bluuebunny/crossref_metadata_2025 huggingface dataset:
The Determination of Micro Amounts of Polythionates. III. A Photometric Method for the Determination of Tetrathionate by Means of Its Cyanolysis
Authors: Koh Tomozo , Iwasaki Iwaji
Published: July 2006

A photometric method capable of determining tetrathionate by exactly the same procedure as that used for pentathionate and hexathionate has been established. The optimum pH ranges for the reactions of tetrathionate, pentathionate and hexathionate with cyanide are 8.3–12.1, 8.0–8.8, and 7.8–8.9 respectively for the recommended procedure. From a consideration of the above experimental facts, it has been concluded that tetrathionate can be determined accurately by exactly the same procedure as that used for pentathionate and hexathionate when the pH value is within the range from 8.3 to 8.8. To the standard tetrathionate solution first the buffer solution and then a solution of sodium cyanide are added in order that the pH value of the mixture solution after the addition of the cyanide solution may be within the 8.3–8.8 range. The mixed solution is kept in the thermostat at 40°C for 30 min.; the tetrathionate is thereby converted into thiocyanate quantitatively. After the addition of a ferric nitrate - perchloric acid solution, the absorbancy of the solution of ferric-thiocyanate complex formed is measured at the wavelength of 460 mμ.
Ion-pair Formation of Some Substitution-inert Complexes and Sulfate Ions. Determination of Association Constants Using Polarographic Diffusion Current
Authors: Tanaka Nobuyuki , Ogino (née Ebata) Kazuko , Sato Gen
Published: July 2006

The polarographic diffusion current of some tervalent substitution-inert complex cations decreases by the addition of sulfate. From the change in diffusion current the association constants of substitution-inert complex and sulfate ions are obtained at ionic strength 0.1 (NaClO4) and 25°C. The values are 69±8, 58±8 and 4×10 for [Co(NH3)6]3+–SO42−, [Cr(NH3)6]3+–SO42− and [Cr(H2O)6]3+–SO42 respectively. The formation of [Co(NH3)6]3+–HSO4− is negligibly small compared with that of [Co(NH3)6]3+–SO42−.
The Reaction of Thiols with Propylene Oxide in the Presence of Free Radical Sources
Authors: Takebayashi Matsuji , Shingaki Tadao , Mihara Takakimi
Published: July 2006

The effect of free radical sources on the reaction of thiols with propylene oxide has been studied. In the presence of free radical sources, such as benzoyl peroxide, tetraphenylhydrazine and tetra-methylthiuram disulfide, the reaction gives a single addition product, 1-aryl(or aralkyl)thio-2-propanol, in the same manner as when alkaline catalysts are employed. When l(+)-propylene oxide is used, an optically-active 1-thio-2-propanol is obtained. However, azobisisobutyronitrile manifests no catalytic influence on the reaction. Mercury-vapor light also has no effect on the interaction of thiols and propylene oxide, while the light leads to the decomposition of thiols. The mechanism of the reaction has been discussed in terms of a thiyl anion intermediate.
Color Reactions of Dinitrobenzyl Pyridine and Related Compounds
Authors: Hiraoka Hiroyuki , Hardwick Russell E
Published: July 2006

Upon treatment with certain reagents, the photochromes, α- and γ-(2,4-dinitrobenzyl)pyridine and 2, 4, 2′, 4′-tetranitrodiphenylmethane form stable, blue-colored compounds which probably have chromophoric structures similar to those of the photochromic modifications of the original compounds (two examples of the permanently colored compounds are the n-methyl bases and the products from reactions with epoxy compounds). Kinetic and spectrophotometric studies of these colored compounds and of the anions of the original photochromes are reported. These results are compared with data on the photochromic tautomers.
Electrical Conduction of Organic Semiconductors under High Pressure
Authors: Shirotani Ichimin , Inokuchi Hiroo , Minomura Shigeru
Published: July 2006

The electrical conductivity and the temperature dependency of the organic semiconductors, five simple polycyclic aromatic compounds, two charge transfer complexes and a free radical, have been observed up to 1.6×105 kg./cm2. The conductivity thus increases to 105–107 times that at atmospheric pressure, while the band gaps decrease to about one fifth of the ordinary values. These abrupt changes may be caused by the overlapping of π-electron clouds of adjacent aromatic molecules.
Thermal and Radiation Oxidations of Benzene to Phenol in Aqueous Solutions Containing Metal Ions at Elevated Temperatures. VII. The Mechanisms of Phenol Formation as Studied by Stable Isotopes
Authors: Hotta Hiroshi , Suzuki Nobutake , Abe Toshihiko
Published: July 2006

When benzene was oxidized to phenol in an oxygen-18 enriched aqueous solution of iron and copper sulfates, the oxygen-18 was much concentrated to phenol. The oxygen-18 content depended on the kind of metal ion and on the temperature. This suggests that the oxygen in the phenol produced is donated not only by the molecular oxygen, but also by the water. Therefore, it is assumed for the termination process that phenol is formed by the ionic reactions. Furthermore, when an equimolar mixture of benzene and benzene-d6 was oxidized, the isotope effect of hydrogen, kH/kD, as estimated from the isotopic composition of the phenol produced, was about 1.2. This value seems to be small for the hydrogen abstraction reaction of radicals. Therefore, when we compare these results with the other facts reported previously, the main reaction of the propagation process may be supposed to be the abstraction reaction of hydrogen by phenyl peroxide. In this experiment, it was also found that phenol exchanges hydrogen with water. The rate constant of the exchange reaction was estimated by Bateman’s equation. The rate constant is the highest in the ferric sulfate solution.
The Heterogeneous Adsorption of Carbon Dioxide on the Nickel Surface as Studied by the Isotopic Desorption Method
Authors: Kobayashi Yasushi , Hirota Kozo
Published: July 2006

