bluuebunny/crossref_metadata_2025 huggingface dataset:
Studies on Crystal Hydrates. IV. Dehydration and Rehydration, Stable and Metastable Equilibria and Transition between Hydrate Modifications of Potassium Mercury(II) Chloride Monohydrate, K2HgCl4·H2O
Authors: Chihara Hideaki , Seki Syûzô
Published: July 2006

The dehydration pressures of the crystalline K2HgCl4·H2O are measured and given by logP=8.538–(2161⁄T) with P expressed in mmHg. No thermal hysteresis effect was observed. Production and some experiments for partly amorphous hydrate are briefly discussed. A consideration of the entropy of dehydration led to the conclusion that the dehydration is zeolitic. The differential thermal analysis revealed that there is a non-dehydrating transition at 114°C and that the dehydration occurs at 123°C. Infrared spectra of the solids showed that the 6-micron band of water persisted between 114 and 123°C. The X-ray study of the transition at the supercooled condition showed that this is a transition quite different in nature from those of ordinary nucleation-and-growth mechanism. The rehydration of dehydrated crystals was followed by the X-ray diffraction method and found to be relatively rapid at room temperature.
Studies on the Silk-Palladium Catalyst. III. Physicochemical Characterization
Authors: Izumi Yoshiharu
Published: July 2006

1. From the infrared absorption measurements of silk fibroin, silk fibroin-PdCl2 complex, and silk-palladium catalyst, it was concluded that the NH, OH, COOH and CONH groups of the fibroin participate in the chelate formation with palladous chloride. On reduction of the chelate with hydrogen, the chelate bonds are broken and the fibroin restores its original form.

2. X-ray diffraction pictures of the above-mentioned samples and of the corresponding preparations of the 6-Nylon series suggest that a part of the palladium atoms in the silk-palladium catalyst is assembled in fine crystaline particles and the other part of the palladium probably becomes regularly arranged in the micelle structures of the fibers. However, the possibility that certain regular structures have emerged in the carrier protein itself can not be excluded.

3. Part of the palladium in silk fibroin-PdCl2 complex can be readily released with p-nitrosodimethylaniline, while the rest appears to be strongly kept in the fiber structure.
The n–π* Transition Band of Acenaphthenequinone
Authors: Kuboyama Akira
Published: July 2006

The weak absorption band (α-band) (εmax∼20) near 500 mμ of acenaphthenequinone was measured in various solvents. This band was determined as the n−π* transition band on the basis of the observed results on intensity and solvent effect. In dioxane, the n−π* transition bands of the o-quinones, including the α-band, largely shift towards shorter wavelengths. This fact, which is thought to be due to molecular complex formation, was discussed from the qualitative point of view. The relative height of the two main peaks of the α-band markedly depends upon solvents. The similar, though less marked, fact is seen in β-naphthoquinone. The two main peaks of the α-band were assumed to be due to the two n–π* transitions, whose transition energy difference is ca. 700 cm−1. It was found that the n–π* transition bands of the quinones, especially of p-benzoquinone, are markedly intensified in carbon disulfide. This fact is probably attributed to the large refractive index of this solvent.
Infrared Spectra of Diacetyl Monoxime and Isonitrosoacetone
Authors: Kimura Masao , Kuroda Yoko , Takagi Hitoshi , Kubo Masaji
Published: July 2006

The infrared absorption spectra of diacetyl monoxime and isonitrosoacetone in solutions were recorded in the rock-salt region. The assignment of observed bands was carried out, taking into account the concentration dependence of the spectra, the effect of deuteration, and the absorptions in the solid state. All the observed frequencies could be interpreted in terms of the molecular form of an oxime type, the presence of molecules in a nitroso form being presumed to be unlikely.
On the Thermal Dissociation of Organic Compounds. XIV. The Effects of the Solvents and of the Substituents on the Thermal Dissociation of Urethans in Amines
Authors: Mukaiyama Teruaki , Akiba Toyohiko , Asahi Tamio
Published: July 2006

N-phenyl-phenyl carbamates dissociate into their component compounds very readily in the presence of a base. Unlike the case of N-phenyl-alkyl carbamates, N-phenyl-phenyl carbamates dissociate in the presence of an equimolar amount of an amine at lower temperature. The kinetics of the dissociation of N-phenyl-phenyl carbamates were of the first order with respect to carbamates and of the first order with respect to base.

The rate constants, the activation energies and the entropies of activation of the dissociation of N-phenyl-phenyl carbamates in various amines and solvents were measured throughout temperature interval 0∼140°C.

The effects of amines, solvents and substituents on the dissociation of urethans in amines were studied.
Oxidation of Terpene Compounds with tert-Butyl Chromate. VI. Oxidation of Terpinolene
Authors: Matsuura Tamon , Saito Kozo , Shimakawa Yasuo
Published: July 2006

Oxidation of terpinolene with tert-butyl chromate was carried out, and piperitenone, 8-hydroxy-p-cymene, p-cymene and α,p-dimethyl-styrene were obtained as reaction products. In this oxidation it was found that the active methylene group at C(3) position in terpinolene was oxidized to a carbonyl group, and that the aromatization of carbon ring in terpinolene molecule took place. This could not be recognized in the oxidation of terpene compounds already reported by this oxidant.
Thermal Decarboxylation of p-Chlorobenzoic Acid
Authors: Muhammad S S
Published: July 2006

The decarboxylation of p-chlorobenzoic acid has been studied in the solvent resorcinol. The activation energy, frequency factor and free energy and entropy of activation have been calculated. It is shown that the reaction follows the SE2 mechanism.
Stereoregular Polymers. VI. Copolymerization with the Ziegler Catalysts
Authors: Murahashi Shunsuke , Nozakura Shun’ichi , Sumi Masao
Published: July 2006

Binary copolymerization of styrene, allyltri-methylsilane and 3-butenyltrimethylsilane was investigated using the Ziegler catalyst at 70°C. It was found to be possible to separate the crystalline part of copolymers by fractional extraction into two kinds of genuine crystalline copolymers, each of which has an extremely different composition from the other.

