aqueous solutions at 20°C in the pH range between 6.3 and 11.9. The reaction was first-order with respect to ammonia and second-order with respect to formaldehyde. The rate increased sharply with the increasing pH to a maximum between 9 and 10, and then it decreased gradually. These results may be explained by a mechanism involving a rate-determining attack of methylolamine on free formaldehyde to form dimethylolamine, followed by the formation of hexamine through cyclotrimethylenetriamine and 1,5-endomethylene-1,3,5,7-tetrazacycloöctane.
On the Electrolytic Rectification Effect in Ion-exchange Membranes
Authors: Sen\={o} Manabu , Yamabe Takeo
Published: July 2006

The electrolytic rectification effect has been observed in a double-membrane system. The static and dynamic current-voltage characteristics have been measured, and it has been demonstrated that the mechanism of the rectification similar to that of the p-n semiconductor junction holds true for this system. Reasonable values have been estimated for the characteristic parameters, although there are many discrepancies requiring further examination.
Studies of the Organic Reactions of Metal Carbonyl. II. The Reaction of Olefin Oxide with Cobalt Hydrocarbonyl
Authors: Takegami Yoshinobu , Yokokawa Chikao , Watanabe Yoshihisa , Masada Hiromitsu
Published: July 2006

The reactions of olefin oxides with cobalt hydrocarbonyl have been studied.

The effect of the reaction conditions on the nature of the reaction, especially that of propylene oxide, has been examined in detail. Propylene oxide gave only the products with β-hydroxy-n-butyryl structure under these reaction conditions: temperature, 25∼45°C; atmosphere; nitrogen or carbon monoxide; and mole ratio of propylene oxide, 1.4∼6.2. The inhibitory effect of a nitrogen atmosphere on the formation of carbonylated products (ester and aldehyde) has been observed ; under nitrogen, some side reaction was highly promoted, and the formation of carbonylated products was thereby prevented.

The reactions of ethylene oxide, cyclohexene oxide, styrene oxide and epichlorohydrin have also been studied. In the reactions of styrene oxide, the mole ratio of styrene oxide had a significant effect on the nature of the reaction; at a relatively small mole ratio, the reduction gave, mainly two isomeric alcohols, but as the mole ratio increased, the carboxylation reaction seemed to increase. Epichlorohydrin gave a product with a γ-chloro-β-hydroxy-n-butyryl structure, which corresponds to that which propylene oxide gave.

The order of the reactivity of these olefin oxides is as follows: cyclohexene oxide (about 5) and styrene oxide>propylene oxide (1)>ethylene oxide>>epichlorohydrin (1⁄20∼40) ; (the numbers indicate the relative reactivities).

This fact seems to indicate that, in general, internal (and conjugated) olefin oxides are more reactive than terminal olefin oxides. By analogy with the relative reactivity of propylene oxide and epichlorohydrin with cobalt hydrocarbonyl, perchloric acid and ammonia, it may reasonably be considered that cobalt hydrocarbonyl reacts as an acid.

Pentene-1 appeared to be less reactive than propylene oxide.
Studies of the Organic Reactions of Metal Carbonyl. III. The Hydroformylation of Olefin Oxides
Authors: Yokokawa Chikao , Watanabe Yoshihisa , Takegami Yoshinobu
Published: July 2006

The hydroformylation reactions of ethylene oxide and propylene oxide have been carried out; the character of this type of reaction may be summarized as follows:

1) Propylene oxide reacts with water gas, in the presence of dicobalt octacarbonyl serving as a catalyst, to give β-hydroxy-n-butyraldehyde as the major product, but it is important to keep the reaction temperature between 80 to 100°C in order to hold the high selectivity of this reaction.

2) At temperatures below 80°C, the reaction does not take place; on the other hand, at temperatures above 100°C, the isomerization of propylene oxide to acetone predominates, and the other side-reactions, such as the dehydration of the hydroformylation products, hydrogenation, condensation and polymerization, take place simultaneously.

