bluuebunny/crossref_metadata_2025 huggingface dataset:
Study of Motion of D2O in Ba(ClO3)2D2O by Transient NMR
Authors: Chiba Takehiko , Kakiuchi Yoshinobu
Published: July 2006

Deuteron spin lattice relaxation time T1 and the reorientation rate of D2O have been measured at various temperatures on a single crystal of Ba(ClO3)2D2O by transient nuclear magnetic resonance method. Temperature dependence of T1 is similar to that of corresponding proton resonance but three to four orders of magnitude smaller than the latter. From the slope of logT1  vs. 1/T curve, activation energy of reorientation of D2O of 6.5–6.8 kcal/mol is obtained in agreement with that from line width transition. Theoretical values of T1 minima were in good agreement with the observed. Direct measurement of reorientation rate is made by observing a signal recovery from saturation of one of the two deuteron sites of D2O due to the exchange with unsaturated spins at the other site. The Arrhenius plot of the reorientation rate down to −170°C determined in this manner smoothly connects to that derived from the line width transition. A revision of the previous treatment of line width change is described and the reorientation rates of Ba(ClO3)2D2O are re-evaluated according to this method. A satisfactory agreement is found among the conclusions from the three different types of experiment, T1, the line width transition and the directly measured reorientation rate. The motion is a random reorientation of D2O with a rate governed by an activation process of 7 kcal/mol.
Copper Catalyzed Oxidation of As(III) by Peroxydisulphate
Authors: Bhargava A P , Gupta Y K
Published: July 2006

A kinetic study of the oxidation of As(III) by peroxydisulphate catalyzed by Cu(II) has been made. The rate has been measured by estimating As(III) by the permanganate. The data follow the rate expression,

(Remark: Graphics omitted.)

A chain mechanism has been suggested in which the decomposition of peroxydisulphate is the chain initiating step. Cu(II) and As(III) participate in the chain propagating steps. Allyl acetate and Mn(II) inhibit the reaction. The mechanism also involves a complex formation between Cu(I) and As (III) with an equilibrium constant, K2, having a value of about 1475 m−1at 35°C. Energy and entropy of activation have been found to be 24190 calories and +10.46 e. u. respectively.
Distribution of Some Minor Elements in Sulfide Ores from the Hitachi Mine, Ibaraki Prefecture, Japan
Authors: Hamada Shuichi , Sato Ryuji , Shirai Toshiaki
Published: July 2006

The contents of some minor elements in copper-bearing ores from the Fujimi ore deposit No 5, the Hitachi mine, were determined. The selenium content in 46 samples was found to vary from 0.5 to 117 ppm. Though selenium seems to be concentrated in the ores rich in chalcopyrite, that is not always the case, as there are pyrite-rich ores with higher selenium contents than those rich in chalcopyrite. The average value of the atomic ratio of Se/S in the pyrite ores was calculated to be 3.48×10−5; this value was larger than those found for the ores from the Minenosawa and the Chichibu mines, and about the same as those found for the ores from the Nakase, the Ashio, and the Hanaoka mines. The variations with depth in the atomic ratios of Se/S and Co/Ni are closely related to each other. The atomic ratio of Se/S increased with an increase in that of Co/Ni. It has been concluded that selenium is concentrated in the pyrite ores of the high-temperature-type rather than in those of the low-temperature-type. The mercury content was small in general, but a large content of mercury was observed at the depth where the values of the atomic ratios of Se/S and Co/Ni were at their maxima.
Spectroscopic Studies of Mixed Amine Carbonyl Complexes of d6 Structure. II. Solvent Effect on the Ultraviolet and Visible Absorption Spectra of Diamine-tetracarbonyl Complexes of Chromium(0), Molybdenum(0) and Tungsten(0)
Authors: Saito Hide , Fujita Junnosuke , Saito Kazuo
Published: July 2006

Absorption bands, especially metal to amine charge transfer bands of bipyridyl- and phenanthroline-tetracarbonyl chromium (0), molybdenum (0) and tungsten (0) are shifted in various solvents by less than 4500 cm−1. The shift is discussed in accordance with McRae’s equation, which was derived with the point-dipole approximation. The solvents can be classified into two groups, the alcohol and the ester group. When three constants corresponding to (1) the interaction between induced dipoles of the solute and of the solvent, (2) the interaction between permanent dipole of the solute and induced dipole of the solvent, and (3) the interaction between permanent dipoles of the solute and of the solvent, are duely chosen for the two groups of solvent individually, the experimental values are satisfactorily accounted for. Short range interactions, such as hydrogen bonding can be ignored.
A Kinetic Study of the Free-Radical Bulk Polymerization of Ethylene
Authors: Machi Sueo , Sakai Takashi , Suganuma Fujio , Kagiya Tsutomu
Published: July 2006

The bulk polymerization of ethylene was carried out under mild conditions, i. e. pressures of from 183 to 400 kg/cm2 and temperatures of from 30 to 140°C, using azobisisobutyronitrile as an initiator. In polymerization at the low temperature of 40°C, both the polymerization rate and the molecular weight of the polymer formed increased with the reaction time. At the above temperature, the polymerization rate was shown to be proportional to the amount of initiator, and the molecular weight was found to be independent of it. Furthermore, both the polymerization rate and molecular weight were found to be proportional to the 2.5th power of ethylene fugacity. The dependencies of the polymerization rate and the molecular weight on the reaction time decrease with the rise in reaction temperatures from 30 to 100°C. A kinetical discussion indicated that the rate of termination is almost zero at 30–40°C, but that it increases with the temperature. The polymerization rate and the molecular weight were shown to be proportional to the 0.8 and 0.2th powers of the amount of the initiator. The activation energy of the initiation reaction was evaluated to be ca. 27 kcal/mol.
Mechanism of the Gas-phase Oxidation of Propylene in a Propylene-excess Atmosphere under Pressure
Authors: Masai Mitsuo , Echigoya Etsuro , Morikawa Kiyoshi
Published: July 2006

