bluuebunny/crossref_metadata_2025 huggingface dataset:
Formaldehyde Resins. LXXV. Novolak Resin from p-Chlorophenol and Formaldehyde
Authors: Imoto Minoru , Nakade Shin-ichi
Published: July 2006

A novolak resin of a higher molecular weight, as described by Burke et al., was not obtained. It was considered that the reaction of p-chlorophenol with s-trioxane proceeded as follows: (1) At first, a normal reaction of novolak formation proceeded. The molecular weight distribution was explained by Imoto’s theoretical equation (120°C, 4 hr.). The analytical value of C1% was rather close to the calculated value. (2) Then “ reformation reaction” started (120°C, 7 hr. and 150°C, 2 hr.).(3) Reformation took place rather vigorously, and the molecular weight distribution became close to Poisson’s distribution (150°C, 8 hr.). (4) A three-dimensional compound was formed, and the molecular weight of the soluble part was lowered (150°C, 11 hr.). (5) The molecular weight of the soluble part increased by the decomposition of the threedimensional compound and by the dehydrochlorination reaction (150°C, 24 hr.).
The Activation Energy of Bromine Absorption by Carbonaceous Materials
Authors: Mukaibo Takashi , Takahashi Yoichi
Published: July 2006

In the present paper, the temperature dependence of the rate of bromine absorption by the carbonaceous materials has been studied. The apparent energies of activation of the reaction have been found to be 5∼7 kcal./mol. and had a dependence upon the degree of graphitization of carbonaceous materials. The value of the activation energy became smaller with an increase in the degree of graphitization. The results indicate that the mobilities of reactant molecules of the interlamellar compounds increase with the growth of the net plane of graphite crystals.

The saturation concentration of bromine in carbonaceous materials, under a saturated vapor pressure of bromine, was found to decrease with an increase in the temperature at temperatures above 30°C.
On the Permeation of Iodine through Graphite
Authors: Mukaibo Takashi , Takahashi Yoichi
Published: July 2006

The rate of iodine permeation through graphite has been studied and the following results were obtained:

(1) The process of iodine permeation through graphite has been found to consist mainly of a simple gas flow through the pore volumes, just as in the case of inert gases. The chemical interaction between iodine and graphite has been observed to be negligibly small.

(2) At tempeatures ranging from 90 to 160°C, and under a corresponding pressure of iodine vapor below 400 mmHg the rate of iodine permeation has been observed to be almost linearly proportional to the pressure of iodine. It has been concluded that the Knudsen flow was the predominant element of the total flow.

(3) The ratio of the flow rates for air and iodine, which were interpolated to the value under the same conditions, has been calculated to be 2.68∼2.85, close to the value 2.96, namely (MI2/Mair)1⁄2, as was expected from the Knudsen flow model.

(4) The rate of iodine permeation has been observed to decrease in the presence of argon gas, even in the region of Knudsen flow. It has been found that the rate is roughly inversely proportional to the pressure of argon gas. The “ dusty gas model ” discussed by Evans et al. has been adapted to give a reasonable explanation of this phenomena.
Solvent Effects on the Absorption and Fluorescence Spectra of Naphthylamines and Isomeric Aminobenzoic Acids
Authors: Mataga Noboru
Published: July 2006

The absorption and fluorescence spectra of naphthylamines and isomeric aminobenzoic acids in various solvents have been measured.

From the observed results, the difference in the dipole moments in the fluorescent and ground states respectively, i. e., \overrightarrowΔμ=\overrightarrowμe–\overrightarrowμg, has been estimated for naphthylamines.

The effect of hydrogen bonding between solute and solvent molecules on the spectral shifts has been discussed. The hydrogen bonding between alcohol and amino nitrogen exerts a especially remarkable influence on the spectra, and the reorganization of this hydrogen bond during the life time of the excited solute molecule has been concluded from the observed results.

The intramolecular hydrogen bond of o-aminobenzoic acid considerably decreases the \overrightarrowΔμ value and the effect of the intermolecular hydrogen bonding on the spectra. This result has been explained as due to the charge transfer through the intramolecular hydrogen bond.

The \overrightarrowΔμ values for naphthylamines and naphthols have been calculated using the ASMO CI method and compared with the observed results.

This comparison, together with the theoretical interpretation of the characteristics in the spectra of α- and β-isomers, respectively, has indicated that the lowest excited singlet state in the light absorption is 1Lb, whereas the fluorescent state is 1La in the case of α-naph-thylamine and 1Lb is the relevant excited state for both light absorption and fluorescence in the case of β-naphthylamine and naphthols.

The mechanism of this level reversal has been discussed as being due to the change in the structure of the amino group during the life time of the excited state.
The Separation and Determination of Ruthenium in Fission Products by Liquid-Liquid Extraction with Pyridine
Authors: Kiba Toshiyasu , Miura Akiko , Sugioka Yasuyuki
Published: July 2006

The present paper has described a method of separating, by liquid-liquid extraction with pyridine, radioactive ruthenium from fission products and technetium in an aqueous solution containing sodium hydroxide and hypochlorite. In the process, ruthenium in various ionic forms and various oxidation states is oxidized to perruthenate with the hypochlorite, and the perruthenate is transferred into pyridine from the aqueous solution. The partition coefficient of perruthenate was estimated for the carrierfree and the carrier-containing cases, as well as for the case where other fission products were present. Good separation of radioactive ruthenium from other fission products was achieved by this method, with a large decontamination factor. The results were examined by a γ-ray spectrum measured at each step of the extraction process.
The Kinetics of Substitution Reactions Involving Metal Complexes. VI. Reaction between Lead(II) and Ethylenediaminetetra-acetatocobaltate(II) Complexes in Aqueous Solutions
Authors: Tanaka Nobuyuki , Osawa Hisao , Kamada Minoru
Published: July 2006