3) Ethylene oxide seems to undergo hydroformylation under the same conditions as those used for the propylene oxide, but only a small amount of acrolein is obtained as the hydroformylation product. The expected product, i.e., β-hydroxypropionaldehyde, is formed, but this compound is easily converted into acrolein and the latter seems to polymerize to give a large amount of a resinous or oily material.
An Automatic Recording Analyzer for the Determination of Dissolved Oxygen in Boiler Feed Water
Authors: Tanno Kazuo
Published: July 2006

An automatic recording analyzer for the determination of dissolved oxygen (in concentrations up to 50 p.p.b.) in boiler feed water by Winkler’s method has been described. The instrument is so designed as to perform automatically most of the operations involved in manual analysis, such as sampling, the addition of reagents, titration, recording, and cleansing. The series of required operations (all of the operations in both sample and blank analyses) is completed in 30min. and is automatically repeated. A more important feature of the instrument is that hydrazin-treated feed water, as well as feed water not treated with hydrazin, can be analyzed with accuracy. The oxygen content, however, cannot be read directly on the recorder chart and must be calculated from the recorded quantities of the titrant used. The precision of oxygen determination is within 2 p.p.b. The reproducibility is better than that of manual analysis.
Heat Capacity and Thermodynamic Functions of K2CuCl4·2H2O and (NH4)2CuCl4·2H2O from 13 to 310°K
Authors: Suga Hiroshi , Sorai Michio , Yamanaka Tadashi , Seki Syûzô
Published: July 2006

The heat capacity of copper potassium chloride dihydrate and copper ammonium chloride dihydrate crystals have been measured between 13 and 310°K. The latter crystal shows a λ-type anomaly in the heat capacity curve which seemed to be due to the orientational order-disorder process of ammonium groups. The heat capacity of (NH4)2CuCl4·2H2O exhibits a maximum value of 76.290 cal. deg.−1 mol−1 at 200.50°K. By plotting the temperature derivative of heat capacities, the normal contribution from the lattice to the heat capacity of (NH4)2CuCl4·2H2O has been estimated. In this case the corresponding values for K2CuCl4·2H2O has been taken as a reference. By subtracting the estimated normal heat capacity from the experimentally measured one, approximate values of the entropy change, ΔS=1.945 cal.deg.−1 mol−1, and the heat capacity jump, ΔCp=13.24 cal. deg−1 mol−1, associated with the orientational ordering of the linearly-arranged ammonium ion system have been given.

The values of the heat capacity, entropy, enthalpy, and Gibbs free energy of both crystals have been tabulated at selected temperatures. The standard values of the entropy and enthalpy are: K2CuCl4·2H2O, S0=84.95 cal. deg−1 mol−1, H0–HO0=11980 cal. mol−1; (NH4)2·CuCl4·2H2O, S0=92.30 cal.deg.−1mol−1, H0–HO0=14220 cal. mol-−1.
An Attempt to Determine Eosine’s S*→T Transition Probability and Evidence for the Participation of a D–D Redox Mechanism
Authors: Ohno Takeshi , Usui Yoshiharu , Koizumi Masao
Published: July 2006

Using ATU and EDTA as a reducing agent, an attempt was made to determine the transition probability of the singlet excited state to the triplet state. The values obtained are 0.032 for ATU and 0.080 for EDTA. The cause of this difference is not known at present.

Deactivation of the triplet state by a leuco dye as well as by the ground state dye was confirmed. In the case of ATU, it was established that a D-D mechanism operates when the concentration of ATU islow and the con centration of dye is high. This conclusion was supported by the fact that at a constant low concentration of ATU the 1/φ—[D]o plot deviates from linearity, when the dye concentration becomes high.
The Pectic Acid from the Pulp of Jackfruit (Artocarpus Integrifolia). II
Authors: Gupta U K Sen , Das A
Published: July 2006

The jackfruit pectic acid has been converted into ethylene glycol ester, which, on reduction with sodium borohydride, gives a galactan. Methylation studies of the original polysaccharide and of the reduced pectic acid suggest the presence of chains of 1→4 linked α-d-galacturonic acid residues in the pectic acid which is associated with a glucan.
Structure of the Polysaccharides from Unripe Mango (Mangifera Indica LINN). III
Authors: Das A , Gupta U K Sen
Published: July 2006

The polysaccharide isolated from the mesocarp of unripe mango has been found to be a mixture of three component polysaccharides, viz., a glucan, and araban and a galacturonan. By a methylation study, the glucan has been found to have the same structural pattern as that of the glucan isolated from ripe mango. The araban portion yielded 2,3,5-, 2,3- and 2-O-methyl-l-arabinose. On the basis of these results, a probable structure has been assigned to the araban. The isolation of only 2,3-di-O-methyl-d-galacturonic acid shows that the galacturonan portion is 1→4 linked.
On the Sn–H Bond in Some Organotin Hydrides
Authors: Kawasaki Yoshikane , Kawakami Katsuhiko , Tanaka Toshio
Published: July 2006