The nature of the active sites on the catalytic surface was discussed in order to elucidate the above fact.

The constitution of the individual crystalline fractions appeared to vary case by case, i.e., the structure of blockcopolymer might be assigned to some cases and random copolymers to some other cases.
Amylose-Iodine Complex. II. Effects of Inorganic Salts
Authors: Kuge Takashi , Ono Sôzaburo
Published: July 2006

The relations between the light absorptions of the amylose-iodine complex and the concentrations of various added salts have been investigated. The iodide ion appears to be indispensable for the formation of the blue complex. The complex formation can be greatly aided by certain salts when the concentration of iodide is low. This salt effect suggests that the parallel-oriented aggregation of amyloseiodine helical complex is essential for the formation of the stable blue complex.
The Structure of Aureothin. XI. On the Structure of Some of the Isoaureothin Derivatives
Authors: Yamada Kiyoyuki , Naito Takayuki , Okuhara Kunio , Nakata Hisao , Hirata Yoshimasa
Published: July 2006

During the course of the investigation of isoaureothin (I), several derivatives were obtained, the structure of which still remains unknown. The structure of these derivatives is presented in this paper on a basis of spectral and chemical evidence. The reduction of isoaureothamine (IIa) with lithium borohydride yielded an unexpected acidic substance, aminol H (IIIa) the formation of which, taken in conjunction with that of N-acetyl aminol A (IVa), provides an unusual type of reduction by complex metal hydride. Treatment of N-acetyl iso-aureothamine (IIb) with alkali yielded an optically inactive substance, Lactol, which was formulated as VIII. The action of acetic anhydride on Lactol resulted in the formation of racemate of N-acetyl isoaureothamine (IIb).
Studies on Organic Peroxides. VI. Thermal Analysis of the Decomposition of Benzoyl Peroxide by Ferrous Ion
Authors: Hasegawa Shigeo , Nishimura Norio , Miura Kimpei
Published: July 2006

The thermal analysis method was applied to follow the rate of the decomposition of benzoyl peroxide catalysed by ferrous ion in methanol, ethanol, n-propanol and n-butanol.

The apparent rates were of the first order and no fundamental difference in the reaction mechanism was observed among these alcohols. However, the reaction rates in methanol were much slower than in three other alcohols. Solvent effects on the reaction rate were discussed.

Linear enthalpy-entropy relationship was deduced, assuming that the free energy of activation is the linear function of an intensity factor in a series of reactions. This was found to be true in our case.
The Thermal Decomposition of Acetaldehyde in the Presence of Methanethiol
Authors: Imai Naomi , Toyama Osamu
Published: July 2006

Acetaldehyde has been decomposed thermally in the presence of methanethiol over the temperature range from 400° to 440°C. The presence of methanethiol markedly enhances the rate of decomposition. Analysis of the initial rates of decomposition obtained under various experimental conditions suggests: a) one of the chain-carrying steps CH3+CH3CHO=CH4+CH3CO (5) in the decomposition of acetaldehyde alone is replaced by CH3+CH3SH=CH4+CH3S (10) and CH3S+CH3CHO=CH3SH+CH3CO (11) in the presence of methanethiol; b) the reaction CH3SH=CH3+SH (7), in addition to CH3CHO=CH3+CHO (1), contributes to the chain initiation; c) the chain terminates by the combination of methylthio radicals in contrast to the decomposition in the presence of hydrogen sulfide where the chain-ending step is the combination of methyl radicals under similar experimental conditions; d) k5⁄k11=0.8exp(−2,800⁄RT) and k1⁄k7=130exp(−11,000⁄RT), the latter expression being less certain.
Thermodynamic Studies on Cobalt Complexes. VII. Solubility of Erdmann’s Salt and Related Complexes
Authors: Mori Motoshichi , Tsuchiya Ryokichi , Kyuno Eishin , Nishide Takashi
Published: July 2006

The solubilities of Erdmann’s salt, NH4[Co(NH3)2(NO2)4], and the following complexes which have the same complex anion, K[Co(NH3)2(NO2)4], cis- and trans-[Co(NH3)4(NO2)2] [Co(NH3)2 (NO2)4], [Co(NH3)5NO2] [Co(NH3)2(NO2)4]2, [Co(NH3)5Cl] [Co(NH3)2(NO2)4]2] and [Co (NH3)6] [Co(NH3) 2(NO2)4]3were measured. Based upon the thermodynamic functions calculated from the above measurement, the free energy of solution, the lattice energy and the free energy of formation of these complexes were calculated and discussed.
Density Measurement in Dilute Aqueous Solution of Polyvinyl Alcohol
Authors: Nakanishi Koichiro , Kurata Michio
Published: July 2006

The solution density of polyvinyl alcohol dilute aqueous solution is measured by the use of the method of floating equilibria. This method is proved to be useful for the purpose of precise density and concentration determination of PVA dilute solution. An experimental formula for the density of PVA aqueous solution both as a function of the concentration and polymerization degree of PVA is proposed. The excluded volumes between solute and solvent are estimated from the molecular weight dependence of apparent and partial specific volumes obtained.
Crystal Habit Modification of Strontium Sulfate. I. Habit-Modifying Action of Foreign Substances
Authors: Otani Sadaichi
Published: July 2006

The effect of various impurities on the crystal habit of strontium sulfate were investigated. Solutions containing citrate ion produced a nearly disk-shaped single crystal whose nearly flat surface was parallel to the (001) plane. Nearly two-dimensional spherulite is obtainable from a solution containing EDTA. A minute amount of sodium triphosphate or sodium hexametaphosphate caused the deposition of a relatively large spherulite having a spherical form, which is composed of numerous needle- or wedge-shaped crystallites elongated in the direction of c axis. The habit-modifying action of impurities is discussed in detail.
Flow Properties of Aluminum Soaps-Hydrocarbon Systems
Authors: Shiba Sukekuni
Published: July 2006

Flow properties of aluminum soap-hydrocarbon systems as viscous liquids or plastic bodies are studied with a concentric rotational viscometer. Results are obtained under the rate of shear up to 103 sec−1.