The kinetic study of the substitution reaction of lead(II) and ethylenediaminetetraacetatocobaltate(II) complexes in aqueous solutions has been carried out by a similar method as reported previously. The reaction was found to proceed through four simultaneous reaction paths and to be characterized by involving the dissociation of ethylenediaminetetraacetatocobaltate(II) complexes as a rate-determining process. The rate constants of the rate-determining steps of four reaction paths were determined at ionic strength 0.2 at 5 and 15°C. It was confirmed also that this substitution reaction proceeds through both hydrated and monoacetato lead(II) ions.
Anomalies in the Counting Rate of the Solid Thin Film of Tritiated Lauric Acid in Relation to its Film Structure
Authors: Tajima Kazuo , Sasaki Tsunetaka , Muramatsu Mitsuo
Published: July 2006

A thin film of α, β-ditritiated lauric acid CH3(CH2)8(CHT)2COOH deposited from benzene on a stainless steel dish and put in a 2π gas-flow windowless counter gave a counting rate which decreased far more rapidly than was expected from the natural decay of the β-activity of tritium. We observed a distinct break point in the decay curve ten days after the deposition of the film, independent of the amount of sample taken, provided that the film was sufficiently thin.

Various factors, such as impurities, surface migration, exchange reaction and evaporation, were considered to explain the phenomena; among these the evaporation of the lauric acid from the deposited surface film of the composite structure was proved to be the main factor responsible for these phenomena.
The Color Reactions of Lower Oxoacids of Phosphorus with Molybdate and their Application to Colorimetric Determinations of \overset4P–\overset3P–\overset4P– and (–\overset3P–)6–Acid
Authors: Ohashi Shigeru , Yoza Norimasa
Published: July 2006

The color reactions of twelve lower oxoacids of phosphorus, as well as of \overset5P– and \overset5P–O–\overset5P–acid with molybdate, have been described. Of these compounds, \overset2P–\overset4P, \overset4P–\overset3P–\overset4P– and (–\overset3P–)6–acid react with molybdate in the acid solution to produce a bluish-green color without any reducing agent.

The bluish-green color caused by \overset2P–\overset4P–acid is not reproducible. Since the colors caused by \overset4P–\overset3P–\overset4P– and (–\overset3P–)6–acid are stable and since their intensities are proportional to their concentrations, one can detect and determine minute amounts of \overset4P–\overset3P–\overset4P– or (–\overset3P–)6–acid colorimetrically in the presence of the other oxoacids of phosphorus. When both \overset4P–\overset3P–\overset4P– and (–\overset3P–)6–acid are present in a given sample, one can determine each component by combining the method described above with the usual heteropoly blue method for the total phosphorus.
Decomposition of Peroxybenzoic Acid in Solution. V. Decomposition of Peroxybenzoic Acid and of Benzoyl Peroxide in Binary Mixtures of Carbon Tetrachloride with Cyclohexane, Toluene, or Diethyl Ether
Authors: Tokumaru Katsumi , Simamura Osamu
Published: July 2006

Decompositions of peroxybenzoic acid and of benzoyl peroxide were carried out in binary mixtures of carbon tetrachloride with cyclo-hexane, toluene or diethyl ether. The results of the product study strongly support the radical mechanism established previously and show that the oxygen to oxygen bond of peroxybenzoic acid is attacked by radicals more readily than that of benzoyl peroxide, but even peroxybenzoic acid is hardly attacked by the trichloromethyl radical.
Polarographic Determination of the Formation Constants of Sulfato, Acetato and Sulfatoacetato Complexes of Nickel(II) at Ionic Strength 1.0
Authors: Tanaka Nobuyuki , Saito Yu , Ogino Hiroshi
Published: July 2006

The formation of nickel(II) complexes with sulfate and/or acetate has been studied at 25°C and ionic strength 1.0 by the polarographic method reported previously1). The results obtained reveal that complex species, NiOAc+, NiSO4, Ni(SO4)22−, Ni(OAc)(SO4)− and Ni(OAc)(SO4)23−, are present in the solution. The formation constants determined are:KNioAc=1.9, KNiSO4=3.7, KNi(SO4)2=2.6×10, KNi(OAc)(SO4)=1 and KNi(OAc)(SO4)2=∼3 at ionic strength 1.0.
The Surface Activities of Bivalent Metal Alkyl Sulfates. II. The Solubilization of Some Hydrocarbons in Aqueous Solutions of Bivalent Metal Alkyl Sulfates
Authors: Satake Iwao , Matuura Ryohei
Published: July 2006