The nuclear magnetic resonance spectra of the proton attached directly to the tin atom in several organotin hydrides (RnSnH4−n ; n= 1, 2, 3) have been measured. The observed shielding values increase in the order of i-C3H7<n-C4H9\simeqn-C3H7\simeqC2H5<CH3 in tri-alkyltin hydrides. This order is consistent with that of the hyperconjugation effect of the alkyl group. On the other hand, the change in the shielding of the protons bound directly to the tin atom with a step-by-step substitution of SnH4 by an alkyl group is similar to that of hydrocarbons or alkylsilanes. The infrared spectra of organotin hydrides show that there is a close correlation between the τ values and the Sn-H stretching frequencies.
Vibrational Assignments and Intramolecular Force Field of Trimethylaluminum
Authors: Ogawa Teiichiro , Hirota Kozo , Miyazawa Tatsuo
Published: July 2006

A vacuum infrared cell for reactive or intermediate species has been devised by the use of polyethylene sheets as optical windows. The infrared spectra in the 4000–3100cm−1, 2500–1500 cm−1, 1250–750 cm−1 and 700–65 cm−1 regions can be measured with this liquid cell.

The vibrational assignments of the observed spectra have been carried out. The band at 367 cm−1 has been assigned to ν17, and the band at 175 cm−1, to ν18 and ν14.

The normal vibrations have been calculated, and the potential function of this molecule has been studied. A bond has been concluded to lie between two aluminum atoms. The characteristics of the potential function and the bond structure of trimethylaluminum have also been discussed.
Studies of the Liquid-Liquid Partition Systems. I. The Distribution of Radon(0) between Various Organic Solvents and Aqueous Solutions
Authors: Sekine Tatsuya , Yamasaki Akira
Published: July 2006

(1) The distribution of radon between various organic solvents and water has been determined at 25°C. Radon is always distributed better into the organic phase. The distribution constants of radon in these liquid-liquid partition systems are in the range from 25 to 80.

(2) The distribution of radon between aqueous calcium chloride solution of various concentrations and carbon tetrachloride has been determined at 25°C. A remarkable salting-out effect for radon has been observed.

(3) A solvent extraction method for the separation of radon from radium(II) and the decay products in aqueous solutions has been suggested.
Thermodynamic Properties and Order-Disorder Phase Transitions of the Potassium Cyanide Crystal
Authors: Suga Hiroshi , Matsuo Takasuke , Seki Syûzô
Published: July 2006

The heat capacities of the potassium cyanide crystal have been measured over the temperature range from 13 to 310°K by using a low temperature adiabatic calorimeter. It has been found that there are two regions of anomalous heat capacity, with maxima at 82.9±0.2°K and 168.3±0.1°K respectively. The heats and entropies of transition have been evaluated by utilizing a ΘD-versus-temperature plot. The entropy of the lower transition amounts to about R ln 2, which means that the transition is due to the orientational order-disorder rearrangement of the cyanide ion with respect to its head and tail. A perfectly-ordered structure for the orientation of the cyanide ions has been suggested. A certain small anomaly in heat capacity has been found around 190°K, one which seems to be associated with some change in higher-order structural defects created by the upper transition phenomenon.

The torsion-rotational heat capacity of the cyanide ions has been separated from the total on some reasonable assumptions. The results show that the cyanide ions below the lower transition point are subjected to torsional oscillation with the wave number of about 160 cm−1, a value which corresponds to the barrier height of 7.5 kcal. mol−1 based on a simple harmonic oscillator model. On the other hand, they are in a hindered rotational state with a barrier height of approximately 1.35 kcal. mol−1 in the cubic phase, the barrier height diminishing from 7.5 kcal. mol−1 gradually in a single phase or abruptly via the transition points.

The thermodynamic functions for this crystal have been evaluated by integrating the heat capacity data. The values at 298.15°K are, in units of cal.mol−1deg−1: Cp°=15.84, S°=30.71, (H°–H°O)⁄T=13.94 and –(G°–H°O)⁄T=16.77 respectively.
Oxidation of Alcohols with t-Butyl Chromate. II. The Oxidation of Primary Aromatic Alcohols
Authors: Suga Takayuki , Kihara Keiichi , Matsuura Tamon
Published: July 2006

The oxidation with t-butyl chromate has been carried out with benzyl alcohol, its p-substituted derivatives and trans-cinnamyl alcohol, and also with β-phenylethyl alcohol. In the former alcohols, the corresponding aldehyde was obtained as the main product, but the corresponding ester was not formed. On the other hand, the latter alcohol, containing a methylene group adjacent to the hydroxymethyl group, produced the corresponding ester, aldehyde and acid, as in the case of a saturated primary aliphatic alcohol.
The Synthesis of dl-Muscarine and dl-Allomuscarine
Authors: Maekawa Haruki , Ichihara Akitami , Matsumoto Takeshi
Published: July 2006