(1) The systems behave as dispersions of soap crystallites with network structures combined by secondary interactions of the particles, and they exhibit marked viscosity increase.

(2) The rheological structures suffer shear breakdown under shear, resulting in decrease in viscosity.

(3) Recovery from the broken structures is impossible, that is, this change is not thixotropic but shear breakdown.

(4) Flow properties change with time while standing at rest.

(5) The effects of concentration, temperature and fatty acids constituting soaps are clarified.
The Adsorption of Dye Mixtures by Cellophane Sheet. I. Temperature and Concentration Dependence of Adsorption from Some Binary Mixtures
Authors: Horiki Yukio , Tanizaki Yoshié , Ando Noboru
Published: July 2006

1) The amount of dyes adsorbed by Cellophane from two mixture dyeings of Chlorazol Sky Blue FF and Chrysophenine G, and Chlorazol Sky Blue FF and p-nitroaniline →γ acid (α-coupling) was measured. Further, the amount in case of single dyeing was also measured.

2) It was assumed that the reduction in adsorption of dyes from mixture dyeing is due to an interaction between the two dyes in the dyebath, and that this interaction means only the formation of complexes. On this assumption, the instability constant in the case of the pair of Blue dye and Yellow dye was calculated, according to the mass action law, but it was impossible to calculate it in the case of the pair of Acid dye and Blue dye, because the composition of complexes of this pair was not constant.

3) How the amount of Blue dye adsorbed from mixture dyeing varies with the sort and the concentration of its partner dye and with the dyeing temperature was discussed from the standpoint of the instability constant and the affinity.
The Anodic Behavior of Cathodically Prepolarized Bright Platinum Electrode in Sulfuric Acid Solution
Authors: Shibata Shigeo
Published: July 2006

The anodic charging curves of a cathodically prepolarized bright platinum electrode in 1 n sulfuric acid solution saturated with hydrogen have been studied by means of a mechanical oscillograph.

The behavior of stage α′ for anodic polarizing c. d. can be explained on the assumption that its stage is due to the molecular hydrogen accumulated in the vicinity of the electrode during the cathodic prepolarization, and that the concentration of the accumulated hydrogen decreases in the same manner as the chemical reaction of first order.
Absorption Spectra of Nitrobenzene Derivatives. I. Spectral Features of o-, m- and p-Isomers
Authors: Semba Kimio
Published: July 2006

The intramolecular charge transfer spectra of some nitrobenzene derivatives were measured in n-hexane. The general features of the absorption spectra and the effect of substituents on the absorption spectra were considered from the concept of the intramolecular charge transfer. The migration effect of electron donating groups was discussed for the nitroaniline in aqueous and hydrochloric acidic solutions. Also other absorption due to the n→π* transition of nitro group was considered.
Synthesis of Several Ketones from Acetaldehyde and Propylene by Gamma-ray Irradiation
Authors: Hirota Kozo , Hatada Motoyoshi
Published: July 2006

It has been found that methylpropylketone and other higher ketones are synthetized with relatively high G values by gamma-ray irradiation on mixtures of acetadehyde and propylene at room temperature, and that the reaction proceeds by a chain mechanism, with acetyl radical produced thereby as the initiator.
A Kinetic Study of Addition Reaction of Vinyl Ether with Carboxylic Acids
Authors: Mukaiyama Teruaki , Nohira Hiroyuki
Published: July 2006

The rate constants, the activation energies and the entropies of activation of the addition reactions of n-butyl vinyl ether with carboxylic acids in dioxane, anisole and toluene were determined. It was found that the reaction is first order with respect to vinyl ether and second order with respect to carboxylic acid, and the rate of the reaction increases as the acidity of carboxylic acid increases and a linear Ham-mett relation is observed in the reaction of meta and para substituted benzoic acids. In the presence of a catalytic amount of phosphoric acid, the rate increases linearly with its concentration. The addition involves two stages, namely the initial formation of intermediate complex from vinyl ether and carboxylic acid, followed by the reaction of the complex with another carboxylic acid. In addition, the solvent effect has been clarified and a general acid catalyzed reaction has been discussed in view of these results.
Spectrophotometric Determination of Nitrous Acid with Disodium 1-(4′-Aminobenzeneazo)-amino-8-hydroxynaphthalene-2′, 6-disulfonate
Authors: Katsube Yukiteru , Yoe John H
Published: July 2006

A procedure has been developed for the spectrophotometric determination of trace amounts of nitrous acid with disodium 1-(4′-aminobenzeneazo)-2-amino-8-hydroxynaphthalene-2′, 6-disulfonate. The method is accurate and precise and has a sensitivity of 0.004 γ of nitrous acid per sq. cm. Beer’s law is obeyed up to about 2 p. p. m. of nitrous acid. A study of the effect of many ions on the color reaction has been made. The interference of ferric ion is eliminated by the use of EDTA.
Radiation-induced Polymerization of α-Methylstyrene
Authors: Hirota Kozo , Makino Kenji , Kuwata Keiji , Meshitsuka Gisuke
Published: July 2006