The solubilizing power of the bivalent copper, cobalt, nickel and magnesium dodecyl sulfates, and of copper tetradecyl sulfate towards benzene, toluene, m-xylene and n-hexane has been determined over the concentration range from 10−3 to 1.5×10−2 mol./1. at various temperatures. There were approximately linear relationships between the amounts of hydrocarbons solubilized and the detergent concentration. No fundamental difference could be observed among the solubilizing powers of the various bivalent salts studied, in accordance with such other micellar properties as CMC or micellar aggregation number. The solubilizing power, in moles of hydrocarbon solubilized per equivalent detergent, was found to be about 2.0 for the solubilization of benzene by bivalent metal dodecyl sulfates, which is about 1.5 times that by sodium dodecyl sulfate. This increased solubilizing power of bivalent salts was ascribed to the increased micellar volume and to the increased micellar aggregation number compared with that of sodium dodecyl sulfate. The increasing chain length causes a normal increase in solubilizing power. The ratio of the amount of hydrocabons solubilized by copper tetradecyl sulfate to that solubilized by copper dodecyl sulfate was about 1.5.
The Electronic Spectra of Aromatic Molecular Crystals. I. Substitued Benzene Molecules
Authors: Tanaka Jiro
Published: July 2006

The electronic absorption spectra of some substituted benzene molecules p-nitroaniline, benzoic acid, acetanilide, trans-cinnamic acid, and durene have been measured in ethanol or n-heptane solutions and as single crystals, using polarized light. The measurement of the crystalline spectra reveals in many respects the properties of the transitions of substituted benzene molecules. The 277 mμ of durene, which is reasonably regarded as a band analogous to the 260 mμ of benzene, is shown to be polarized perpendicular to the two-fold symmetrical axis of the molecule. Bands of the same type occur at 264 mμ in p-nitroaniline (crystal), at 284 mμ in benzoic acid, at 282 mμ in acetanilide and at 299 mμ in trans-cinnamic acid. In addition, those molecules in which the benzene ring is substituted by the electron-accepting groups, show a strong band, associated with intramolecular charge transfer, in the near ultraviolet region. The 370 mμ band of p-nitroaniline is shown to be polarized parallel to the long axis of the molecule, and the 230 mμ band of benzoic acid has a polarization parallel to the line connecting the centers of the benzene ring and the carbonyl group. The directions of the transition moments of the 240 mμ band of acetanilide and the 276 mμ band of trans-cinnamic acid are also shown to be on the line connecting the substituents and the benzene ring. Davydov splitting is observed in the crystal of p-nitroaniline; this splitting is in good agreement with the values calculated by the exciton theory.
The Effects of Stationary Liquids on the Separation of the Isomers of Aromatic Hydrocarbons in Gas Chromatography
Authors: Araki Takeo
Published: July 2006

1) The gas chromatographic separation of the isomer of aromatic hydrocarbons has been investigated on the aromatic stationary liquids.

2) It has been established from the experimental results on the xylene series that the S12–σp diagram of Fig. 1 of the previous paper4) is applicable to the separation of the ethyltoluene series.

3) ΔS12 has been defined, and it has been proven that this value was roughly constant between two series of dialkylbenzenes. Moreover, this value seems to throw a light on the prediction of the separation of the isomers of aromatic hydrocarbons.

4) This separation seems to be affected by π-complex formation between aromatic hydrocarbons and aromatic stationary liquids of both the π-acidic and π-basic types.
Consideration on the Q-e Scheme. III. Q-e Factors in Ionic Polymerization
Authors: Kawabata Nariyoshi , Tsuruta Teiji , Furukawa Junji
Published: July 2006

The authors have tried to divide the conjugation-stabilization energy between monomer and attacking polymer cation, ECM, and that between monomer and attacking polymer anion, EAM, into four terms by means of the equations ECM=ECoMo+EC+EM++E′CM and EAM=EAoMo+EA+EM−+E′AM, respectively. Here, ECoMo is the stabilization energy between polyethylene cation and ethylene monomer, EC and EM+ are the increments in the stabilization energies of systems of (substituted polyethylene cation–ethylene monomer) and (polyethylene cation–substituted ethylene monomer) with respect to ECoMo as standard. E′CM is the surplus increment in the stabilization energy of the system of substituted polyethylene cation and substituted ethylene monomer. EAoMo, EA, EA, EM− and E′AM have the significance analogous to ECoMo, EC, EM+ and E′CM, respectively. The E′CM values for most cation-monomer pairs have been found to be negligibly small. This result correlates with the experimental findings that the products of r1r2 are nearly equal to unity for all the cationic copolymerization systems investigated so far. The equation, kCM=PC+QM+exp(–eCM+), is assumed to be applicable to cationic polymerization, the e+-terms being, however, negligible for any cation-monomer pair. Here, Pc+ is the reactivity associated with polymer cation, QM+ is the general reactivity term of monomer in cationic polymerization, and e+ is the corrective term characteristic of polymer cation and monomer. On the other hand, the E′AM values were often found to play a large part in EAM. This result is consistent with some experimental findings by Szwarc et al. The relative reactivity value of vinyl monomers toward carbonium ions is considered to be the general reactivity term in cationic polymerization, Q+. A good correspondence of Q+ with EM+ has been observed.
Steady-state Studies by the ESR Method of the Photopolymerization of Vinyl Acetate and Methyl Methacrylate
Authors: Kuwata Keiji , Nishikida Ko-ichi , Kawazura Hiroshi , Hirota Kozo
Published: July 2006

It has been attempted, by the ESR technique, to study the steady-state photopolymerization of vinyl acetate and methyl methacrylate, using hydrogen peroxide as the initiating substance. The observed steady-state radical concentration has been found to coincide within a factor of two with the calculated value, Eq. 3, derived under the assumption of a simple kinetic treatment. Although, it has been shown that the calculated decay curve deviates from the observed curve in the later period of decay, especially in the case of methyl methacrylate; such a discrepancy seems to be explainable if the reaction rate decreases with the chain length of the polymerizing radicals.
The Thermal Annealing of Phosphorus-32 Formed by the Neutron Irradiation of Several Inorganic Phosphorus Compounds
Authors: Baba Hiroshi , Tanaka Kichizo , Yoshihara Kenji
Published: July 2006

Thermal annealing curves given from the chemically-distributed phosphorus-32 formed by neuton irradiation in a nuclear reactor were obtained by heating several orthophosphates, sodium pyrophosphate, and disodium hydrogen phosphite samples in crystal. The separation was accomplished by one-dimensional paper chromatography. The amounts of phosphorus-32 in the chemical species different from the parent species decreased upon the heating of the salts, except in the case of sodium dihydrogen phosphite, whereas retention always increased.