Further evidence on the adsorptive heterogeneity of the nickel surface has been presented by the use of the technique described in our previous paper. The results support the conclusion already proposed that more than 20–30% of the surface can adsorb carbon dioxide strongly over the temperature range between −78° and 300°C.
The Photolysis of cis-2-Butene and Its Implications for Radiation Chemistry
Authors: Hatano Yoshihiko , Shida Shoji
Published: July 2006

The direct photolysis at 1849 Å and the mercury-photosensitized reaction at 2537 Å of cis-2-butene have been studied in the gas phase at room temperature. It may be considered that the excited singlet state of cis-2-butene is formed in the former, and that the excited triplet state of cis-2-butene is formed in the latter. trans-2-Butene is predominantly produced in the latter, while the decomposition products (e. g., hydrogen, methane, ethane, ethylene, propylene, etc.) predominate in the former. The rates of the formation of all the products are pressure-independent in the former, while in the latter those of all products except trans-2-butene decrease rapidly with an increase in the initial pressure. The rate of trans-2-hutene formation in the latter, however, increases gradually with an increase in the initial pressure until it becomes constant above 100 mmHg. By comparing the pressure-dependence and the product-distribution of these two reactions with the results of the radiolysis of liquid cis-2-butene, one may conclude that the excited triplet state of cis-2-butene contributes chiefly to the formation of trans-2-butene in the radiolysis, while the excited singlet state of cis-2-butene contributes chiefly to the decomposition products.
The Synthesis of Novel α,ω-Oxaalkanedioic Acids with Long Methylene Chain Units
Authors: Saotome Kazuo , Sato Kenichiro
Published: July 2006

α,ω-Oxaalkanedioic acids with the general formula HOOC(CH2)mO(CH2)nCOOH (m, n=3–10, but in unsymmetric structures m=3 or 4) were synthesized. The symmetric acids were prepared by the catalytic dehydration of ω-hydroxyalkanoic acids or by the condensation of ω-chloroalkanoic acids in the presence of alkali hydroxide. The unsymmetric acids (m=3 or 4) were prepared by the reaction of γ-butyrolactone or δ-valerolactone with alkali alcoholates of ω-hydroxyalkanoic acids. The reaction mechanisms were also discussed. In the plots of the melting points of the two unsymmetric series (m=3, 4 in m⁄n) against the carbon atoms in a molecule, the minimum melting points are found at 3/5 and 4/5 respectively.
The Chemistry of Protactinium. I. The Preparation of Protactinium-233 and the Purification of Protactinium-231
Authors: Suzuki Shin , Inoue Yasushi
Published: July 2006

Many methods, such as the co-precipitation method, the solvent extraction method and the ion exchange method, had previously been proposed for the separation and the purification of protactinium. However, these methods have some defects for the separation of Pa-233 produced by the thermal neutron irradiation of thorium dioxide and the purification of commercial Pa-231, when an attempt is made to study the chemistry of protactinium. From the above point of view, a combined method of solvent extraction and anion exchange was investigated. In the present paper, the detailed conditions for the TBP extraction of protactinium from a hydrochloric acid solution and the method for its final purification by anion exchange were described. The present method is comparatively simple and rapid, and chemically- and radiochemically-pure protactinium can thus be obtained.
The Crystal Structure of the Pyrene-Tetracyanoethylene Complex
Authors: Kuroda Haruo , Ikemoto Isao , Akamatu Hideo
Published: July 2006

The crystal structure of the pyrene-tetracyanoethylene (TCNE) complex has been determined by the two-dimensional Fourier method. The monoclinic unit cell dimensions are: a=14.58, b=7.34, c=8.09 Å and β=92.4°. The space group is P21/a. Two pyrene and two TCNE molecules are contained in a unit cell. Pyrene and TCNE molecules are stacked alternately along the c-axis direction, making their molecular planes parallel to each other. The center of a TCNE molecule is not directly above that of the neighboring pyrene molecule, but is displaced considerably along the long axis of pyrene. The mean separation of the molecular plane is 3.32 Å.
The Color Reaction between Chromium(III) Ion and Potassium Ferrocyanide
Authors: Matsumoto Yoshio , Shirai Michiko
Published: July 2006

The observation of the orange-coloring reaction between potassium ferrocyanide and the chromium(III) ion on filter paper and its application in the paper chromatographical analysis of the chromium(III) ion has been reported on previously by the present authors. The color reaction has now been observed in an aqueous solution as well and studied in relation to the reaction temperature, the reaction time, the characteristic absorption, the species of chromium(III) salts, the chromium(III) ion concentration, the pH level, and the presence of an acetic acid buffer, by measuring the absorption spectra of the reaction solutions. The recommended conditions for getting a satisfactory color reaction and a suitable wavelength for the measurement of this color reaction have been presented.
The Coprecipitation Behavior of Strontium with Calcium Oxalate by Precipitation from a Homogeneous System
Authors: Matsui Masakazu
Published: July 2006

The coprecipitation of strontium with calcium oxalate was studied using dimethyloxalate to precipitate calcium from a homogeneous solution. The several effects of the coprecipitation conditions on the distribution coefficients were investigated in the fractional precipitation process of calcium-strontium oxalate mixtures. Regardless of the pH value, the concentration of acetic acid and other factors, the coprecipitation curves of strontium showed similar shapes in almost all cases, although the curves well shifted up and dawn to some extent. It appears to be an anomalous system, because an increase in the fraction of the calcium precipitated tends to decrease the distribution coefficients. It is considered that two coprecipitation mechanisms are involved in the coprecipitation system; one is the surface adsorption on fine crystals, while the other is a normal systematic type. When the adsorption part was removed, it was found that the modified system obeyed the Doerner and Hoskins logarithmic distribution law and that the coefficient gave nearly a constant, 0.1.
The Separation of Alkali Metals as Poly-Iodides by Reversed-Phase Partition Chromatography
Authors: Akaza Ikuko
Published: July 2006