It has been shown that (a) α-methylstyrene polymerizes at room temperatures by gamma-ray irradiation; that (b) the reaction proceeds by a radical mechanism, considering from the effect of solvents, additives and ultraviolet light; that (c) ceiling temperature for this monomer is exceptionally low (ca. 70°C) among vinyl monomers, so that it is hard to obtain high polymers by the usual method; that (d) the experimental fact that the velocity of polymerization is proportional to dose rate and not to square root of dose rate can be explained by the assumption that degradative chain transfer occurs more frequently than the termination between active polymers.
Heats of Formation of Lower Members of Dimethyl- and Methylisopropoxy-cyclopolysiloxanes
Authors: Tanaka Toshio
Published: July 2006

Heats of combustion of lower members of dimethyl- and methylisopropoxy-cyclopolysiloxanes have been measured at 20°C and a constant volume, and the corresponding heats of combustion and formation in isobaric process have been calculated. From the results, the heats of formation of structural units, (Remark: Graphics omitted.) and (Remark: Graphics omitted.), of these compounds from mono-atomic gases have been derived, and it has been found that the ring structures of the cyclic-tetramer and pentamer would be free from strain. Further, the effect of distortion of Si–O–Si valency angle in the cyclic trimer on the heat of formation has been discussed.
Studies on Organic Reagents for Inorganic Analysis. VI. Absorption Spectrum of Phenylfluorone-Metal Chelate and the Nature of the Chelating Bond
Authors: Sano Hirotoshi
Published: July 2006

The absorption spectra of phenylfluoronefourth group metal chelates were investigated by the acid of Kuhn’s free electron gas model method. If the chelating bond formation does not cause an essential change in the π-electron system of the dye molecule, in the more ionic chelating bond, the absorption maximum of the chelate must be closer to the maximum wavelength of the dye anion. Based on the conception in valence-bond method and ionic-covalent resonance, it was theoretically and experimentaly shown that there was a certain relationship between the absorption maximum wavelength of the chelate and the ionicity of the chelating bond. (The ionicity of the bond was estimated from the difference of electronegativity between the metal and the terminal oxygen atom). The results obtained here for the relationship between the ionicity and the electronegativity difference show too close an agreement with the results obtained from the nuclear quadrupole coupling data by Dailey and Townes.
Antioxygenic Activity of Lecithin and its Hydrolysis Products. III. Lecithin, Glycerophosphorylcholine, Phosphorylcholine, Phosphatidic Acids, Choline and Glycerol
Authors: Urakami Chieko , Kameyama Haru
Published: July 2006

Purified ovo-lecithin, Dl-α-glycerophos-phorylcholine, choline and glycerol were found to exhibit no antioxygenic property against carefully purified methyl oleate. Phosphorylcholine, its chloride and natural phosphatidic acids, on the other hand, showed activity.

The order of activity efficiency at 60°C was found to be orthophosphoric acid > phosphatidic acid and phosphorylcholine > phosphorylcholine chloride > α-glycero-phosphoric acid > β - glycerophosphoric acid. The discussion is presented to show that the phosphoryl moiety is predominantly responsible for antioxygenic activity.
Neutron Activation Analysis of Iodine in Silicon
Authors: Nozaki Tadashi , Baba Hideo , Araki Hidemaro
Published: July 2006

A trace quantity of iodine in silicon was determined by the neutron activation analysis. A chemical separation process, which involves potassium hydroxide fusion with potassium iodide as a carrier, was proved satisfactory by the use of 131I produced by the neutron irradiation of tellurium diffused in silicon. By this method, the iodine was converted into silver iodide ready for counting and weighing within an hour, with a yield exceeding 50%. When it is assumed that a counting rate of 100 cpm is enough for accurate detection of activities, the limit of detection is 0.002 μg. of iodine with a neutron flux of 6×1011n/cm2sec. and by the use of a 2π counter.
Synthesis of 1, 2, 5- Trisubstituted Naphthalene Derivatives
Authors: Matsumoto Takeshi , Suzuki Akira
Published: July 2006

A synthesis of 2-methoxy-5-hydroxy-1-naphthylacetic acid has been described.
On The Mechanism of the Extraction of Uranyl Nitrate by TBP (Partition Study)
Authors: Naito Keiji
Published: July 2006

The method of analysis using the distribution coefficient to confirm the mechanism of extraction was proposed and the formation of the complex UO2(NO3)2·(TBP)2 and HNO3·TBP was confirmed. The extraction behavior of uranium from a nitric acid solution was concluded as a result of the competition of uranium and nitric acid. The thermochemical functions ΔH0, ΔF0 and ΔS0 for the complex formation reaction:

UO_2^+2(aq.)+2NO_3-(aq.)+2TBP(org.)=UO_2(NO_3)_2(TBP)_2(org.)

were determined roughly from the measurement of the distribution coefficient as follows: ΔH0(25°C) ≅−4.3 kcal., ΔF0 (25°C) ≅−2.0 kcal., ΔS0(∼25°C) ≅−7.7 e.u.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. V. Stilbene
Authors: Suzuki Hiroshi
Published: July 2006

(1) The quantitative relations between the degree of deviation from the coplanarity of the molecular configuration and the ultraviolet absorption spectrum as well as the quantities such as the extra-resonance energy and the π-bond orders have been determined for the stilbene-type compounds by calculations based on the simple LCAO molecular orbital method.