By the analysis of thermal annealing curves obtained from the initial distribution of activation energies, it was found that there was a difference between the thermal-annealing behavior of the polyphosphate fraction and that of the reduced species fraction. The activation energies of the polyphosphate fractions were in the range of 0.60 to 1.0 eV., but the pyrophosphate sample showed an exceptionally high value, i. e., 0.78 to 1.3 eV. Higher activation energy values were estimated for the annealing of the reduced species fraction than for those of the polyphosphate fractions.
ESR Studies on Negative Ions of Biphenyl Derivatives. I. Electron Spin Resonance Hyper fine Spectra of 4-Methyl Biphenyl and p, p′-Bitolyl Mononegative Ions
Authors: Ishizu Kazuhiko
Published: July 2006

The electron spin resonances of 4-methyl biphenyl and p, p′-bitolyl mononegative ions were observed in either dimethoxyethane or tetrahydrofuran, using potassium metal as a reducing agent. Well-resolved proton hyperfine spectra were observed in each case, and the g-value, the overall width, and the hyperfine splitting coefficients due to the methyl protons and ring protons were determined.

The theoretical spectra were constructed according to the spin densities calculated by Hückel’s MO treatment, and these results were compared with the observed spectra.
The Photochemical Decomposition of α,α-Diphenyl-β-picrylhydrazyl (DPPH) in Solution. II. Products of the Photolysis and Its Reaction Mechanism
Authors: Suzuki Atuo , Takahasi Makoto , Shiomi Kengo
Published: July 2006

1. DPPH in a benzene solution was decom-posed by sun-light on a relatively large scale in the presence of air, and the prducts were separated on a cellulose column. The products were identified as α,α-diphenyl-β-picrylhydrazine (I), α-phenyl-α-(p-nitrophenyl)-β-picrylhydrazine (II), and a third component (III) with a chemical composition of (C18H10−11-N3O3)n (the n is greater than 3).

2. The method of separation by means of a cellulose column was applied in the quan-titative estimation of the reaction products. The ratios of the products in the course of the decomposition were determined. From the ratio at the final stage, the over-all reaction can be written as follows:

4 DPPH→I+2II+III

3. The physical and chemical properties of the third component have been described, and a possible structure for III has been pro-posed.

4. From the material balance and the chemical compositions of the reaction products, it is presumed that the early stage of the decomposition of DPPH induced by light is an intermolecular nitration of DPPH.
The Intramolecular Force Field and Normal Vibrations of Isotactic Polypropylene and Deuterated Derivatives
Authors: Miyazawa Tatsuo , Ideguchi Yoshiko
Published: July 2006

The infrared active normal vibrations of isotactic polypropylene and its deuterated derivatives in the crystalline state have been treated. The modified Urey-Bradley-Shimanouchi force field has been used for the calculations. A total of 23 potential constants have been adjusted by the method of least squares with reference to a total of 166 frequencies observed by Peraldo and Farina. The standard errors of the potential constants have also been calculated. The r. m. s. deviation of the calculated frequencies from the observed ones is as small as 0.9%. The potential energy distributions have also been calculated for the discussion of the nature of the observed infrared bands. Vibrational assignments of the liquid bands of isotactic polypropylene have also been made.
The Colorimetric Determination of Minute Amounts of Iodide and Iodate in Sea Water by Means of Their Catalytic Effects
Authors: Yonehara Norinobu
Published: July 2006

In the presence of 2000 p.p.m. chloride, iodide and iodate show. the same catalytic effect on the color-fading reaction of a solution of ferric thiocyanate. The total iodine content in sea water may be determined by estimating the absorbance of a sample diluted about ten times.

The iodide in the sample is first oxidized to free iodine by a sodium nitrite solution and a nitric acid solution of ferric ammonium sulfate. The resulting free iodine is removed by extraction with carbon tetrachloride. The iodate which remains quantitatively in the aqueous layer is determined by a similar procedure. The difference between the total iodine and the iodate-iodine gives the iodideiodine.

By this method, the iodate and total iodine contents in sea water can be determined rapidly and accurately. It takes only about 2 ml. of sea water to determine both the total iodine and the iodate-iodine.
Thermogravimetric Analysis of Polyoxymethylene
Authors: Igarashi Shoichi , Mita Itaru , Kambe Hirotaro
Published: July 2006

The character of the thermal decomposition of polyoxymethylene, acetylated polyoxymethylene and Delrin in air and in nitrogen has been studied by thermogravimetric analysis. Two peaks have been observed in each atmosphere in the derivative thermogravimetric analysis curves for these samples.

It has been confirmed that the feature of doublet peaks is related to the concentration of oxygen during the decomposition and, thus, that the first stage is due to the chain depolymerization as well as to the oxidative decomposition, and that the second stage is to be attributed to the random degradation of a stable fragment formed during the first stage decomposition.