The synthesis of dl-muscarine (I) and dl-allomuscarine (II) starting from ethyl crotylmalonate has been described. Trans oriented methyl and hydroxyl groups in these compounds have been introduced stereospecifically into the tetrahydrofurane ring.
The Synthesis of cis- and trans-Demethylmuscarines
Authors: Ichihara Akitami , Yamanaka Tsutomu , Matsumoto Takeshi
Published: July 2006

Two stereoisomeric dl-demethylmuscarines have been prepared by the procedure described for the synthesis of dl-muscarine, starting from ethyl allylmalonate.
The Determination of the Water Content in Acetaldehyde by Means of the Karl Fischer Reagent
Authors: Muroi Kaname , Ogawa Kunihiko , Ishii Yaeko
Published: July 2006

Approximately 5 ml. of the sample has been added to 5 ml. of a 3:1 solvent mixture of of pyridine-propylene glycol in a titration flask. The difference in boiling point between acetaldehyde and water made it possible to evaporate almost all the interfering acetaldehyde from the solution with nitrogen gas passed into the flask at a velocity of about 0.91./min. The water remaining in the solution was titrated with the Karl Fischer reagent SS (Mitsubishi).

Because this reagent is free from alcohol, which would show an interfering reaction in Eq. 1, and because it is somewhat lower than the general Karl Fischer reagent in its concentration of C5H5N·SO2, which is the main component responsible for the interfering reaction in Eq. 3, it proves to be the most satisfactory for the present titration method.

A small quantity of water in purified acetaldehyde was determined by the present method, and subsequent anlysis of water content values showed an excellent reproducibility.
A Theoretical Treatment of the Kinetics of the Oxidation of Metals
Authors: Yoshisaki Hiroshi , Isano Toyojiro
Published: July 2006

We have attributed the deficiency of the parabolic law to its original assumption of a uniform gradient of the concentration of the reactant, and, beginning with a general assumption of a turbulent gradient, we have deduced an alternative equation, one somewhat more complicated than the parabolic one. In discussing the behavior of the new equation, it was found that the mode of progression largely changes its profile as a result of the fluctuation of the coarseness of the surface to be oxidized.
A Study of Monolayer Penetration by the Radiotracer Method
Authors: Matsubara Akira
Published: July 2006

The surface pressure - area isotherms of monolayers of cholesterol, hexadecyl alcohol and octadecyl amine on sodium alkyl sulfate solutions and the surface excess of alkyl sulfate have been measured by the film balance and the radiotracer methods respectively. These measurements were carried out with (1) the monolayers spread on the alkyl sulfate solutions, (2) those below which the detergent solutions were injected, and (3) those formed by the spreading of the insoluble speciesdetergent mixtures on water.

All the surface pressure - area curves showed remarkable expansions; the results were essentially the same as those observed by Schulman et al. and by others.

On the other hand, the surface excess of alkyl sulfates showed no appreciable increase in the case of cholesterol and hexadecyl alcohol, and it was too low to form a stoichiometric complex between the insoluble species and the alkyl sulfate; only in the presence of the octadecyl amine did it increase to an amount sufficient to form the 1 : 1 stoichiometric salt.

Thus it has been concluded that the expansion of the surface pressure - area curve can not be an indication of the stoichiometric complex formation. It has been pointed out that the surface pressure of the detergent solution increases with the compression, even in the absence of a monolayer; this is the main cause for the expansion of the surface pressure - area curve of the penetrated monolayer. The phenomenon of monolayer penetration has been explained in terms of the formation of the adsorbed layer of alkyl sulfate, and the reactivity for penetration has been related to the surface activity of detergents.
Complex Compounds of Gallium with Mandelic Acid
Authors: Srivastava T N , Rupainwar D C
Published: July 2006

pH and conductometric studies of the gallium chloride - mandelic acid - water system show the existence of three chelates in solution with a metal-to-ligand ratio of 1:1, 1:2 and 1:3. The solubility of freshly-precipitated gallium hydroxide in aqueous solutions of mandelic acid of varying concentrations, however, indicates the presence of only, 1:2- and 1:3-type species. These two complexes have here been isolated in the crystalline state. Their structures may be represented by

(Remark: Graphics omitted.)

and

(Remark: Graphics omitted.)

respectively. The 1:1 complex indicated by electrometric titrations appears to be fairly unstable, as it could neither be inferred from solubility experiments nor isolated in the crystalline state.