The liquid-liquid extraction of alkali metal ions as their poly-iodides had previously been investigated by the present author. In order to attain a good separation of each metal, this extraction system has now been extended to a reversed-phase partition chromatography in which Kel-F powder was used to support the organic phase of nitrobenzene-iodine-iodide. Column chromatographic separation was carried out in the presence of relatively large amounts of the metals by elution with water and 1 n or 6 n hydrochloric acid - eluting solutions. Chromatographic behavior of each metal ion was investigated and the elution from the column was found to be in the order of Li-Na-K-Rb-Cs. The distribution ratio of the metal ions varied with the quantity of the ions loaded on the column; the smaller the quantity of the ions used, the larger was the distribution ratio obtained. The actual separation of individual metal ions from the mixture was successfully achieved; a minute amount of cesium could be particularly isolated from large amounts of other alkali metals, even in a large volume of the sample solution. Elution curves of various amounts of metal were obtained as an aid to a discussion of the partition on the column. A comparison of the distribution ratio in the liquid-liquid extraction with that in the column chromatography showed that the extraction of the same mechanism proceeded in both cases.
The Formation of Phenolic Ethers by the Acid-catalyzed Condensation of Phenols and Alcohols
Authors: Oae Shigeru , Kiritani Reiko
Published: July 2006

The reaction of phenol with ethyl alcohol in strong acidic media at a somewhat high temperature gave phenyl ethyl ether in a 61% yield. The product isolated from a similar reaction between phenol and n-propyl alcohol was practically pure phenyl n-propyl ether, and no isopropyl isomer was detected. When 18O-labeled phenol was treated with unlabeled ethyl alcohol, the phenetole isolated was found not to contain any excess 18O. The reaction of phenol with ethyl alcohol in the presence of hydrogen chloride gave no isolable amount of phenetole. The mechanism for these reactions was then discussed.
The Reaction of Diphenyl Sulfoxide with Bromine in Aqueous Acetic Acid
Authors: Tagaki Waichiro , Kikukawa Kunihiko , Kunieda Norio , Oae Shigeru
Published: July 2006

When diphenyl sulfoxide was allowed to react with bromine in a mixture of acetic acid and 18O-enriched water, the sulfoxide was recovered, together with a small amount of diphenyl sulfone. The sulfoxide recovered incorporated a very small amount of 18O from the water. Meanwhile, diphenyl sulfoxide was found to undergo a facile oxygen exchange reaction with water in the presence of hydrobromic acid. Possible mechanisms for these reactions have been discussed.
A Kinetic Study of the γ-Radiation-Induced Polymerization of Ethylene at a Normal Temperature
Authors: Machi Sueo , Hagiwara Miyuki , Gotoda Masao , Kagiya Tsutomu
Published: July 2006

The gamma-radiation-induced polymerization of ethylene was carried out in the intermediate pressure region from 70 to 400 kg./cm2 with a dose-rate from 5×103 to 4.3×105 rad./hr. and at a temperature of 30°C. An overall G-value of the 104 order was usually obtained. No induction period for polymerization was observed. The polymerization rate and the molecular weight of the polymer formed were shown to increase almost proportionally with the reaction time and with the pressure of ethylene. The dose-rate exponents of the rate and the molecular weight were found to be 0.9 and 0 respectively. These results indicate that the stationary-state hypothesis, i. e., that the rate of initiation is equal to that of termination, is not realized in this polymerization. From the kinetic discussion of the initial stage of polymerization, where the concentration of monomer remains essentially constant, it was concluded that the rates of termination and transfer reaction are very small; the life of polymer radicals is, therefore, quite long and the growing of polymer radicals proceeds successively under irradiation.
The Determination of Micro Amounts of Polythionates. V. A Photometric Method for the Determination of Polythionates When Two Species of Them, Tetra-, Penta- and Hexathionate, are Present Together
Authors: Koh Tomozo , Iwasaki Iwaji
Published: July 2006

In the previous papers of this series, the present authors have found the conditions under which all three polythionates (n=4, 5 and 6) are quantitatively converted into thiocyanate. When one mole of polythionate undergoes cyanolysis, one mole of thiosulfate and (n–3) moles of thiocyanate are formed. The thiosulfate formed from polythionate is then converted into thiocyanate by the addition of a cupric chloride solution. A photometric method for the determination of polythionate when two species of polythionates, tetra-, penta- and hexathionate, are present toghther has been devised; it depends upon the determination of the different amounts of thiocyanate formed from the cyanolysis of polythionates both in the presence of cupric ions and in their absence. The mean number of sulfur atoms, n, in the formula, SnO62−, for polythionate, was determined; the polythionate composition of the solution was also evaluated from the n value
Studies of the Synthetic Inorganic Ion Exchanger. V. The Separation of Zirconium-95 and Niobium-95 by Means of a Stannic Phosphate Cation Exchanger
Authors: Sat\={o} Akiko , Inoue Yasushi , Suzuki Shin
Published: July 2006

With the aim of developing a method for the separation of 95Zr and 95Nb, various eluants were investigated, a sulfuric acid solution was found to be most suitable for this purpose. After the stannic phosphate exchanger column had been conditioned with 1 n nitric acid, the sample solution was passed through it to adsorb 95Zr and 95Nb. By using a 2 n sulfuric acid solution and a 3 n sulfuric acid - 0.01 N hydrofluoric acid solution as eluants, 95Zr and 95Nb could be eluted respectively. The separation was not quantitative, however, because of the unfavorable tailing of the elution curves. On the basis of the above results, the posibility of the total radiochemical separation of a long-lived fission product and the mechanism of the adsorption of these ions were discussed.
The Copolymerization of the Vinyl Monomer with a Cyclic Compound. III. The Cationic Copolymerization of Styrene with Substituted Ethylene Oxides
Authors: Aoki Shuzo , Fujisawa Kazuo , Otsu Takayuki , Imoto Minoru
Published: July 2006

The copolymerization of styrene with substituted ethylene oxides catalyzed by boron trifluoride - diethyl ether has been investigated. In all cases, rather low-molecular-weight copolymers were obtained. The copolymerization reactivity of the substituted ethylene oxides with styrene varied with the substituents, in the order of: isobutene oxide>propylene oxide>styrene oxide>epichlorohydrin. This has been explained in terms of cross-propagation or the reaction of the growing oxide cation with styrene.