An increase of carbonyl groups in the polymer molecule with the degradation was confirmed by infrared spectroscopy.
Calculation of the State Energies of Benzaldehyde. I. Semi-Empirical Molecular Orbital Method
Authors: Inuzuka K\={o}z\={o} , Yokota Toshio
Published: July 2006

The electronic structure and the nature of the electronic transitions in the benzaldehyde molecule have been elucidated by the use of a semi-empirical MO method assuming a C2v symmetry. The results of the calculations conform to the observed values for the singlet and triplet states in spite of the use of a crude approximation. In benzaldehyde, it has been found that the n,π triplet state is the lowest. The charge transfer band may be explained by means of our calculations.
The Spectrophotometric Determination of a Small Amount of l-Ascorbic Acid with the Iron(III)-1, 10-Phenanthroline Reagent
Authors: Onishi Isao , Hara Tadashi
Published: July 2006

A simple and accurate spectrophotometric method with the iron(III) -1, 10-phenanthroline reagent has been established for the determination of a small amount of l-ascorbic acid ; it has been applied to the measurement of the catalytic effects of metal ions on the autoxidation of l-ascorbic acid.
The Mechanism of the Thermal Decomposition of Hexamminecobalt(III) Chloride
Authors: Tanaka Nobuyuki , Nanjo Michio
Published: July 2006

The thermal decomposition of hexamminecobalt(III) chloride has been investigated by thermogravimetric, polarographic and infrared spectroscopic method. The results indicate that the reaction is initiated by the electron transfer from either a ligand molecule or an outersphere ion to the central cobalt atom, forming a less stable cobalt(II) complex, which immediately dissociates ammonia molecules and undergoes decomposition.
Electrical Conductivity of Organic Semiconductors at High Pressure
Authors: Harada Yoshiya , Maruyama Yusei , Shirotani Ichimin , Inokuchi Hiroo
Published: July 2006

In order to study the effect of high pressure on the electrical conductivity of organic semiconductors, the band structure of the anthracene crystal has been calculated at atmospheric pressure and also at 160 kilobars, using the treatment of the tight-binding approximation. The total band widths of both electrons and holes at 160 kilobars are 5∼6 times as large as those at atmospheric pressure. Although the mobilities of both carriers, on the whole, increase in magnitude by several tens times at 160 kilobars, the sharp drop in the resistivity at high pressure may be due mostly to the great increase in the concentrations of the charge carriers (103∼104 times).
The Electrical Properties of the Poly (N-vinyl Carbazole)-Tetracyanoquinodimethane Charge Transfer Complex
Authors: Taniguchi Akimasa , Kanda Seiichi , Nogaito Takeshi , Kusabayashi Shigekazu , Mikawa Hiroshi , Ito Kazuo
Published: July 2006

Poly (N-vinyl carbazole) (specific resistivity, above 1017Ω cm.) gives a dark-green charge transfer complex with tetracyanoquinodimethane. The specific resistivity of the complexes at room temperature is 1014∼1016Ωcm. and the band-gap energy is 1.1∼1.5 eV. The film-forming property of poly(N-vinyl carbazole) is retained in the complex. The charge transfer band is observed at about 620 mμ.
The Addition Reactions of Propanol-2 to Ethylene Induced by Gamma-ray Irradiation in the Gaseous Phase
Authors: Kurihara Tadashi , Hotta Hiroshi
Published: July 2006

When a mixture of propanol-2 and ethylene was irradiated in the gaseous phase by cobalt-60 gamma-rays at 100°C to 200°C, thirtyseven products were found by gas chromatography from the samples above 150°C in addition to the telomers already reported, while fifteen products were found at 100°C. While the yield of these products increased with an increase in the temperature, the yield of the telomers increased not only with an increase in the temperature but also with a decrease in the temperature below 125°C. The identified products show that all the kinds of radicals, which were expected from propanol-2 are present as the precursors of these products. It has been concluded from these facts that the various radical transfer reactions and disproportionation reactions occur in the gaseous phase, especially above 150°C, although the addition reactions are predominant in the liquid phase at lower temperatures. On the other hand, although 1-hydroxyethyl radical ions are predominant in the electron impact of propanol-2, the 1-hydroxyisopropyl radical is predominant among the precursor radicals. This shows that the present processes are radical and not ionic.
On the Melting Temperature of Nucleic Acid in Solution
Authors: Tsuboi Masamichi
Published: July 2006

The mass action law has been applied to the “melting” process of nucleic acids and also to the binding process of small ions or molecules. On the basis of previously-obtained data on the variation of the melting temperature of nucleic acids caused by interaction with small ions and molecules, some of the enthalpy, entropy, and free energy changes involved in the processes have been estimated. A model has been proposed of how the spermine molecule may interact with the deoxyribonucleic acid molecule to stabilize the double-helical conformation of the latter molecule.
Electronic Spectrum of Fluorenone
Authors: Kuboyama Akira
Published: July 2006

The electronic spectrum of fluorenone in various solvents has been measured; from these results and from the results obtained with the simple MO method for the π-electronic system of fluorenone, the nature of each absorption band of fluorenone has been studied. It has been concluded that fluorenone has four π→π* absorption bands (near 380 mμ, 310 mμ, 290 mμ, and 250 mμ respectively) in the near-ultraviolet region. The assignments of the 380 mμ and 310 mμ bands to the transition (A1→B2) and the 290 mμ and 250 mμ bands to the transition (A1→A1) are favorable in view of the obtained results.
Studies of the Hydration and the Structure of Water and Their Roles in Protein Structure. III. Proton Magnetic Resonance Shifts of Water in Aqueous Solutions of Electrolytes and Their Relation to the Structure of Water
Authors: Goto Sachio , Isemura Toshizo
Published: July 2006