(2) The ultraviolet absorption spectra of trans-stilbene in the crystalline state, in the solution state, and in the vapor state have been discussed in reference to the spatial configurations of the molecule in the various states. The conjugation band in the vapor spectrum is at considerably shorter wavelengths than that in the solution spectra as well as the crystal spectra, a fact which has been considered as probably indicating that the most likely configuration of the molecule in the vapor state deviates considerably from coplanarity. The magnitude of the red-shift of the conjugation band in the crystal spectra measured by the pressed KCl-disk technique relative to the band in the spectrum of the n-heptane solution has been found to be smaller than the value anticipated for the rigid molecule. From this fact it has been inferred that the most probable configuration of trans-stilbene in solution does not significantly differ from the one in the crystalline state and is planar or nearly planar.

(3) On the basis of the above inference, the calculations have been applied to cis and trans-stilbenes, and the interplanar angles in the most probable configuration of cis-stilbene have been estimated at about 28° from the position of the conjugation band, in fairly good agreement with the value estimated from the scale model. The results of the calculations have been discussed.

(4) In addition, the solvent effects of various solvents on the spectra of trans-stilbene and its p-methoxy- and p-nitroderivatives have been discussed with special reference to the effect of benzene which has been found to cause a large bathochromic displacement of the conjugation band and a remarkable redistribution of intensity among the vibrational bands of the conjugation band of each compound.
Relations between Electronic Absorption Spectra and Spatial Configurations of Conjugated Systems. VI. Triphenylethylene, Tetraphenylethylene and Tolan
Authors: Suzuki Hiroshi
Published: July 2006

The most probable configuration of triphenylethylene as well as that of tetraphenylethylene has been inferred to be the one in which all of the phenyl groups are rotated out of the plane of the ethyl-enic bond, on the basis of the analysis of the ultraviolet absorption spectra by application of the method based on the simple LCAO molecular orbital method described in the preceding part of this series. Some physical and chemical properties of these compounds have been discussed with reference to the spatial configurations.

The method has been applied also to tolan (diphenylacetylene), and it has been shown that the calculated wavelengths of the bands agree fairly well with the observed ones.

In addition, it has been shown that the spectrum of tolan in the crystalline state measured by the pressed KCl-disk technique resembles the spectrum of the solution in n-heptane on the whole, and that the red-shift of each band associated with the change of the state from the n-heptane solution to the crystalline state increases with almost complete regularity with the wavelength of the band from about 1.3 mμ at 217.2 mμ to about 4.4 mμ at 297.2 mμ, the shifts observed here being appreciably smaller than the analogous shifts observed by Dale in the spectra of naphthalene and anthracene.
Visible and Ultraviolet Absorption Spectra of 1,3,5-Trinitrobenzene in Water in the Presence of Sodium Hydroxide
Authors: Abe Takehiro
Published: July 2006

(1) Absorption spectra of the colored solutions of 1,3,5-trinitrobenzene and various concentrations of sodium hydroxide in water have been measured at 25°C. The colored solution shows absorption bands at 260, 300 and 440∼500mμ. The absorbances of the visible absorption bands increase below the sodium hydroxide concentration, about 0.6 n, but decrease above the sodium hydroxide concentration, as the concentration of sodium hydroxide increases. On the other hand, the 260 and 300 mμ bands, observed above the sodium hydroxide concentration, about 0.4 n, increase their absorbances with an increase in concentration of sodium hydroxide. These lead to the suggestion that the visible absorption bands are due to [Trinitrobenzene·OH]− and the 260 and 300 mμ bands are due to [Trinitrobenzene·2OH]2−.

(2) Below the sodium hydroxide concentration, about 0.6 n, Benesi and Hildebrand’s equation holds for the colored solutions, giving an equilibrium constant of 2.7 for the reaction between trinitrobenzene and hydroxyl ion in water at 25°C.

(3) On keeping the colored solution to stand for long hours, the 260 and 300 mμ bands and the visible absorption bands decrease their absorbances, while an absorption band appears at about 350 mμ.

(4) When an aqueous solution of hydrochloric acid is added into the colored solution with a high concentration of sodium hydroxide, the absorbances of the visible absorption bands increase. The 260 mμ band and the visible absorption bands disappear by adding a solution of hydrochloric acid, enough to neutralize the sodium hydroxide contained in the solution. By the addition of acids, [Trinitrobenzene·OH]− and [Trinitrobenzene·2OH] 2− seem to change into trinitrobenzne reversibly.
Interaction of Surface Active Agent with Amylose
Authors: Takagi Toshio , Isemura Toshizo
Published: July 2006

It was found that a specific precipitate is formed when some ionic surface active agents are added to amylose solution and it was confirmed by X-ray diffraction study that this phenomenon is due to the formation of the helical complex between amylose and a surface active agent.

It is also inferred that the same complex is formed even in the dissolved state from the study on the effect of the surface active agent on the viscosity of amylose solution and on the absorption spectrum of amylose-iodine complex.
Some Characteristics of Zinc Oxide Phosphor
Authors: Maeda Keiji
Published: July 2006

Zinc oxide phosphors were prepared under various conditions. From measurements on the characteristics of the green luminescence of the phosphors fired in reducing atmosphere, the following features were observed. (1) In the excitation spectrum, there is a sharp peak at the position of the absorption edge and a gradual decrease toward shorter wavelengths with some structures. The observed maximum value of excitation efficiency is 0.31. (2) The luminescence intensity decreases with increasing temperature. The plot of intensity against temperature has an unusual shape in the neighborhood of 0°C. (3) The decay of luminescence is exponential and the time constant, 0.4 μ sec., is smaller than that previously reported by an order of magnitude. Long persistent phosphorescence is observed indicating the presence of deep hole traps. (4) The luminescence intensity decreases in a gaseous ambient of molecules having the hydroxyl group.