The mechanism of the oxidation of propylene is studied through the addition of t-butyl hydroperoxide, acetaldehyde, or propionaldehyde to the reactant (propylene and oxygen), and also through the direct addition of the products of the (C3H5Br+O2 or CH3CHO+O2) reaction to propylene. The following conclusions are reached: acetaldehyde and not propionaldehyde is responsible for chain-branching, acetaldehyde is formed from the allyl peroxy radical alone, propylene oxide is formed mainly by the reaction of the acetyl peroxy radical with propylene, the allyl peroxy radical probably contributes to the formation of propylene oxide, propionaldehyde, and acrolein in an equal extent, and the recombination of radicals is highly retarded in this propylene-excess system. On the basis of the data obtained, a plausible reaction scheme is proposed.
Reactions of Triethylaluminum with α,β-Unsaturated Carbonyl Compounds
Authors: Baba Yoshio
Published: July 2006

The reactions of triethylaluminum and its various ether adducts with α,β-unsaturated ketone, aldehyde, ester, and methyleneanthrone have shown that the addition occurs mainly at the 1,2-positions of the carbonyl function, and not at the 1,4-positions as has been observed in the Grignard reaction. The mode of addition was discussed in view of the reactivity of the organometallic compound and the steric factor of the unsaturated carbonyl compounds.
On the Structures of Alkali Polyaluminates
Authors: Yamaguchi Goro , Suzuki Kazutaka
Published: July 2006

Besides the so-called β-Al2O3 (R2O·11Al2O3; R=Na or K), there have been found two kindred compounds with approximate formulas, R2O·7Al2O3 (β′-Al2O3) and R2O·5Al2O3(β″-Al2O3). The structure determination of the latter two compounds was undertaken; the results are compared with the structure of β-Al2O3 in the present paper. These three structures are composed of spinel layers of the same configuration. The structures of β and β′ are very similar to each other, both equally bearing a layer-stacking according to a two-fold screw symmetry, while β″ differs from these two in exhibiting another way of layer-stacking, according to a three-fold screw symmetry.
Dihydroxyquinoxaline Studies. Solubility, Ionization Constant, and Chelating Behavior
Authors: Oguchi Shoshichi
Published: July 2006

The solubility, ionization constant, and chelating behavior of dihydroxyquinoxaline,. mainly 5,8-dihydroxyquinoxaline (5,8-DHQ) derivatives, have been measured and will be discussed. The introduction of a hydroxyl group into quinoxaline greatly lowers the solubility. The order of the decreasing solubility of 2,3-disubstituted 5,8-DHQ in water (at 20°C) is: O(CH2)2OC2H5<H<OH<CH3<C6H5<OC2H5<Cl<SH<SC2H5. For 5,8-DHQ the introduction of electron-repelling groups into 2,3-positions raises both the pKNH and pKoH values, while the introduction of electron-attracting groups into the same positions lowers both pKNHand pKoH. 5,8-DHQ, and its derivatives form colored precipitates with metal ions, but some derivatives which have pKNH values lower than zero fail to show any precipitation or coloration. 6,7-DHQ forms precipitate, and the precipitation colors distinctively with Cr(III) or Fe(II). The composition and stability constant (K) of copper(II) chelates of 5,8-DHQ and its derivatives in a dioxane-water (10 : 90 v/v) solution were studied spectrometrically. The copper chelate of 5,8-DHQ had a metal: ligand ratio of 1 : 1 and a logK value of 6.28 at pH 4.0. The structures of these copper chelates will be proposed.
Study on Fragmentation Process of Thymidine by Mattauch-Herzog Geometry High Resolution Mass Spectrograph
Authors: Tsunakawa Sukenari
Published: July 2006

High resolution mass spectra of thymidine were studied by Mattauch-Herzog geometry mass spectrograph. The element map of it was presented and the fragmentation processes were shown by solid or dotted lines on the map. The spectra were measured with higher accelerating voltages (about 0.1%) in order to obtain many metastable peaks on the photographic plate. By a single focusing mass spectrometer ten metastable peaks were measured and “intentionally defocused” high resolution spectra gave twenty five diffused peaks with slight shifts to the high mass region though no metastable peaks were observed under normal operating conditions.
The n→π* Bands of Phenyl Carbonyl Compounds, α-Diketones, and Quinones at Low Temperatures
Authors: Kuboyama Akira , Yamazaki Ryuichi , Yabe Sanae , Uehara Yoshio
Published: July 2006

The positions and intensities of the n→π* absorption bands in solutions at 77°K (in the rigid glass state) and at 201°K (in the liquid state) have been studied in comparison with those at room temperature. At 201°K the positions and intensities are similar to those at room temperature. At 77°K some distinct facts have been found in EP (ether-isopentane (1:1) mixture) which are different from those which hold in the liquid state: 1) In desoxybenzoin the absorption is remarkably weak in intensity. 2) In some α-diketones and β-naphthoquinone, the n→π* bands shift greatly to the blue. 3) In β-naphthoquinone the absorption is remarkably strong in intensity. Discussions of the obtained results have been presented.
Studies of the Interaction between the Hexyl Anion and Alkali Metal Ions
Authors: Motomizu Shoji , Tôei Kyoji , Iwachido Tadashi
Published: July 2006