The effects of various electrolytes and organic compounds on the structure of water, and particularly on hydrogen bonding, have been investigated by measuring the chemical shift of water protons in the nuclear magnetic resonance frequency. The chemical shift observed for salt solutions has been corrected for the bulk diamagnetic susceptibility, using methyl protons of acetone as a reference. The chemical shifts of water protons in aqueous solutions of various solutes have been considered.
Studies of the Hydration and the Structure of Water and Their Roles in Protein Structure. IV. The Hydration of Amino Acids and Oligopeptides
Authors: Goto Sachio , Isemura Toshizo
Published: July 2006

The numbers of hydration of various amino acids, oligopeptides and saccharides in aqueous solutions and their dependence on the temperature have been determined by the method of ultrasonic interferometry. The hydration on ionic, hydrophilic and hydrophobic sites has been discussed. Particularly, evidence for the: hydration around hydrophobic groups has been obtained. Also, we have established the hydration of the peptide bond.
Acid-base Concept and Catalytic Activity of Oxides
Authors: Tanaka Ken-ichi , Tamaru Kenzi
Published: July 2006

The catalytic activity of metal oxide has been correlated with the acidity of the oxide surface. The acidity depends upon the partial charge on the oxygen in the oxide and also upon the heat of the formation of the oxide. Consequently, the catalytic behavior may be correlated with the heat of the formation of the oxide, as in the cases of the chemisorption of gases and catalytic activity by metals.

The decomposition of formic acid and alcohol and the polymerization of isobutylene have treated on the basis of this concept, and the selectivity, or activity, of these reactions, their reaction kinetics, and also the effect of heat treatment have been discussed.
Spectroscopic and Theoretical Studies of Charge-Transfer Type Molecular Complexes between Monoölefins and Metal Ions: Selective Complex Formation Abilities of Copper(I), Silver(I) and Mercury(II) Ions
Authors: Hosoya Haruo , Nagakura Saburo
Published: July 2006

The ultraviolet, infrared and Raman spectra of the cyclohexene-silver perchlorate complex have been measured under various conditions. A new band has been found in the 220∼230 mμ region for the complex in an aqueous solution; it has been found to have the mixing character of the charge-transfer from the olefln to the metal ion and of the Rydberg transition within the olefln molecule. The equilibrium constant (pK) has been evaluated spectro-photometrically as 0∼−2 for the equilibrium

C6H10+Ag+\ightleftharpoonsC6H10…Ag+

The 1653 cm-−1ν(C=C) and 716 cm−1δ(=C–H) bands of pure cyclohexene have been found to shift to about 1585 and 745 cm−1 respectively by means of complex formation with silver perchlorate, both in solids and in solutions. This and other facts concerning the vibration spectrum of the complex show that the C=C bond is weakened by the complex formation.

The very selective complex formation ability of Cu+, Ag+ and Hg2+ toward monoölefins has been explained by the calculation in which we explicitly took into account the charge number, the ionization potential, the electron affinity, the ionic radius, the hydration (solvation) energy, and the various atomic excitation energies of the ions. It has been pointed out that the roles of the d-electrons of the metal ion and the 3sσ-electrons of the olefln molecule are important in the ground state and the lowest excited state respectively, while the effect of the hydration (or lattice) energy is important in both states.
The Radiation-induced Addition of Hydrogen Sulfide to Propylene
Authors: Sugimoto Ken’ichi , Ando Wataru , Oae Shigeru
Published: July 2006

The radiation-induced free radical addition of hydrogen sulfide to propylene to give n-propylmercaptan and di-n-propylsulfide has been studied. The direction of the addition to propylene is consistent with that of the radical addition to such olefins previously studied, suggesting that the SH is both the adding and chain-carrying species. The addition of the thiol to propylene has been found to undergo a free radical chain reaction, readily yielding di-n-propylsulfide in the succeeding step.
The Diamagnetic Study of the Nature of Association in Acetic Acid
Authors: Sriraman S , Shanmugasundaram V
Published: July 2006

The magnetic susceptibilities of acetic acid in the pure and dissolved states have been investigated, and the results obtained have been attributed to the changes that take place in the association of acetic acid molecules.
Electron Microscopic Study of the Dehydration of Brucite and the Recrystallization of Periclase upon Further Heating
Authors: Yamaguchi Goro , Tokuda Toshio
Published: July 2006

1) The hexagonal plate crystals of the brucite, about 1 μ across, have been obtained by the hydrothermal treatment of chemicallypure magnesium hydroxide.

2) The brucite crystals transformed themselves upon dehydration into aggregates of the minute periclase crystallites oriented in such a way that (111) is parallel with (0001) of the original brucite crystal and (220) is parallel with (11\={20}).

3) The dehydration seems to take place in two steps. The escape of water molecules and the gradual shrinkage of the lattice take place at the first step of the dehydration. The slip of the oxygen layers and the crystallization take place at the second step.