Standing on the present experimental results, discussions have been undertaken on the luminescence center as well as on the theoretical explanation of the observed characteristics.
An Electron Diffraction Investigation on the Molecular Structure of Hydrazine
Authors: Morino Yonezo , Iijima Takao , Murata Yoshitada
Published: July 2006

By the sector-microphotometer method of electron diffraction the molecular structure of hydrazine was obtained as shown in Table II. The bond distances are in good agreement with the values obtained by the infrared vibration-rotation spectrum. The mean amplitudes agreed with the calculated values within the limits of errors.
The Bischler-Napieralski Reaction in Liquid Sulfur Dioxide. Formation of N,N′-bis-β-Phenethyl Acet- and Benz-amidines and N,N′-Diphenyl Acet- and Benz-amidines
Authors: Tada Ritsuro , Sakuraba Hisanori , Tokura Niichiro
Published: July 2006

The Bischler-Napieralski reaction of N-β-phenethyl acetamide in liquid sulfur dioxide resulted in the formation of N,N′-bis-β-phenethyl acetamidine in addition to the expected 1-methyl-3, 4-dihydroisoquinoline. And the reaction product from N-β-phenethyl benzamide were N,N′-bis-β-phenethyl benzamidine and N-benzoyl-N,N′-bis-β-phenethyl benzamidine in addition to the expected 1-phenyl-3,4-dihydroisoquinoline. In the case of acetanilide,N,N′-diphenyl acetamidine was produced. Benzanilide afforded N,N′-diphenyl benzamidine and N-benzoyl-N,N′-diphenyl benzamidine under a similar condition. The similar reaction of benzyl acylamides in liquid sulfur dioxide failed to yield such amidines.
Benzylideneaniline. II. Iodine Complexes of Benzylideneaniline and its Derivatives
Authors: Ebara Nozomu
Published: July 2006

Absorption spectra of the mixtures of iodine with benzylideneanilines in various concentrations have been measured, and from the optical densities of the solutions the equilibrium constants have been calculated.

The equilibrium constants are unexpectedly small. But for methoxy-derivatives and especially for ortho-compound, the equilibrium constants are considerably large.

For o-methoxy- and o-chloro-derivatives, the charge-transfer bands appear at the longer wavelengths.

These experimental evidences are also adequately explained by the perpendicular structure of benzylideneaniline.
The Kinetics of Substitution Reactions Involving Metal Complexes. III. Reaction between Copper(II) and Zinc-Ethylenediaminetetraacetate Complexes in Aqueous Solutions
Authors: Kato Kiyoko
Published: July 2006

The kinetic study of the substitution reaction of copper (II) and zinc-EDTA complexes in acetate buffer solutions was carried out with the same procedure as reported previously. The reaction was found to proceed simultaneously through three different reaction paths under the experimental conditions. The rate constants for three elementary reactions of those reaction paths were determined at 15 and 0°C, and the heats of activation and the entropies of activation for the reactions were calculated.
Absorption Spectra of Dyes. V. The Composition and Intermodular Charge Transfer Spectra of Complexes Formed in Aqueous Solution of the Mixture of Chlorazol Sky Blue FF and Chrysophenine G
Authors: Kobayashi Teruaki , Tanizaki Yoshié , Ando Noboru
Published: July 2006

1. The change in absorption spectra of mixtures of Chlorazol Sky Blue FF and Chrysophenine G in aqueous solution was stoichio-metrically studied in detail and a 1:1 complex and a 1:2 complex were proved to be formed.

2. The absorption spectra of the complexes were drawn from experimental results by use of the calculated equilibrium constants, and the phenomena of these absorptions were qualitatively explained according to VB and MO methods, with the conclusion that charge transfer spectra from Chlorazol Sky Blue FF to Chrysophenine G appear in the complexes.
The Equilibrium between the Sn-Pb Liquid Solution and the H2–H2O Gaseous Mixture
Authors: Atarashiya Koji , Uta Masahiro , Shimoji Mitsuo , Niwa Kichizo
Published: July 2006

Equilibrium in Sn (in liquid alloy)-H2O–SnO2–H2 system has been determined from 750 to 800°C by measuring the ratio of pressures between H2O and H2 gas mixtures. From this the activity of tin liquid tin-lead solutions has been calculated, and the following equation has been derived at 775 °C.

\barGSne=2330(1−xSn)2−600(1−xSn)3 cal./mol.

The temperature dependence of \barGSne could not be determined. However, if this value is calculated by combining Kleppa’s value for the excess heat, calorimetrically determined, with that of Elliott and Chipman for the excess entropy, the agreement between the value thus obtained and that of the present investigation is quite reasoable, taking into consideration the accuracies of these experiments. Theoretical considerations have been given for the excess functions of this system. It shonld be emphasized that the electrochemical effect of charge transfer is very small or may be regarded as zero in the lead-tin system and that the size factor is important.
Electrophotoluminescence of Zinc Sulfide Phosphors
Authors: Kotera Yoshihide , Naraoka Kiyotaka
Published: July 2006

The effects of the electric field on the luminescence of ultra-violet excited zinc sulfide phosphors are shown as a function of kinds of activator and chemical composition of matrix. All phosphors were measured in an electroluminescent cell of common construction. The electric field was obtained from 50c.p.s. alternating line. The Gudden-Pohl effect of both hexagonal and cubic ZnS: Cu increased with increasing copper content and reached a maximum at a content of 10−5 mol. The effect of cubic ZnS: Cu (10−5) is the strongest in the zinc sulfide phosphors at room temperature. Cubic sulfide phosphors activated by copper are sensitive to both momentary stimulation and field quenching.