The Hexyl(2,4,6,2′,4′,6′-hexanitrodiphenylamine) anion forms ion-pairs with alkali metal cations to some extent in an aqueous solution. The association constants of these ion-pairs were determined both in nitrobenzene by conductivity measurements and in water by the solvent extraction method. The association constants in nitrobenzene (KoMR) decrease in the following order: Li>Na>K>Rb>Cs. The plot of log KoMR against the ionic potential of the alkali metal ions was found to be linear. In nitrobenzene saturated with water, however, the constants vary from 2 to 4. In water the asscoiation constants (KaMr) vary from about 10 to 400, and the value increases as follows: Li<Na<K<Rb (<Cs). A plot of log KaMR against the reciprocal of the effective diameter of the hydrated alkali metal ions was found to be linear.
The Spectrophotometric Determination of Palladium with Chromazurol S
Authors: Ishida Ryoei
Published: July 2006

A simple spectrophotometric method for the determination of palladium was studied, using chromazurol S as a reagent. Palladium (II), in a slightly acidic or a nearly neutral solution, reacts with chromazurol S to form blue or red complexes, each consisting of one molecule of the reagent and one atom of palladium. The maximum absorption wavelengths of blue and red complexes are respectively 596 mμ and 500 mμ, against the reagent blanks. The color development of the blue complex formed in a slightly acidic medium is more sensitive, therefore, it was applied to the spectrophotometric determination of palladium. Several conditions for the color development were investigated; a calibration curve was made under the optimum conditions; and the influences of coexisting ions were also investigated. The blue complex gives a maximum absorbance at 596 mμ in the pH range from 4.3 to 5.3. About a 2-fold excess of the reagent over the palladium concentration is necessary in order to obtain the maximum color intensity. The color development is almost instantaneous, and the absorbance remains constant for at least 4 hr. The order of the addition of reagents has no effect upon the absorbance. The color system obeys Beer’s law over the concentration range up to 70 μg of palladium per 10 ml. The molar extinction coefficient at 596 mμ is 18600, which corresponds to a sensitivity index of 0.0058 μg/cm2 for an absorbance of 0.001. Sulfate, chloride, fluoride, phosphate and acetate ions do not interfere with the color reaction. Thiosulfate ion and polycarboxylate ions such as oxalate, citrate and EDTA etc. bleach the color of the complex. Cations such as Sc(III), Y(III), Th(IV), U(VI), Be(II), Al(III) and Cu(II) ions cause an over-estimation of palladium; the interference by these cations except copper, however, could be eliminated by the addition of appropriate amounts of either sodium fluoride or sodium phosphate as masking agent.
Catalysis in Peptide Synthesis with Active Esters. II. Effects of Concentrated Carboxylic Acids on the Aminolysis of Benzyloxycarbonyl-l-phenylalanine p-Nitrophenyl Ester in Dioxane
Authors: Nakamizo Nobuhiro
Published: July 2006

The kinetics of the aminolysis reaction of benzyloxycarbonyl-l-phenylalanine p-nitrophenyI ester with glycine t-butyl ester in dioxane were studied in the presence of high concentrations of several carboxylic acids. Bell-shaped curves were obtained when the rate constants observed for the trimethylacetic acid-, acetic acid-, and monochloroacetic acid-catalyzed reactions were plotted against the logarithms of the reciprocals of the acid concentrations. Cyanoacetic acid and trichloroacetic acid did not accelerate, but, rather, retarded the reaction. In the mathematical derivation the catalyst apparently exhibits no accelerating effect, if k0K>kcat, where k0 and kcat are the uncatalyzed and the true catalyzed rate constants respectively, and where K is the acidbase equilibrium constant between the nucleophile and the catalyst in a given solvent. The true catalyzed rate constants, kcat, from which the effect of the protonation of the nucleophile had been eliminated were estimated for the trimethylacetic acid- and acetic acid-catalyzed reactions. The fact that the kcat value (63m−2 min−1) for trimethylacetic acid, the weaker acid, was greater than that (53m−2 min−1) for acetic acid strongly supports the bifunctional, concerted mechanism presented in the preceding paper.
Spectrophotometric Studies of the Copolymer of l-Tryptophan and l-Glutamic Acid in an Aqueous Solution
Authors: Ohnishi Akio , Hayashi Katsuya , Noguchi Junzo
Published: July 2006

The synthetic copolymer of l-tryptophan and l-glutamic acid exhibited two specific bands, around 292 mμ and 234 mμ, in the difference spectrum at pH 4.68 vs. pH 7.60 in a 0.1m phosphate buffer. The former, that at 292 mμ, might be caused by the red shift of the ordinary absorption band around 280 mμ, and the latter, that at 234 mμ, by the red shift of the far-ultraviolet absorption band, around 220 mμ, of the tryptophanyl residue in the copolymer. This specific peak at 234 mμ in the difference spectrum of the tryptophan copolymer may be distinguished from that at 222 mμ, which is due to the hyperchromisity (n→π* transition) of the amide group in the peptide bond reported with poly-l-glutamic acid. The peak at 230–235 mμ appearing in the difference spectrum between native and denaturated proteins may be due to the same red shift (π→π* transition) of the far-ultraviolet absorption band of the tryptophanyl residue as that shown by the tryptophan copolymer. The difference in absorption at 234 mμ was five times larger than that at 292 mμ, and both of them increase proportionally with a lowering of the pH. The relation between the difference absorption and the pH was quite similar to that between the helical content and the pH. The relative fluorescence intensity of the tryptophanyl residue was also depressed with a lowering of the pH, and the profile of the pH-dependence curve on the fluorescence intensity was almost identical with the titration curve of the copolymer. Therefore, it may be said that the appearance of the difference spectrum at 234 mμ corresponds to the formation of the α-helix in polypeptide and that the protonation of the glutamyl residue induces the quenching of the fluorescence of the tryptophanyl residue.
The Optical Resolution and Circular Dichroism of Cobalt(III) Complexes of the [Co(O–O)2(O–N)]2− Type
Authors: Yamasaki Kiyoshi , Hidaka Jinsai , Shimura Yoichi
Published: July 2006