4) Upon further heating after complete dehydration, the orientation of the crystallites remained unchanged in many crystals. In a few crystals, however, the orientation changed in the several ways shown in Table I. This phenomenon is a kind of sintering in the grain.
Fundamental Conditions and Reaction Mechanisms in Formation of Phosphomolybdenum Blue
Authors: Namiki Hiroshi
Published: July 2006

The effects of acidity and molybdate concentration on the development of phosphomolybdenum blue have been studied in detail and the relationships among these three factors shown by a graph, called a “phosphomolybdenum blue color field” by the author. A further investigation was undertaken in order to explain the mechanisms of color development and the fundamental properties of reaction products under the optimum conditions established by the author for the determination of phosphate. The acidity and molybdate concentration in the graph was divided into 4 fields, the fields denoting the concentration conditions given below.

Field 1: All phosphate forms phosphomolybdate, and then forms phosphomolybdenum blue. No blue color due to the reagent blank is obtained. This field is suitable for the phosphomolybdenum blue method.

Field 2: All phosphate forms phosphomolybdate, and then forms phosphomolybdenum blue. However, the reagent blank also becomes blue. This field is suitable for the phosphomolybdate method.

Field 3: Only a part of the phosphate forms phosphomolybdate and then phosphomolybdenum blue. Heating promotes the reaction, making it suitable for the phosphomolybdenum blue method.

Field 4: No phosphomolybdate is formed. This field is not applicable for determinations.

When the reaction of phosphomolybdenum blue development is carried out in a solution containing 0.65 n sulfuric acid and 0.15% ammonium molybdate, which is optimum for the determination of phosphate, phosphate is completely converted to phosphomolybdate, which in turn is quantitatively reduced by stannous chloride to form phosphomolybdenum blue. At the first stage of the reduction, one phosphomolybdenum blue molecule is regarded as possessing seven molybdenum atoms that have been reduced to molybdenum (V). Reduction by the use of excess amounts of stannous chloride proceeds in the following order:

(1) Phosphomolybdate → Phosphomolybdenum blue

(2) Molybdate reagent → Molybdenum of low valency

(3) Phosphomolybdenum blue → Phosphomolybdenum blue of a low valency

The reduction product in reaction 2 is probably a molybdenum (III) compound. A large excess of stannous chloride fades the blue color of the solution by means of reaction 3. Reaction 3 is negligible compared with reactions 1 and 2 in solutions containing a slight excess of stannous chloride. Under the conditions established by the author for color development, no blue product is formed as a results of the reduction of the molybdate reagent. Molybdate is considered to have been reduced directly to reddish brown molybdenum (III).

The knowledge obtained from these experiments is thought to be enough for the performance of the phosphomolybdenum blue method, although it is still insufficient for a complete explanation of the properties of the reactions and the reaction products.
The Isotopic Hydrogen Exchange between Propene and Deuterium Oxide Catalyzed by Nickel Powder
Authors: Hirota Kozo , Hironaka Yoshie
Published: July 2006

Deuterium exchange between propene and deuterium oxide has been found to occur at room temperature successively on a nickel catalyst, but about six times more easily at the vinyl hydrogen than at the methyl hydrogen at room temperature, although this finding is not concordant with the expectation derived from the scission energy of the bonds concerned and although it is also different from the easier exchangeability of the methyl hydrogen in the similar exchange reaction of paraxylene.

The discrepancy has been explained by assuming the classical chemisorbed species of propene as an intermediate, i. e., a state of propene which forms bonds between nickel atoms and the C=C group, besides the formation of adsorbed allyl type species on nickel.
The Electrokinetic Potential of Titanium Dioxide
Authors: Morimoto Tetsuo , Sakamoto Masashi
Published: July 2006

1) The surface property of titanium dioxide has been investigated by measuring the ζ-potential. The ζ-potential of titanium dioxide in water depends on the temperature of the pretreatment, and its sign changes from positive to negative at about 800°C. This fact has been interpreted in terms of the way of the dissociation of hydroxyl groups on the surface of titanium dioxide, the ways of which depend on its modifications. This phenomenon seems to be supported by crystallographic data.

2) The effects of electrolytes on the ζ-potential of titanium dioxide have been studied. Barium has a chloride greater influence on the ζ-potential of titanium dioxide than does potassium chloride or hydrochloric acid. Hydroxide ions have a fairly great influence on the surface of the solid. The effect of sodium triphosphate is extraordinarily great; by the addition of the electrolyte, the positive potentials of titanium dioxide are inverted to negative potentials and the negatively-charged rutile surface becomes more negative, and this development suggests the formation of a complex compound on the surface of titanium dioxide.
Analytical Studies Using the Convection Electrode. VIII. A. C. Polarography with the Pushed-out Mercury Drop Convection Electrode
Authors: Suzuki Junsuke , Ozaki Tokuro
Published: July 2006

A.C. polarography with the PMDCE has been investigated, using cadmium in 1 m hydrochloric acid.

A satisfactory proportionality between the summit current and the concentration is obtained in the range from 1×10−4 to 2×10−6m, and the summit current obtained with the PMDCE (in the presence of dissolved oxygen at the stirring rate of 600 r.p.m.) for the cadmium depolarizer is about thirty times as large as the corresponding diffusion current obtained with the DME.

The a.c. polarogram obtained with the PMDCE shows a gradual decrease in the summit current as the stirring increases; this decrease is considered to be due to the quasiirreversibility at the electrode reaction because of the increase in the rate of mass transfer caused by the convection. The relation between the summit current and the stirring rate is exponential in the range from 600 to 1200 r.p.m.
Planar Quadri-co-ordinate Complexes of Cobalt(II) with Schiff Bases Derived from Salicylaldehyde
Authors: Nishikawa Hiroaki , Yamada Shoichiro
Published: July 2006

In order to establish the electronic absorption spectra of quadri-co-ordinate, square-planar cobalt(II)-complexes, the absorption spectra of bis(salicylaldehyde)ethylenediiminato- and bis-(salicylaldehyde)propylenediiminato-cobalt(II) in solution have been determined, with the utmost care taken to avoid undesirable oxidation of the complexes. These compounds show characteristic ligand field band, with a comparatively sharp peak in the near-infrared region.