The styrene unit content of the copolymer of styrene and epichlorohydrin increases with an increase in the solvent polarity and with an increase in the temperature. It has been concluded from the experimental results that the copolymerizability of alkylene oxide toward styrene is increased by the introduction of electron-releasing substituents into the oxide and by the use of a polar solvent at a moderate temperature.
A Phase Study of the Iron(III) Sulfate, Sodium Sulfate and Sodium Chloride System
Authors: Sugiyama Kohzoh , Takahashi Takehiko
Published: July 2006

A phase diagram was drawn by using the results of a differential thermal analysis of the samples sealed in vicolglass and X-ray diffraction techniques undertaken in connection with the study of chlorine formation by the reaction of sodium chloride with sulfur dioxide and oxygen in the presence of iron compounds. In the two-component sodium sulfate - iron(III) sulfate system, the eutectic point was found at 562°C, the peritectic point, at 780°C, and the peritectoid point, at about 380°C. The former two values differ from those found by K. A. Bol’ shakov et al. (Zhur. Neorg. Khim., 8, 2577 (1963)). In the trigonal diagram, two eutectic points were found, one at 465°C with a composition of about 13.5 mol.% iron sulfate, 53.5 mol.% sodium chloride and 33.0 mol.% sodium sulfate, and the other at 454°C with 15.0 mol.% iron(III) sulfate on the line of sodium chloride - iron (III) sulfate. It was confirmed that the peritectic point corresponding to the Fe2(SO4)3+Na2SO4(1)=2NaFe(SO4)2 reaction shifted from 780°C on the line of sodium sulfate - iron(III) sulfate to 680°C on that of sodium chloride - iron(III) sulfate. From the diagram, the retarding tendency of the reaction rate of the final period of chlorine formation was attributed to diffusion control coming from the formation of solid phases.
The Electron Spin Resonance of Oxovanadium Sulfate Dispersed on Porous Materials
Authors: Tanaka Hazime , Matsumoto Akira
Published: July 2006

Oxovanadium sulfate was fixed on silica and alumina gel bases as a model of the oxidation catalyst. On silica gel the ESR spectra showed an exchange narrowing without hyperfine lines as a result of the formation of small crystallites. In this case, axially-symmetrical g factors were obtained: g⊥=1.969±0.001 and g||=1.915±0.005. When sulfuric salts of alkali metals were added to the system, the dispersion of VO2+ ions became homogeneous and a hyperfine structure was observed in the ESR spectra. On an alumina gel base the spectrum resembled that of the frozen aqueous solution of VOSO4 and showed the hyperfine structure, A⊥=(7.0±0.2)×10−3cm−1 and A||=(1.85±0.05)×10−2cm−1. It may be considered that VO2+ ions are distributed homogeneously in the surfase layer of alumina. In the alumina gel and silica gel with alkali sulfate, the decrease in the V4+ ions with heat treatment was slower than in the silica gel system.
The Flocculation of Kaolin and Precipitated Calcium Carbonate by Polymers
Authors: Sakaguchi Kahei , Nagase Kunihiko
Published: July 2006

The subsidence rate of a suspension of kaolin or precipitated calcium carbonate flocculated by polyacrylamide increases with an increase in the intrinsic viscosity of the polymer, and it shows a marked acceleration above an intrinsic viscosity of 5–6. However, in the case of the flocculation of the precipitated calcium carbonate flocculated by sodium polyacrylate, the subsidence rate depends linearly upon the intrinsic viscosity of the polymer. The results have been discussed in terms of Verwey and Overbeek’s theory. The real unperturbed dimension of polyacrylamide has been calculated from the equations proposed by Kurata, Stockmayer and Fixman. As a consequence, it has been suggested that the dimension of a polymer has a close relationship with its flocculation behavior.
Electronic Spectra of Trivalent Metal Complexes of 3-Phenyl- and 3-Benzyl-2,4-pentanedione
Authors: Murakami Yukito , Nakamura Katsuyuki
Published: July 2006

The 3-phenyl- and 3-benzyl-2, 4-pentanedione complexes of trivalent aluminum, chromium, iron and cobalt were prepared, and their electronic absorption spectra measured in the 220—900 mμ range. The spectral data were interpreted in detail in terms of the π3→π4, the electron transfer (dε→π4) and the d→d* transitions of the various components. In this series of complexes, an inter-ring π-interaction between a phenyl ring and a chelate ring is expected to remain to a limited extent in the metal complexes of 3-phenyl-2, 4-pentanedione, although the twist of both rings from the coplanarity is significant. For the aluminum complexes, π-electrons in the ligand part remain delocalized in a manner similar to that which holds in the corresponding enolate ion. On the other hand, each kind of π3→π4 transition in the transition metal complexes of the 2, 4-pentanedione derivatives was found to depend on the number of dε electrons of the central metal ion and to appear in this increasing order of energy: Cr<Fe<Co. In addition, the metal-ligand π-interaction has a major effect on the π3→π4 transition, and it seems to increase with respect to the ligands in the order: 2, 4-pentanedione, 3-phenyl-2, 4-pentanedione, and 3-benzyl-2, 4-pentanedione. The two major substituent (at the 3-position of 2, 4-pentanedione) effects which may affect the π3→π4 transitions were identified.
Photo-induced Reactions. III. The Synthesis of Biphenyls from Aromatic Bromo-Compounds
Authors: Matsuura Teruo , Omura Kanji
Published: July 2006