Four cobalt(III) complexes of the tris-chelate type containing two dicarboxylate anions and one aminocarboxylate anion have been newly prepared and separated into their optical isomers by a chemical resolution method: they are bismalonatoglycinato-, bismalonato(l-alaninato)-, bisoxalato(l-alaninato)- and bisoxalato(β-alaninato)-cobalt(III) complexes. The diastereomeric isomers of bisoxalato(l-alaninato)cobalt(III) complex have also been separated by the solubility difference between their barium salts. The absorption spectra, circular dichroism spectra and rotatory dispersion of these complexes have been measured and discussed in relation to the splitting of the d–d transition bands. The absolute configurations of the complexes have been inferred from their circular dichroism spectra. The additivity of configurational and vicinal contributions to the optical activity has been substantiated for the bisoxalato- and bismalonato-(l-alaninato)-cobalt(III) complexes, and some considerations concerning the less stereospecific formation of the l-alaninato diastereomeric isomers have been made in relation to the additivity.
Decomposition of Formic Acid on Silver Catalyst —Adsorption Measurement during Surface Catalysis—
Authors: Fukuda Kenzo , Onishi Takaharu , Tamaru Kenzi
Published: July 2006

The mechanism of the decomposition of formic acid over reduced silver catalyst has been studied by means of the adsorption measurement during surface catalysis. It was found that the decomposition of formic acid on the silver catalyst at 100°C was first order at lower pressures of formic acid, while at medium pressures it was zero order, the reaction rate being independent of the pressures of ambient formic acid; in the first region the amount of adsorbed formic acid was proportional to the pressure of formic acid, and in the second region it was constant, independent of the pressure of formic acid in the ambient gas. The second region corresponds to “saturation” in an ordinary sense. At pressures of formic acid higher than that in the “saturation” region the amount of adsorbed formic acid increases again linearly with the pressure of formic acid. The linear relation between the reaction rate and the amount of formic acid adsorbed during the reaction was observed over the whole range of the pressure of formic acid studied. It is accordingly concluded that a surface unimolecular reaction in terms of the adsorbed formic acid is the ratedetermining step. The exchange reaction of surface formic acid with those in the ambient gas was studied and it was demonstrated all the formic acid in the adsorbed layer accordingly participated in the exchange reaction. The numbers of surface silver atoms occupied by one molecule of adsorbed formic acid at the saturation points at various temperatures are estimated from the number of surface silver atoms and the amount of formic acid adsorbed at the zero-order kinetics. The number of surface silver atoms occupied by one molecule of adsorbed formic acid increases linearly with temperature.
Spectroscopic Studies on Radicals Produced from Acridine and Acridan in γ-Irradiated Rigid Solutions at −196°C
Authors: Shida Tadamasa , Kira Akira
Published: July 2006

Dilute solutions of acridine in ethers and amines were frozen at −196°C to a glassy solid and were γ-irradiated. Electrons ejected by ionization are effectively scavenged by acridine to produce acridine anions which are the sole species having an electronic absorption band in the visible region. In alcohol and ester matrices the anion abstracts a proton from the matrix molecule even at −196°C and yields a semiquinone radical equivalent to the species formed by H-atom abstraction at the 9-position of acridan (dihydroacridine). Acridan in γ-irradiated butyl chloride matrix forms acridan cation which has a characteristic absorption band at 500–750 mμ. Detachment of a proton from the acridan cation produces another semiquinone radical identifiable with the species formed by H-atom abstraction at the 10-position of acridan. Both radicals have a similar yet clearly distinguishable absorption band in the visible region.
The Effects of Organic Additives on the Solubilities and CMC’s of Potassium Alkyl Sulfates in Water. I. The Effects of Several Hydroxy Compounds
Authors: Shirahama Keishiro , Hayashi Makoto , Matuura Ryohei
Published: July 2006

The solubilities and critical micelle concentrations (CMC) of potassium dodecyl sulfate (KDS) and hexadecyl sulfate (KHS) were measured in methanol-, ethanol-, 1-propanol-, ethylene glycol-, 1,2-propanediol-, and glycerol-water mixed solvents over the temperature range from 0 to 40°C. It was found that the higher the hydroxy group density in the solvent, the less the effects on both the solubility and the CMC, and that the presence of an alkyl group in the solvent causes a greater temperature-dependence in the solubility. The solvent effects on the CMC and on the single-ion dispersion were discussed separately. An effect of a net-work structure formed between the hydroxy compound and water on the solubility is suggested. Solvent effects on the alkyl group and the ionic group of a surfactant molecule were separated by considering the difference between the standard free-energy change for the solution process of KHS and that of KDS. The effects on the Krafft point were also discussed in term of the above suggestions.
Paramagnetic Susceptibilities of Some DPPH Derivatives
Authors: Ohigashi Noriko , Inokuchi Hiroo
Published: July 2006

The static magnetic susceptibilities of poly crystalline samples of 1,1-bis(p-chlorophenyl)-2-picrylhydrazyl (Cl-DPPH), 1,1-bis(p-bromophenyl)-2-picrylhydrazyl (Br-DPPH), and 1,1-bis (p-methoxyphenyl)-2-picrylhydrazyl (CH3O-DPPH) were measured in the temperature range from 10°K to 300°K. These three substances showed strong paramagnetism comparable to that of DPPH, having relatively weak interaction energies between their unpaired electrons. Of these, the paramagnetic susceptibility of CH3O-DPPH was analysed on the basis of the singlet-triplet model with the energy separation of 2J/k=33.8°K.
Electrophoretic Behavior of Micelles of a Polyether-sulfate Type Surfactant
Authors: Tokiwa Fumikatsu , Ohki Kenji
Published: July 2006