Further, a relation between electron traps and the Gudden-Pohl effect was studied. From the temperature dependence of the Gudden-Pohl effect and glow curves, it might be assumed that the deeper trap which corresponds to a glow peak at 55°C does not produce the Gudden-Pohl effect at room temperature, rather the increase of the effect at higher temperature may be ascribed to the emptying of the deeper traps which can release their electrons thermally at higher temperature.
Effect of Oxygen Pretreatment on Hydrogen and Carbon Monoxide Chemisorption on Zinc Oxide
Authors: Kubokawa Yutaka
Published: July 2006

The effect of oxygen treatment at about 500°C of zinc oxide upon the chemisorption of hydrogen as well as of carbon monoxide was investigated in order to clarify the relation between the electronic state of the adsorbent and the chemisorption. In the case of hydrogen chemisorption, the amount adsorbed was reduced only slightly and the rate of desorption remained practically unaltered after oxygen treatment. On carbon monoxide chemisorption the oxygen treatment gave no effect. It was concluded from these results that both the chemisorption of hydrogen and that of carbon monoxide are essentially independent of the electronic state of zinc oxide. On the basis of such a conclusion combined with other results, the inapplicability of the model of hydrogen chemisorption proposed by Morrison was pointed out.
Hydrogen Chemisorption on ZnO·Cr2O3, ZnO·MoO3 and Cr2O3
Authors: Kubokawa Yutaka
Published: July 2006

For hydrogen chemisorption on ZnO·Cr2O3, ZnO·MoO3 and Cr2O3, the rates of adsorption and desorption, and adsorption equilibrium were investigated. The activation energy of adsorption ranged from 8 to 12 kcal./mol. for ZnO·Cr2O3, and from 15 to 25 kcal./mol. for ZnO·MoO3. The value for Cr2O3 was about 13 kcal./mol. In the cases of ZnO·MoO3 and Cr2O3, where desorption is negligible during adsorption, the rate of adsorption was proportional to P0.8, while with ZnO·Cr2O3 desorption was found to occur appreciably. The activation energy of desorption increased with a decreasing amount adsorbed from 10 to 35 kcal./mol. for ZnO·Cr2O3, and from 15 to 45 kcal./mol. for Cr2O3, while an approxi-mately constant value of 41 kcal./mol. was obtained with ZnO·MoO3 except in the initial stage of desorption. The maximum heat of adsorption estimated from adsorption isotherms was about 25 kcal./mol. for both ZnO·Cr2O3 and ZnO·MoO3. For all the systems studied, desorption experiments suggested the existence of surface heterogeneity with the activation energy of adsorption and heat of adsorption varying inversely in the cases of ZnO·MoO3 and Cr2O3, while with ZnO·Cr2O3 the variation in the same direction was observed. On the basis of the results hitherto obtained, the general characteristics of hydrogen chemisorption on oxides were discussed.
Spectrophotometric Determination of Tellurium(IV) by Extraction with Tributylphosphate
Authors: Hikime Seiichiro
Published: July 2006

Spectrophotometric determination of tellurium-(IV) by means of extraction with 100% TBP was studied. Tellurium forms yellow complex, as seen in the literature, with thiourea in a dilute hydrochloric acid solution, and the complex is extracted into TBP whenever potassium thiocyanate is present in excess in the solution.

Conditions on the extraction and the determination of tellurium were examined. It was found that addition of 2 ml. of thiourea solution (80g./1.) and 2 ml. of potassium thiocyanate solution (500 g./1.) to the sample solution is enough to extract 1 to 500 γ of tellurium per 20 ml. from the dilute hydrochloric acid solution with 20 ml. TBP. Tellurium complex was extracted thoroughly with TBP at pH 1. For the determination of tellurium, the absorbance of the TBP phase was measured spectrophotometrically at 400 mμ.

The effect of the diverse ions on the absorb-ance of tellurium complex was examined and also pre-extraction test on the removal of interference ions was carried out.
Partial Molal Volumes of Butyl Alcohols and of Related Compounds in Aqueous Solution
Authors: Nakanishi Koichiro
Published: July 2006

Partial molal volumes of four isomers of butyl alcohol and ethylene glycol in water are evaluated from the density measurement. They are compared with those of other monohydric alcohols and all the available data which have a common characteristic in the dependence upon the alcohol fraction are summarized.
On the Hydrolysis Products of Abietic Acid-Maleic Anhydride Adduct
Authors: Abo Masahiro
Published: July 2006

Hydrolysis of abietic acid-maleic anhydride adduct was carried out in two ways. The elementary analytical data of both resulting products were in good agreement with that calculated for the hypothetical tricarboxylic acid C24H34O6, and at about 100 to 120°C these products lost the weight, which corresponded to the loss of one molecule of water from one molecule of the acid, to revert to the original anhydride adduct. But, they showed only an apparent acid number when the titrations were carried out in ethyl alcohol, similarly to the case of the anhydride adduct. Their infrared spectra suggested an existence of five-membered ring anhydride structure and a hydrated water. On the basis of these facts, we offered an anhydride adduct monohydrate structure II for the above hydrolysis products.
Effect of Additives on the Hydrogen Reduction of Nickel Oxide
Authors: Iida Yoshio , Shimada Kenzo
Published: July 2006

The effect of additive impurities on the hydrogen reduction of nickel oxide has been studied. The additives have no influence on the reduction unless they dissolve into nickel oxide crystal. The reduction is promoted by the dissolution of cupric oxide and is retarded by the dissolution of lithium oxide and aluminum oxide. The effect of additives on the reduction is not explained reasonably by their catalytic behavior. There is no direct correlation between the reductive properties of nickel oxide and the type of additives from the point of the semiconducting behavior of these materials. The effect of additives on the reduction is related to their heats of formation.
Spectrophotometric Determination of Traces of Boron in Uranium
Authors: Onishi Hiroshi , Ishiwatari Nasumi , Nagai Hitoshi
Published: July 2006