Various bromobenzene derivatives were irradiated in benzene with a low-pressure mercury lamp. The corresponding biphenyl derivatives were formed as the main products. A mechanism for the reaction has been discussed.
t-Amyloxycarbonyl as a New Protecting Group in Peptide Synthesis. II. Synthesis of a Hexapeptide Amide Related to Eledoisin by the t-Amyloxycarbonyl Method
Authors: Sakakibara Shumpei , Fujino Masahiko
Published: July 2006

The synthesis of a hexapeptide amide, l-lysyl-l-phenylalanyl-l-isoleucylglycyl-l-leucyl-l-methionine amide, has been carried out as a demonstration of the t-amyloxycarbonyl method. This peptide is known to possess strong biological activity which is similar to that of eledoisin and bradykinin. During the synthesis, no complication occurred involving the t-amyloxycarbonyl group, and the final product had the expected activity. Therefore, it is considered that the t-amyloxycarbonyl method is useful for the synthesis of complicated peptides.
Organic Sulfur Compounds. III. The Reactions of Toluenesulfinic Acid with Acyl Chlorides
Authors: Kobayashi Michio
Published: July 2006

Sodium p-toluenesulfinate reacts with acetyl chloride to form acetic anhydride, p-toluenesulfinyl chloride, thiolsulfonate, and sodium p-toluenesulfonate. A reaction with benzoyl chloride gives benzoic anhydride in a good yield. A mixed anhydride of sulfinic acid and carboxylic acid is postulated as an intermediate, one which survives for a few hours at −60°C. The reaction mechanism is discussed.
SOME NOTES ON THE THEORY OF ELECTRO-OSMOSIS. PART I
Authors: Komagata Sakuji
Published: July 2006

(1) Under some assumptions, the distributions of potential and electric charge in capillary are given by the equations (15)–(22) … (Section 2.)

(2) The quantity of liquid flowed out electro-osmotically W′ is given by the equation (40), and W′/πR2 is expressed by the function of radius R. The relation between permeability of membrane and electro-osmotic transfer has already been pointed out(1) to be different from that given by the Helmholtz’s equation in which W′/πR2 is constant for any R, although it is only considered to be caused from the “free-osmosis”—that is, equivalent to the first term in right hand member of equation (39)… (Section 3.)

(3) The current in capillary differs from that in the large vessel, because of its non-uniform distribution of electric charge. This is given by the equation (50). And, the relation between so-called surface conduction and ζ-potential seems to be slight, as D.R. Briggs(1) has stated. (Section 4.)

The writer wishes to express his hearty thanks to Prof. Setoh for his kind advice.
Polarography of Halides in Dimethylformamide. I. Bromide Ion and Its Mercuric Compounds
Authors: Matsui Yoshihisa , Kawakado Ryuji , Date Yoshio
Published: July 2006

The complex formation between tetraethylammonium bromide (TEB) and mercuric bromide in dimethylformamide was observed conductometrically, and a complex, tetraethylammonium tribromomercurate (TETM), was isolated. Voltammetric studies of TEB, TETM, and mercuric bromide were made, using the dropping mercury electrode in dimethylformamide containing 0.1 m tetraethylammonium perchlorate. It was found that TEB gives two reversible anodic waves, of which the more negative one is due to the oxidation of mercury to TETM, and the more positive, to the oxidation of mercury to mercuric bromide. The electrode reaction mechanism was also investigated by means of large-scale electrolysis with a controlled potential.
Metal-Containing Initiator Systems. III. Polymerization of Styrene by Some Activated Metals in the Presence of Organic Halides
Authors: Otsu Takayuki , Yamaguchi Masami
Published: July 2006

The polymerization of styrene with systems of various metals and organic halides was investigated at 60°C. It was found that the metals which could be used as hydrogenation catalysts were effective as initiators and that the organic halides with a weak carbon-halogen bond showed a high initiating activity for styrene polymerization. From the kinetic studies of the polymerization of styrene by reduced nickel and chloroform, the rate of polymerization was shown to be proportional to the monomer concentration and to the square-root concentration of both nickel and chloroform in the lower concentration range of chloroform. Some radical inhibitors were also found to inhibit this polymerization. These results indicated that this initiator system could induce the radical polymerization. The apparent overall activation energy for the polymerization by this system was estimated as 11 kcal/mol. The resulting polystyrene was found to be a relatively-low-molecular-weight atactic polymer.
Studies of the Organic Reactions of Metal Carbonyls. XIV. The Reaction of Potassium Iron Carbonylates with Isoprene
Authors: Takegami Yoshinobu , Watanabe Yoshihisa , Kanaya Isao , Mitsudo Takeaki , Okajima Toshiharu , Morishita Yoshihiko , Masada Hiromitsu
Published: July 2006

The reaction between potassium iron carbonylates (KHFe(CO)4, K2Fe(CO)4 and K2Fe2(CO)8) and isoprene has been studied. Isoprene is reduced at room temperature to give three olefins (3-methyl-1-butene (I), 2-methyl-1-butene (II), and 2-methyl-2-butene (III)). The reaction conditions (solvents, atmospheres, additives such as water) have a great effect on the yield and distribution of the olefins. Under carbon monoxide in the presence of water, the reduction is highly promoted, giving 2 mol/mol-Fe(CO)42− of the olefins. The percentage of II is almost constant (about 15%) in any case, but the percentages of I and III, very dependent on the conditions, change in the 3–40 and 50–80% ranges respectively. The reaction is suggested to proceed via some kinds of σ- and π-allyl iron carbonyl complexes. Under carbon monoxide the carbonylation of isoprene also occurs.
Copolymerization of Vinyl Chloride with Ethylene by the VO(OEt)3-Alkylaluminum Catalyst Systems
Authors: Misono Akira , Uchida Yasuzo , Yamada Kunikazu , Saeki Tadashi
Published: July 2006