The electrophoretic properties of the micelle of sodium dodecyltrioxyethylene sulfate have been studied in the presence of various types of inorganic z+-z− electrolytes and in the presence of organic electrolytes (RNH3Cl and RCOONa) of various sizes. The effect of the type of electrolytes on the zeta potential of the micelle, ζ, is similar in tendency to the effect to be expected on the basis of the Gouy-Chapman equation for spherical colloid particles. The valence of counterions has a considerable effect on ζ, but that of the co-ions has only a slight effect. With respect to the size of ions, counter-ions (RNH+) appreciably influence the potential of the micelle, whereas co-ions (RCOO−) influence the potential almost not at all. The value of ζ slightly increases, and then steeply decreases, with an increase in the size of the cations through a maximum value.
Reactions of Singlet Oxygen and Half-reduced Oxygen which are Produced Simultaneously by the Interaction of Triplet Dye and Oxygen
Authors: Usui Yoshiharu , Iwanaga Chieko , Koizumi Masao
Published: July 2006

Under experimental conditions in which the interaction between triplet dye and oxygen is an initiating process (D–O mechanism), the photosensitized oxidation of leucofluorescein in the aqueous solution (reaction (1)) has been found to decrease in rate with the increasing oxygen concentration and that the magnitude of the retarding effect of oxygen is almost the same independent of sensitizing dye. This is in sharp contrast to the kinetic feature of the oxidative photobleaching of dye (reaction (2)), where the rate becomes constant beyond a certain small oxygen concentration. On the basis of these findings, it has been proposed that in reaction (1), 1O2 plays a dominant role and it is deactivated by process 1O2+3O2→23O2. As to reaction (2), strong evidence has been presented for the view that the interaction of triplet dye and oxygen in the aqueous solution produces a rather stable D+···O2− of which only a small portion decomposes irreversibly. The principal evidence is as follows; 1) the free half-oxidized dye (produced by the reaction between triplet dye and [Co(Ox)3]3− was found to oxidize FH2 with a high rate and its decay was found to be accelerated by the addition of FH2; 2) the decay of the half-oxidized species (first order decay!) produced in the aerated aqueous solution, on the other hand, was not affected by FH2 under otherwise similar conditions as in (1).
An MO-Theoretical Study of the E2 Reaction of Ethyl Chloride
Authors: Hao Hideyuki , Fujimoto Hiroshi , Fukui Kenichi
Published: July 2006

The change in the electronic state in the course of the E2 reaction of ethyl chloride was followed by means of the extended Hückel calculation. A model is adopted in which the nucleophilic reagent approaches the trans-β-hydrogen atom. The valence-inactive population of the trans-β-hydrogen atom in the lowest unoccupied (LU) molecular orbital (MO) was employed as a theoretical reactivity index. The theoretical conclusion derived was consistent with the experimental results.
On the Order of Isotopic Exchange Reactions
Authors: Takaishi Tetsuo
Published: July 2006

The conditions for the applicability of the McKay law were studied. It was concluded that the first order kinetics no longer holds when the concentrations of intermediates cannot be disregarded when compared with those of reactants and products and when the rate determining step cannot be specified. Some reactions were illustrated in which McKay’s law cannot be applied.
On the Presence of Tetrafluoroborate Ions in Natural Waters
Authors: Onishi Tomio
Published: July 2006

Tetrafluoroborate ions (BF4−) can be formed only in a strongly acid solution. Certain acid thermal waters and volcanic gases in the active volcanic zone can be expected to be the media of BF4− formation. When BF4− is supplied to natural waters, its rate of hydrolysis is relatively low, suggesting the possibility of the occurrence of BF4− in natural waters. The contents of BF4− have been determined in various thermal water samples from a volcano in Satsuma Iwo-jima, and the presence of BF4− confirmed. The BF4− content in the condensed water of volcanic gas from a fumarole with the high temperature of 745°C is 304 mg/l, which is 26% of the total F, and 79% of the total B content. The BF4− content in a sample of water from Kitabira Spa (pH 1.1) is 8.0 mg/l, which is about 50% of the total F or B. However, the presence of BF4− can not be confirmed in ordinary natural waters such as land and sea waters.
Gas Chromatography of Rare Earth Chelates of Pivaloyltrifluoroacetone
Authors: Shigematsu Tsunenobu , Matsui Masakazu , Utsunomiya Kei
Published: July 2006

The gas chromatographic behavior of Sc, Y, and rare earth chelates of a new β-diketone, pivaroyltrifluoroacetone (PTA), was investigated. PTA was synthesized by a Claisen condensation from pinacolin and ethyltrifluoroacetone. Sc, Y, Nd, Sm, Eu, Gd, Tb, Dy, Er, Yb, and Lu PTA chelates were prepared. Their elemental analyses and infrared spectra indicated that they were anhydrous tris chelates, and the TGA curves of the chelates proved their good volatile characteristics, showing approximately a 100% weight loss. Gas chromatograms of all the chelates and of mixtures of Sc, Y, and several rare earth chelates were obtained. Some relationships were observed between the retention time, the volatilization temperature, and the ionic radius of the central metal: With the decrease in the ionic radius, the retention time of the chelate decreased and the volatilization temperature became lower.
Crystal Growth of the Phosphate Coating on Iron and Steel
Authors: Umegaki Takao , Okabe Taijiro , Omori Keiichi
Published: July 2006