Procedure is described for the spectrophoto-metric determination of 0.1∼1 p.p.m. of boron in uranium (metal, U3O8, and uranyl sulfate). Uranium metal was first converted to U3O8, and the oxide was dissolved in sulfuric acid and hydrogen peroxide. Boron was separated by distillation as methyl borate from sulfuric acid solution, and finally determined by the curcumin method.
Magnetic and Spectrophotometric Studies on Decoloration of Thiocyanato Iron(III) Complexes in Solutions. I
Authors: Miyake Chie
Published: July 2006

The decoloration mechanism of thiocyanato iron (III) complex solutions was investigated by means of both the magnetic and spectrophotometric methods. The data for the magnetic measurements supported that the decoloration was caused by the simple reduction of iron(III) to iron(II) by thiocyanate ions. But such a simple model of the reduction was not favourable for the observed decoloration, because the decrease in the absorbance was too small, being only about twenty percent. In order to eliminate this discrepancy, another scheme was proposed, which ascribes the magnetic and spectral observations to the formation of a binuclear complex of iron(III) and iron(II), a so-called dimer, during the decoloring reaction. This dimer possesses only one unpaired electron and accordingly very small magnetic moment, but possesses the significant absorbance due to iron(III). On this model, the greater decrease in magnetic moment and the rather smaller decrease in absorbance which we obtained, were quite satisfactorily clarified.
Rapid Determination of Thorium by Fluoride Titration Using Some Chromotropic Azo Dyes
Authors: Datta Sachindra Kumar
Published: July 2006

The thorium-chromotropic azo dye complexes are found to be fast-reacting with fluorides, in which exchange of dye molecule for fluoride ion takes place. The colored thorium-dye complexes are thereby decomposed with the liberation of the free dye and formation of thorium fluoride. The color changes at the end point enable visual comparison. Three dyes: nitroso-SNADNS-4, SNADNS-6 and CHPADNS have been used here as thorium complexing agents or indicators. The color change with the nitroso-SNADNS-4 at the end point is very sharp. Titrations are best carried out at pH range 2.4∼2.8 and thorium present should not be more than 50 mg. per 50 ml. solution. With the increased precipitation of thorium fluoride the dyes are adsorbed in the precipitate and the end point becomes more obscured. Microgram amounts of thorium may also be determined by this method. A large number of cations and anions interfere in the process, of which the most important are: iron, cerium, rare earth elements, alkaline earth elements, phosphates, borates, oxalates, tartrates and citrates. This method is best applicable to thorium solutions from which the interfering elements have been removed.
Spectrochemical Study of Microscopic Crystals. XXI. The Structure and Absorption Spectra of the Red and the Black Form of Nitrosopentammine-cobalt Salts
Authors: Yamada Shoichiro , Nishikawa Hiroaki , Tsuchida Ryutaro
Published: July 2006

In order to examine the structure of the red and the black nitrosopentammine-cobalt salts, their dichroism in the visible and near-ultra-violet region has been quantitatively determined at room temperature by the microscopic method.

The absorption spectrum of the “black salt” is found to be understandable best on the assumption that the “black salt” has binuclear complexes of cobalt(III), showing a special kind of absorption band due to the interaction between the two cobalt(III) ions through the N2 group.
The Adsorption of Dye Mixtures by Cellophane Sheet. II. A Quantitative Discussion of the Adsorption of Dyes
Authors: Horiki Yukio
Published: July 2006

1. The single dyeings of Chlorazol Sky Blue FF and Chrysophenine G and the mixture dyeing of them were carried out at 50, 70 and 90°C.

2. In the single dyeing, the surface layer volume in Vickerstaff’s equation was adjusted so as to obtain constant values of the standard affinity.

3. In the mixture dyeing, the behavior of dyes was explained quantitatively on the basis of the information of the single dyeing and the interaction between both dyes in the dyebath.
On the Assignment of a Band at 727 cm−1 in Polyethylene Terephthalate
Authors: Miyake Akihisa
Published: July 2006

Infrared spectra of polyethylene terephthalate and polyethylene-d4 terephthalate were investigated in the KBr and CsBr regions. No band attributable to a CO2 out-of-plane bending vibration was found below 700 cm−1. The only band assignable to this mode is a strong and perpendicular band at 727 cm−1. This fact together with the disappearance of the 727 cm−1 band in polyethylene deuteroterephthalate, indicates that two bands at 875 and 727 cm−1 in polyethylene terephthalate can be assigned to coupled vibrations of aromatic C–H and ester CO2 out-of-plane bending modes. This interpretation provides a consistent explanation for the spectral differences between ethylene glycol dibenzoate and 1,2-ethanedithiol dibenzoate and between ethylene glycol bis-(4-methoxycarbonylbenzoate) and 1,2-ethanedithiol bis-(4-methoxycarbonylbenzoate) as well as for the anomalous shifts of C–H out-of-plane frequencies and the appearances of “extra bands” in several aromatic esters.
Application of the Theory of Regular Solutions to Binary Phase Equilibria. I. Method of Application to Binary Liquid Equilibria
Authors: Ishida Kiyoharu
Published: July 2006

The same expression for the correlation of compositions in mutual equilibrium of two liquid phases as that which is immediately obtained from the empirical relations used by Cox and Herington was derived thermodynamically. The method has been given in such a manner as to represent the solubility curve for a binary liquid system symmetrically and to estimate the interchange energy from the mutual solubility data by applying the theory of regular solutions.