The copolymerization of vinyl chloride with ethylene was carried out in n-heptane by using the catalyst systems consisting of VO(OEt)3 and AlEt3, AlEt2Cl, or AlEtCl2 at 50°C. It was found that each of the above catalyst systems produces a random copolymer at Al/V molar ratios below 1.5; however, polyethylene is mainly obtained above the ratio of 1.5. With the VO(OEt)3/AlEt3 catalyst system, its good catalyst activity being in contrast with the inactivity of the Ti(O-n-Bu)4/AlEt3 catalyst system, the maximum catalyst activity was observed at the Al/V molar ratio of 0.5. The copolymerization rate decreased with an increase in the ethylene fraction in the monomer mixture, reaching a minimum value at a 80 mol% ethylene feed; however, the rate increased above this feed ratio with a further increase in the ethylene feed. The contamination of a copolymer with polyethylene which has been observed in the copolymerization by the Ti(O-n-Bu)4/AlEt2Cl or AlEtCl2 catalyst system was not observed in the present case. The monomer reactivity ratios for the copolymerization by the VO(OEt)3/AlEt3 catalyst system were found to be r1(vinyl chloride)=2.48 and r2(ethylene)=0.02. The reaction between VO(OEt)3 and AlEt3 was investigated by means of infrared spectroscopy and gasometry, and it was found that the average valency states of the V of the catalyst system is higher than four at the Al/V molar ratio range where a random copolymer is exclusively obtained.
The Reductive Coupling Reactions of Benzyl Chloride by Copper(I) Complexes
Authors: Wada Keisuke , Hashimoto Harukichi
Published: July 2006

The reactions between benzyl chloride and cuprous chloride were studied. It was found that good yields of bibenzyl were obtained by the addition of ethylenediamine, diethylenetriamine, triethylenetetramine, acetylacetone and EDTA. Nothing of bibenzyl was observed in the cases of ethanolamine, pyridine, dipyridyl, phenanthroline and triphenylphosphine. These facts, together with the spectral studies of copper complexes can reasonably be explained by the formation of reactive species of the type CuI(en)nCl. The course of the reaction was discussed on the basis of the substituent and medium effects. Radical but not free type mechanisms which include the transient organocopper species were considered. Some additional comments were also made.
Sterically Controlled Syntheses of Optically Active Organic Compounds. XIX. Asymmetric Syntheses of Amino Acids by the Strecker Reaction
Authors: Harada Kaoru , Okawara Tadashi , Matsumoto Kazuo
Published: July 2006

The Strecker type syntheses of optically active alanine, butyrine, valine, and leucine by the use of the corresponding aldehydes, hydrogen cyanide, and optically active α-alkylbenzylamines and α-(1-naphthyl)ethylamine were carried out (reaction A). The optical purities were in the range 22–51%. The modified Strecker type syntheses of alanine from acetaldehyde cyanohydrine and optically active amines were also carried out (reaction B). The optical purities of alanine were in the range 44–48%. In reaction B, optically active phenylglycine was also used as an amino source. The optical purities of the synthesized alanine were in the range 12–17%.
Ionic Photodissociation of Electron Donor-Acceptor Complexes
Authors: Shimada Motoo , Masuhara Hiroshi , Mataga Noboru
Published: July 2006

Ionic photodissociation of electron donor-acceptor (EDA) complexes of s-tetracyanobenzene (TCNB) and pyromellitic dianhydride (PMDA) with 2-methyltetrahydrofuran (MTHF) has been investigated by means of nsec flash photolysis and transient photocurrent measurements. The solvent-shared ion-pair of TCNB anion and MTHF cation is formed from the excited charge-transfer (CT) singlet state of a TCNB–MTHF complex, dissociating into solvated ions. TCNB complexes with aromatic hydrocarbons dissociate directly into ions from the lowest excited CT singlet state. Dissociation of PMDA complexes occurs in the CT triplet state in nonpolar solvents and mainly in the excited CT singlet state in polar solvents. The relative rate constant of radiationless process, which competes with ionic dissociation in the excited singlet state, can be deduced from the effect of solvent on ionic photodissociation. It has been confirmed for the first time that the ionic dissociation of a TCNB–benzene–1,2-dichloroethane (DCE) system occurs in the excited Franck-Condon (FC) state. It is pointed out that the latter dissociation mechanism is not inconsistent with all the results obtained for TCNB and PMDA complexes under various conditions.
Dipole Correlation Functions of Non-interacting Symmetric Vib-rotors
Authors: Yamashita Teruyo , Shimizu Hiroshi
Published: July 2006

Dipolar correlation functions of non-interacting symmetric top molecules were obtained by quantum mechanical calculation. The effect of the rotation-vibration interaction on the correlation function is discussed, taking the constant ζ of the Coriolis coupling and the asymmetry Ix/Iz as parameters. It is shown that the decay of the correlation function for perpendicular vibrations very much depends on the sign and the magnitude of ζ. Some relationships between the shape of the correlation function and the value of the parameters are given.
The Photoconductivity of Poly(N-vinylcarbazole). II. Dark Conductivity in a Sandwich-type Cell
Authors: Okamoto Kenichi , Kusabayashi Shigekazu , Mikawa Hiroshi
Published: July 2006