Crystal growth of the phosphate coating on steel and pure iron was investigated by microscopic observation and X-ray diffraction. β-Hopeite was recognized as a main constituent of the phosphate coating. From the experimental results obtained in this investigation and the crystal structure of β-hopeite proposed by Gamidov and Galovachev (Dokl. Akad. Nank, SSSR,  150, 2, 381, (1963)), it was concluded that the bonding of the (010) plane of β-hopeite to the (100) plane of iron is most favorable for atomic arrangement of the phosphate coating.
Nickel(II) and Copper(II) Complexes of C,N-Disubstituted Salicylideneimines with Steric Hindrance
Authors: Yamada Shoichiro , Takeuchi Akira , Yamanouchi Kuniko , Iwasaki Katsumoto
Published: July 2006

Many new nickel(II) and copper(II) complexes (abbreviated as M(X-sal.R)2) of Schiff bases were obtained from C-substituted salicylaldehydes and 2,6-dimethyl- and 2,6-diethyl-aniline, where X denotes 5-Br, 5-Cl, 5,6-benzo, 5-NO2 and 3-CH3O. For X=5-Cl, the corresponding nickel(II) complex with R=2,6-dichlorophenyl was also synthesized. All these nickel(II) complexes consist of square-planar molecules in the solid state and in non-donor solvents. The nickel (II) complexes, when dissolved in pyridine, either take up two pyridine molecules to form six-coordinated complexes or retain the original planar configuration. The configuration in pyridine depends upon the nature of X, demonstrating that the effect of X on the electronic state of the ligand may also be important, besides the steric factor, in determining the configuration of the nickel(II) complexes. The corresponding copper (II) complexes, which are square-planar in the solid state and in non-donor solvents, combine with one or two pyridine molecules, when dissolved in pyridine.
Reaction of Salicylamine with α-Dicarbonyl Compounds. I. Transamination Reaction
Authors: Kanatomi Hajime , Murase Ichiro
Published: July 2006

The reactions of salicylamine with α-dicarbonyl compounds were examined in the hope of obtaining 2,2′-bibenzoxazine derivatives I or Schiff bases II as two-to-one condensation products; however, salicylidenesalicylamine was isolated in every case. It was found that the reaction proceeded through transamination, followed by trans-Schiffization between salicylamine and α-dicarbonyl compounds. The mechanism and the conditions under which the reactions take place were investigated.
Trimethylenediamine Complexes. I. Some Trimethylenediamine Complexes Derived from trans-[CoCl2tn2]Cl in Methanol
Authors: Kawaguchi Hiroshi , Yano Naomichi , Kawaguchi Shinichi
Published: July 2006

Several diacidobis(trimethylenediamine)cobalt(III) complexes including nitrate, nitrite and thiocyanate ions as ligands have been prepared by ligand substitution reactions of trans-dichlorobis(trimethylenediamine)cobalt(III) chloride in methanol. All these compounds were assumed to have the trans configuration according to the Baldwin’s criterion based on the CH2 rocking vibration. Isomeric pairs of chloronitro and chloronitrito complexes were also characterized by means of infrared data.
Solvent Effect in a Partial Asymmetric Synthesis. II
Authors: Inamasu Shuji , Horiike Michio , Inouye Yuzo
Published: July 2006

Further evidence for the unambiguous solvent polarity dependence of the stereochemistry in the base-catalyzed Michael type condensation was provided by the systems involving (−)-menthyl chloroacetate and methyl acrylate, and (−)-menthyl chloroacetate and (−)-menthyl acrylate with a modification of the work-up. The electrostatic control of the stereoselectivity was interpreted by the same theorem developed in the previous study and some novel features found for the present systems were discussed.
Nonequilibrium Thermodynamics of the Relaxing System Subject to Multinomial Distribution
Authors: Ishida Kenji
Published: July 2006

It has been shown that the relaxation process in a system of noninteracting particles in contact with a heat bath, on the assumption that the system is in local equilibrium, can be described by the Markov process homogeneous in time, and that the solution of the Markov process is a multinomial distribution. The nonequilibrium thermodynamics for such a relaxing system was formulated by means of the stochastic entropy production which can be derived by the probabilistic version of classical entropy production. As a special case, the stochastic nonequilibrium thermodynamics for the relaxing system of identical harmonic oscillators was discussed.
Spectroscopic Behavior of Würster’s Blue Perchlorate and N-Ethylphenazyl Crystals
Authors: Sakata Tadayoshi , Nagakura Saburo
Published: July 2006

The electronic absorption spectra of Würster’s Blue perchlorate and N-ethylphenazyl in solid were measured at various temperatures ranging from 48°K to 300°K. In both cases, strong bands due to the charge-transfer between the half occupied orbitals of respective component radicals were observed in near infrared region. This assignment of these bands was supported by the polarized absorption measurement carried out with the Würster’s blue perchlorate single crystal. The charge-transfer band of solid Würster’s blue perchlorate was found to increase its intensity with decreasing temperatures; in particular, the increasing tendency became predominant below the phase transition point (186°K). The similar tendency was also observed for solid N-ethylphenazyl. The temperature dependence of the band was found to be closely related with the population of triplet excitons determined from the measurement of magnetic susceptibility or paramagnetic resonance. The separation J between the ground singlet state and the thermally accessible triplet state was determined from the analysis of the temperature dependence of the charge-transfer band to be 235 cm−1 and 320 cm−1 for Würster’s blue perchlorate and N-ethylphenazyl, respectively.
The Molecular and Crystal Structure of Bis(2-hydroxyethylimino-pyruvato)copper(II) Tetrahydrate
Authors: Iijima Kinya , Oonishi Isao , Muto Fumio , Nakahara Akitsugu , Komiyama Yoshimichi
Published: July 2006