Bis(salicylaldehyde)-α-α′-dimethylethylenediiminato- and bis(salicylaldehyde)-α,α′-diphenylethylenediiminato-cobalt(II) have deen prepared, and their spectra examined. These also show characteristic ligand field bands, with a sharp peak in the near-infrared region.

Bis(salicylaldoximato)- and bis(salicylaldiminato)-cobalt(II) have been prepared, and their spectra examined. On the basis of the results obtained above, it has been concluded that these two complexes take a quadri-co-ordinate, planar configuration.
Semiconducting Properties of Organic Polyiodides
Authors: Kusabayashi Shigekazu , Mikawa Hiroshi , Kawai Shichio , Uchida Madoka , Kiriyama Ryôiti
Published: July 2006

1) The electrical conductivities of ten organic polyiodides have been measured: tetramethylammonium triiodide, tetramethylammonium pentaiodide, trimethylphenylammonium triiodide, trimethylphenylammonium pentaiodide, trimethylphenylammonium heptaiodide, 1-methyl-2-picolinium triiodide, 1-methyl-2-picolinium pentaiodide, 1-methyl-2-picolinium heptaiodide, 1-methylquinolinium triiodide and 1-methylquinolinium pentaiodide. At the room temperature specific resistivities are 107∼1010Ωcm. and the band-gap energies, as calculated from ρ=ρ0exp(ε⁄2kT), are 1.3∼2.6 eV.

2) Both ε and ρ20 decrease with an increase in the number of iodine atoms in the polyiodide anion, not so much difference in these values being observed with different kinds of cations. The iodine framework in the crystal structure is of primary importance in determining the electrical conductivity.

3) For the trimethylphenylammonium triiodide single crystal, an anisotropy of ε values was observed between the normal direction and the direction parallel to the cleavage plane along the growth axis.

4) Preliminary thermoelectric power measurements show that the majority carrier is the hole.

5) The solid absorption spectra of polyiodides have been measured. The band-gap energy, ε,does not agree with the absorption maximum, being rather near the very beginning of the first absorption.

6) All the polyiodides investigated show a photoconductivity response.
Colloid Chemical Studies of Starching Materials. VI. Viscometric Studies of the Interaction between Polyvinyl Alcohol and Sodium Dodecyl Sulfate
Authors: Nakagaki Masayuki , Ninomiya Yukiko
Published: July 2006

The intrinsic viscosity and related constants have been measured for polyvinyl alcohol NM-14 and GM-14 in a sodium dodecyl sulfate solution. At a detergent concentration lower than the first critical micelle concentration (0.008n), the viscometric property of the polymer is close to that in distilled water. At an intermediate detergent concentration between the first and the second critical micelle concentration (0.02n), the viscometric property of the polymer is like that of polyelectrolyte, probably because of the electric charges given by detergent anions combined with the polymer. At a detergent concentration higher than the second critical micelle concentration, the intrinsic viscosity of the polymer is high and the polymer combined with the detergent is more extended than in distilled water. The interaction between the polymer and the detergent is very likely due to the contact of hydrophobic parts of the molecules.
The Paramagnetism of “Violanthrone-B”
Authors: Akamatu Hideo , Maekawa Tsuneo , Iida Yôichi , Kinoshita Minoru
Published: July 2006

The paramagnetic nature of “violanthrone-B” has been studied. The spin concentration in this substance has been determined by the ESR absorption, which is consistent with the value estimated from the magnetic susceptibility and its variation with the temperature. It has been concluded that the molecules of violanthrone-B, in the amount of about 40 per cent of all the molecules, are in a free radical state. It has been suggested, according to the proposed structure of violanthrone-B, that the free radical might result from detaching a hydrogen atom from a peripheral carbon of the tetrahedral type of bonding, which changes thereafter to the trigonal type of bonding.
The Synthesis of Deuterated Polypropylenes
Authors: Murahashi Shunsuke , Nozakura Shun’ichi , Yasufuku Katsutoshi
Published: July 2006

The synthesis of propylene-d6 and propylene-1,1,2-d3 has been attempted for the purpose of an infrared spectroscopic study of the isotactic polymers.

Propylene-d6 has been synthesized by the half-deuteration of the propyne-d4 which had been obtained by the hydrolysis of magnesium carbide with deuterium oxide, and propylene-1,1,2-d3 has been synthesized by the reaction of deuterovinyl magnesium bromide and dimethyl sulfate. In the half-reduction of propyne-d1 with a Lindlar catalyst, it was found that an equilibrium between propyne-1-d1 and allene-1-d1 exists on the catalyst.

The polymerization of these monomers was carried out with a Ziegler-Natta catalyst, and isotactic polymers were obtained. In the copolymerization of propylene and propylene- 1,1,2-d3 with a Ziegler-Natta catalyst, it was observed that some of the infrared crystalline sensitive bands of isotactic polypropylene, 1164,998 and 838 cm−1, do not exist (or at least diminish) in the copolymer but do exist in artificial mixtures of the homopolymers. This fact evidently suggests that these infrared bands are due to an intrachain in the crystalline part of the polymer.