The dark conductivity in a sandwich-type cell of PVCz films was investigated in a high vacuum, taking the temperature, the applied voltage, and the film thickness as parameters. In low fields, the conductivity was proportional to the applied voltage. In high fields, however, it was proportional to the fourth power of the applied voltage. This nonohmic dark conductivity in high fields may be attributed to the Pool-Frenkel effect. A model of the energy-level diagram is presented which can explain the dark conductivity in both low and high fields.
Neutral Salt Effect on the Interaction of Poly-α, l-glutamic Acid with Acridine Orange
Authors: Sato Yukio , Hatano Masahiro , Yoneyama Michio
Published: July 2006

The effect of potassium chloride on the absorption and optical rotatory properties of the poly-α,l-glutamic acid-acridine orange system in an aqueous solution was studied under various conditions. The stability of the helical conformation of poly-α,l-glutamic acid in this system was examined at different potassium chloride concentrations by estimating the helix fraction of the polymer. At pH 4.5, where poly-α,l-glutamic acid exists in the helix, it was found that the added potassium chloride raised the stability of the helical conformation of the polymer in this system. In this case, it was assumed that the added potassium chloride lowers the disturbance of helix formation by the bound acridine orange cation. However, when the solution’s pH was raised, the added potassium chloride lowered the extent of the helix fraction in this system. These phenomena were discussed on the basis of several experimental findings on the circular dichroism of the systems. Furthermore, from the change in the intensities of the circular dichroism with the variation in the potassium chloride concentration, it was presumed that the positive circular dichroism band at about 520 nm was due to the binding of dimeric acridine orange molecules to the polymer.
ESR Studies of Stable Free Radical Pairs in the Diamagnetic Matrix Crystal
Authors: Takizawa Osamu , Yamauchi Jun , Ohya-Nishiguchi Hiroaki , Deguchi Yasuo
Published: July 2006

The radical pair system of a stable free radical, di-p-anisyl-nitric-oxide (DANO), has been observed in the magnetically-diluted crystal of 4,4-dimethoxy-benzophenone. The existence of the radical pair has been ascertained by the characteristic ESR absorptions, which give rise to the zero-field splitting and half-field resonance, of the powdered sample as well as by a comparison of the magnitude of the hyperfine coupling constant of the isolated radical with that of the pair system. The precise ESR measurements were performed using a single crystal containing 7.5% DANO radicals oriented well in the diamagnetic matrix. The fine structure parameters, |D| and |E|, have been determined to be 186 Gauss and 2 Gauss respectively, from which the distance between the two radical molecules in the pair system is estimated to be 5.4 Å. In order to deduce the structures of the radical pair, the g-value and the hyperfine coupling constant of the isolated radical have also been determined.
The Triplet Excitons in the Anion Radical Salts of [(C6H5)3PCH3]1−x+[(C6H5)3AsCH3]x+ (TCNQ)2÷, (0≤x≤1)
Authors: Suzuki Yukio , Iida Yôichi
Published: July 2006

The electron spin resonance (ESR) absorption and its variation with the temperature were measured with single crystals of the anion radical salts containing the mixed cations, [(C6H5)3PCH3]1−x+ [(C6H5)3AsCH3]x+(TCNQ)2\ewdot, (0≤x≤1). The paramagnetic excited state of these salts is triplet in character, as was shown from the anisotropic zero-field splitting at low temperatures. The triplet state is not localized, but, rather, corresponds to the triplet exciton state. The exciton exchange frequency and its temperature dependence were determined by analyzing the line shapes of the ESR spectra. The exciton motion in the mixed crystal system was investigated in order to establish the character of the triplet excitons in ion radical salts.
The G-values of Nitrogen Obtained from the Gas-phase γ-Radiolysis of Nitrous Oxide–Hydrocarbon Systems
Authors: Okazaki Kiyoshi , Yugeta Rei , Sato Shin
Published: July 2006

The gas-phase γ-radiolysis of a N2O-1-butene system has been reinvestigated. The other hydrocarbons used for the substrate are ethylene, propylene, 1,3-butadiene, cyclopropane, propane, and n-butane. The G-value of nitrogen from any system increased with an increase in the pressure of N2O and was saturated at about 4 mol% of N2O. The saturated value, G(N2)max, was much larger than the G-value of electrons estimated from the W-value of the hydrocarbon used and was rather strongly dependent upon the irradiation temperature, the dose rate, and the total dose. Some of the results were not consistent with those reported by the previous investigators. The reason for this discrepancy, and also the possible reaction mechanism to explain the large G(N2)max, have been discussed.
Crystal Structure of μ-Peroxo-bis[nitrobis(ethylenediamine)cobalt(III)] Dinitrate Tetrahydrate
Authors: Shibahara Takashi , Koda Shigetaka , Mori Masayasu
Published: July 2006

The crystal and molecular structure of μ-peroxo-bis[nitrobis(ethylenediamine)cobalt(III)] dinitrate tetrahydrate, [NO2(en)2CoO2Co(en)2NO2](NO3)2·4H2O has been determined using visual intensity data of three dimensional Weissenberg photographs taken with Ni-Kα radiation. The brown-black salt is monoclinic with space group P21/n and cell dimensions a=10.755±0.011, b=12.941±0.008, c=9.709±0.006 Å, and β=100.4±0.1°. The least-squares refinement with anisotropic temperature factors gave an R index of 0.106. The coordinating ligands form nearly regular octahedra about the cobalt atoms, with Co–N(en), Co-N(NO2), and Co–O distances of about 1.95, 1.94, and 1.89 Å, respectively. Both NO2−,s are trans to the O–O bridge, and the geometry of Co-O-O-Co is trans planar with O–O distance of 1.53 Å and Co–O–O angle of 110°. The two Co–(en)2 moieties have δδ and λλ conformations.
The Vibrational Assignments of Propyl Bromide and Its Two Asymmetrically-Deuterated Species
Authors: Hayashi Michiro , Ohno Keiichi , Murata Hiromu
Published: July 2006