A new copper(II) chelate of the Schiff base derived from pyruvic acid and ethanolamine has been prepared. The crystal structure of this complex, [Cu(pyv=etham)2]·4H2O, has been determined from three dimensional X-ray diffraction data. The dimensions of monoclinic cell are a=6.50Å, b=19.75Å, c=7.26Å, β=113.0° and Z=2. The space group is P21⁄n. The structure has been refined by three dimensional difference syntheses to R=0.126. It has been disclosed that copper (II) links to the 2-hydroxyethyliminopyruvate anion through the terminal carboxylate group, and the nitrogen of the Schiff base linkage. Having a center of symmetry, the complex molecule is in the trans-configuration and has normal bond distances and angles. The coordination around copper(II) is square planar; the Cu–O and Cu–N distances are 1.92 and 2.00Å, respectively. Two additional oxygen atoms of the water molecules at 2.57Å complete a distorted octahedron around copper(II). The complex molecules are held together in the crystal by the O–H···O hydrogen bonds, forming a three dimensional network.
Preparation of Star-Type Graft Copolymer through the Polymerization of Methyl Methacrylate with Use of the Potassium Complexes of Polystyrene having a Benzophenone Unit
Authors: Nobutoki Koji , Sumitomo Hiroshi
Published: July 2006

Polystyrene ketone possessing a benzophenone structural unit in the middle part of the chain was synthesized by the coupling reaction of one-ended living polystyrene with 2,4′-dichlorobenzophenone. Polystyrene ketone potassium ketyl was prepared by the reaction of polystyrene ketone with an equivalent amount of potassium naphthalene complex in tetrahydrofuran. Polystyrene ketone potassium dianion was also formed with excess potassium in the solvent. These polystyrene ketone potassium adducts induced a quantitative polymerization of metyl methacrylate. Gross polymer from each of the reaction systems was elution-fractionated into four fractions in which a new class of star-type graft copolymer was included together with polystyrene and polymethyl methacrylate. Each fraction was characterized by means of the measurements of the yield, molecular weight and styrene content. Consideration was also made on a possible mechanism of the polymerization.
Thermodynamic Properties of Galvinoxyl Radical and Its Phenol Derivative; Mechanism of the Phase Transition
Authors: Kosaki Akio , Suga Hiroshi , Seki Syûzô , Mukai Kazuo , Deguchi Yasuo
Published: July 2006

Measurements of heat capacity of Galvinoxyl radical and its phenol derivative were carried out in the temperature region from 12 to 300°K. Galvinoxyl radical exhibits a phase transition of first-order nature at 81.5°K which corresponds to the susceptibility anomaly already measured. The enthalpy and entropy of transition amount to 1504.6 J/mol and 18.67 J/(°K·mol), respectively. The entropy change, which corresponds formally to R In 9.45, cannot be explained by taking only the magnetic contribution. On the other hand, its phenol derivative, the corresponding diamagnetic substance, has not thermal anomaly in the above temperature region. X-Ray diffraction patterns at room temperature for both substances agree well with each other in their diffraction angles. From these experimental findings, it seems to be plausible that a kind of transformation of the crystal structure of Galvinoxyl radical takes place at the transition point which may be induced by a pairing of magnetic spins between neighboring molecules.
Influence of Impurities on Phosphate Coating Formation
Authors: Umegaki Takao , Ito Hiroshi , Okabe Taijiro
Published: July 2006

The applicability of wet-process phosphoric acid containing such impurities as Al3+, Ca2+, Fe3+ and SO42− was examined. From the viewpoint of the corrosion resistivity of the phosphate coating, Al3+ ion was found to be the most undesirable contaminator. NaF was recognized as the most effective masking reagent for an elimination of Al3+ hindrance. SO42− also affected the phosphate coating formation, but the presence of less than 1% SO42− did not disturb the coating formation when an appropriate amount of accelerator was added to the phosphatizing solution.
Transition Energy Diagram for Solvated Electrons and Its Application to the Interpretation of Their Absorption Spectra
Authors: Noda Syozi , Fueki Kenji , Kuri Zen-ichiro
Published: July 2006

The energy levels of solvated electrons have been calculated as a function of the static dielectric constant and of the cavity radius on the basis of a continuous dielectric model with an adiabatic approximation, and a contour diagram has been drawn up for the transition energy of solvated electrons. Using this diagram and the observed absorption spectra, the quantities on solvated electrons in alcohols have been estimated. The cavity radius, R, ranges from 0.9 to 1.6 Å, the charge distribution for the ground state, from 2.4 to 3.2 Å, and the variation in cavity radius, from 0.50 to 0.60 Å, at room temperature. From the calculations of the temperature dependence, d(hv)/dt, of the transition energy, it can be said that, for solvated electrons in alcohols, the contribution to d(hv)/dt of the change in R with the temperature is rather more dominant than the change in the static dielectric constant with the temperature. It has also been found that there exists a correlation between the dR/dt value and the ratio of the number of the OH bond to the total number of bonds involved in each alcohol.
Determination of Kinetic Parameters of the Electrode Reaction of Ethylenediaminetetraacetatoaquochromate(III) Ions by the Potentiostatic Method
Authors: Yamada Akifumi , Tanaka Nobuyuki
Published: July 2006

Kinetic parameters of the electrode reaction of ethylenediaminetetraacetatoaquochromate-(III)/ethylenediaminetetraacetatoaquochromate(II) at the dropping mercury electrode have been determined by the potentiostatic method in sodium chloride solutions of ionic strength 0.5 containing 0.1 m acetate buffer. The measured standard rate constant (ks)ms is 2.1×10−1cm sec−1 and the measured transfer coefficients (αc)ms and (αa)ms are 0.58 for the cathodic and 0.39 for the anodic process. The correction for the effect of the electrical double layer has been made on these parameters. The values obtained are: (ks)corrc=1.7×10 cm sec−1, (αc)corr=0.54 and (αa)corr=0.43. The standard potential −1.220 V vs. SCE determined by the potentiostatic method is compared with −1.218 V vs. SCE obtained by the measurement of the equilibrium potential. These values are in good agreement within the experimental error.
Benzylidenation of l-Sorbose
Authors: Maeda Takashi , Kimoto (née Katsuhara) Mitsuru , Wakahara Shigeru , Tokuyama Kanji
Published: July 2006

The acid-catalyzed benzylidenation of l-sorbose (I) was studied. The reaction by Reichstein’s procedure gave a mixture of two diastereomeric 2,3:4,6-di-O-benzylidene-α-l-sorbofuranoses (III and IV), which were then successfully separated by preparative thin-layer chromatography. The use of slightly acidic conditions yielded l,3:4,6-di-O-benzylidene-β-l-sorbofuranose (XI), l,2:4,6-di-O-benzylidene-α- (XVII and XVIII) and-β-l-sorbofuranoses (XIX and XX), 1,2-O-benzylidene-α-l-sorbopyranoses (XXI and XXII), and 1,3-O-benzylidene-l-sorbose (XXIII). The absolute configurations at the acetal center of the five-membered benzylidene rings were assigned. A reaction sequence (I→(XXI, XXII\ightleftarrowsXXIII)→XI→IV→III) comparable with that of the ethylidenation of I was established.
Polymerization of Formaldehyde in Liquid Carbon Dioxide. I. The Cause of the Polymerizability of the Monomer
Authors: Kagiya Tsutomu , Kondo Masatsune , Narita K\={o}z\={o} , Fukui Kenichi
Published: July 2006

The cause of the polymerizability of formaldehyde in liquid carbon dioxide was studied in connection with the preparation conditions of the monomer. A liquid carbon dioxide solution of the monomer was prepared by two different methods, by means of the pyrolysis of α-polyoxymethylene and by means of that of the hemiformal of polyethylene glycol, under a carbon dioxide stream. By adding various sodium salts to the pyrolysis system of α-polyoxymethylene, the polymerization rate, without the addition of any catalyst, of the monomer thus obtained was found to decrease with an increase in the pKa value of the conjugated acid of the salt. The polymerization rate also decreased with the amount of sodium carbonate added. The hemiformal of polyethylene glycol was prepared by bubbling the gas evolved by the pyrolysis of paraformaldehyde into polyethylene glycol. The amount of acid present in the hemiformal thus obtained increased linearly with the pyrolysis time. The polymerization rate of the monomer obtained by the pyrolysis of the hemiformal increased in proportion to the acid content in the hemiformal. On the basis of these results, the initiation mechanism in the polymerization of formaldehyde without any additional initiator in a liquid carbon dioxide solution was discussed.
Properties of Butyl Acrylate Copolymer with Metal Ionic Crosslinkage
Authors: Hakozaki Jun-ichi , Higashimura Einosuke , Hayashibara Y\={u}ji
Published: July 2006

Some properties of the butyl acrylate-acrylic acid copolymer, which has ionic crosslinkage with a mono- or divalent cation, were observed. The organic solvent resistance tends to increase with an increase in the degree of neutralization with metal ions at room temperature and at 50°C. The tensile and flow properties exhibit a linear with the amounts of metal ions incorporated. The activation energies of the melt viscosity were 7.5, 10.5, and 22.0 kcal/mol for 1, 1/4, and 1/2 of metal-ion equivalents respectively. The stress relaxation behavior was observed at the temperature of 92°C; it was found that relaxation at the highest rate takes place at the initial stage of the relaxation process.
Effect of Some Cationic Detergents on Macromolecularly Stabilised Emulsions with Special Reference to Sodium Alginate and Gum Arabic as Emulsifiers
Authors: Prakash Chandra , Srivastava S N
Published: July 2006

The effect of some cationic detergents viz. cetyl pyridinium bromide, lauryl pyridinium chloride and phenyl trimethyl ammonium chloride has been studied on stabilised by sodium alginate and gum arabic emulsions. Zeta potentials were measured at different concentrations of cationic detergents microelectrophoretically. The particle size was determined microphotographically. With the help of zeta potential and particle size the interaction energies were calculated by summing up attraction and repulsion energies in the light of D.V.O. theory. For attraction energy the van der Waals constant was computed theoretically from the optical data and was obtained to be 6.7×10−14 erg. The interaction energies thus obtained gave very high energy barriers which completely obviated the occurrence of flocculation in primary minima, causing flocculation to occur in secondary minima. The theoretical degrees of aggregation were calculated and plotted at different values of A. The flocculation occurring in the system was observed haemocytometrically by counting the number of singlets and doublets and the degrees of aggregation were calculated. With the help of observed degrees of aggregation the operating value of van der Waals constant has been estimated by interpolating them into the theoretical curves, which is an indirect approach to ascertain the value of van der Waals constant. The values of A obtained are 3.0×10−13 and 2.6×10−13 erg for sodium alginate and gum arabic systems respectively. The binding parameters, number of binding sites available and free energy of adsorption have also been calculated.
Role of Doped Lithium in Nickel Monoxide in the Formation of Higher Valency Nickel Oxides by Anodic Oxidation
Authors: Yoneyama Hiroshi , Tamura Hideo
Published: July 2006

The anodic oxidation and cathodic reduction behavior of a sintered body of lithiated nickel oxide were studied. The electrode with the higher Li content was more active than that with the lower Li content with regard to the electrochemical oxidation and reduction in the potential range between oxygen and hydrogen evolution. The quantity of the higher-valency nickel oxide having an apparent valence state of nickel ions from +8/3 to +4 formed by the anodic oxidation was estimated by measuring the quantity of electricity required for reducing it to −0.14V vs. SCE. This quantity is proportional to the Li content for electrodes containing more than 0.04 atom% of Li.