The vibrational assignments of the observed spectra of propyl bromide and its two asymmetrically-deuterated species have been worked out. Since the two gauche isomers come not to be equivalent for the asymmetrically-deuterated species, the infrared bands of the gauche isomer can be expected to be split into doublets, while the bands of the trans isomer remain singlets. The observed infrared bands for the gauche isomer were actually the doublets for the C–Br stretching and two CH2 rocking modes. The C–D stretching and deformation modes of the β-deuterated species were also in the expected spectral patterns. In order to confirm the vibrational assignments, the normal vibration calculation was carried out using a modified Urey-Bradley force field for the parent and two asymmetrically-deuterated species.
Racemization and Isotopic Exchange of Tris(acetylacetonato)silicon(IV) Perchlorate in Organic Solvents
Authors: Inoue Tomoaki , Saito Kazuo
Published: July 2006

Racemization of trisacetylacetonatosilicon(IV) ions and their isotopic exchange reaction with acetylacetone-14C (Hacac) have been studied in tetrachloroethane (TCE) and acetonitrile (AN). No solvolysis takes place at least below 60°C, and the racemization rate R is expressed as follows: R=[complex] (k1+k2[acid]) (in TCE) and R=[complex] (k3+k4[base]) (in AN). The rate constants and activation parameters at 50°C are as follows: rate constants, 4.79×106 s−1, 1.35×10−4 M−1 s−1, 3.87×10−5 s−1 and 1.19×10−1 M−1 s−1, activation enthalpy (ΔH\eweq/kcal mol−1) 31.6±0.1, 29.3±1.9, 25.7±0.2 and ca. 18, and activation entropy (ΔS\eweq/cal mol−1K−1) 14.6, 14.2, 0.53, −5.75, respectively, for k1, k2 (for trichloroacetic acid), k3 and k4 (for 2,6-lutidine). No isotopic exchange is observed within 6 hr at 60°C in the solvents. The racemization should proceed intra-molecularly and presumably via an intermediate of coordination 5 with one of the ligands as unidentate.
Studies of the Ruthenium(III) Complex. V. Aquation and Anation Reactions of Halogenoacetatopentaammineruthenium(III) Complexes in Aqueous Solutions
Authors: Ohyoshi Akira , Shida Satoshi , Izuchi Shuichi , Kitagawa Futoshi , Ohkubo Katsutoshi
Published: July 2006

The kinetics of aquation and anation reaction have been studied with pentaamineruthenium(III) complexes containing halogenoacetates (fiuoro-, monochloro-, dichloro-, trichloro-, bromo-, and iodoacetates). It has been found that the aquation reaction proceeds through two kinds of paths, i.e. the acid-catalysed path and the aciduncatalysed path, except the cases of dichloro- and trichloroacetate complexes. The aquations of dichloro- and trichloroacetate complexes are not catalysed by a proton because these ligand acids are strong acids. The equilibrium constants between [RuH2O(NH3)5]3+ and [RuO2CRX(NH3)5]2+ (O2CRX=halogenoacetate), Keq, were calculated from the anation and aquation rate constants. The kaq and Keq values for the fiuoro-, chloro-, dichloro-, trichloro-, bromo-, and iodoacetatocomplexes are, respectively: kaq, 10×10−5, 7.5×10−5, 19.1×10−5, 49.0×10−5, 6.8×10−5 and 6.7×10−5 sec−1; Keq, 5.2×10−3, 3.6×10−3, 9.0×10−3, 23×10−3, 3.5×10−3, and 3.3×10−3 M, at 60°C. The free energy plot, logkaq  vs. logKeq, gave a straight line with a gradient of 1.0. It has been concluded that the acid-uncatalysed reaction proceeds via a SN1 mechanism, while the acid-catalysed reaction seems to take place with a SN2 mechanism. Some remarks have been made on the molecular interaction between the complex and the acid catalyst.
Photochemical Reduction of p-Quinones with Hydrogen Donors Studied by CIDNP Technique
Authors: Maruyama Kazuhiro , Otsuki Tetsuo , Takuwa Akio , Arakawa Seiichi
Published: July 2006

Photo-reduction of p-benzoquinone, 1,4-naphthoquinone, and their methyl- or chloro-derivatives has been investigated by means of CIDNP technique. Strongly polarized PMR signals due to unstable reaction intermediates, p-quinones, and hydroquinones were observed during the course of reaction. Structures of the unstable reaction intermediates, none of which accumulated as reaction products, were determined, their polarized PMR signals being compared with those of the unstable reaction intermediates resulting from the deuterated substrates. From these results, a reaction scheme for these photo-reduction was proposed.
The Photoconductivity of Poly(N-vinylcarbazole). V. The Doping Effects of Various Materials on the Photoconductivity
Authors: Okamoto Kenichi , Kusabayashi Shigekazu , Mikawa Hiroshi
Published: July 2006

The photoconductivity and fluorescence spectra of poly(N-vinylcarbazole) (PVCz) films doped with various materials were investigated. The photoconductive properties of doped films may be grouped into three classes according to the kind of dopant. The doping of an electron donor, such as tetramethyl-p-phenylenediamine and 1,5-diaminonaphthalene, reduced the photocurrent in all the wavelength regions by a factor of 102 to 104 because of the hole-trapping effect of the dopant molecule. The exciplex formed between the donor and PVCz does not seem to contribute to the photocurrent. The doping of an acceptor, such as TCNE and dimethyl terephthalate, on the other hand, enhanced the photocurrent. The field-assisted thermal dissociation of an excited CT complex formed between PVCz and an acceptor seems to be a carrier generation process. The doping of anthracene or perylene quenched the fluorescence of PVCz by a factor of 10 to 30 and reduced the photocurrent in the UV region by a factor of 2 to 7, while it enhanced the photocurrent in the absorption region of the dopant.