Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 48 , Issue 12
Showing 1-50 articles out of 77 articles from the selected issue
  • Hiroyuki Shinoda, Tatsuo Akutagawa
    1975 Volume 48 Issue 12 Pages 3431-3435
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The dipole polarizabilities and the anisotropies of several small molecules have been calculated according to a formula derived from the time-dependent perturbation theory. The wave functions and the energies were calculated by means of the CNDO-CI version, with an extended-basis set. The effects on the calculated results of the introduction of the atomic vacant orbitals into the basis set have been discussed.
  • Katsutoshi Ohkubo, Kohji Tsughihashi, Toshiaki Yoshida, Masahide Okada
    1975 Volume 48 Issue 12 Pages 3436-3440
    Published: 1975
    Released: March 27, 2006
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    Several protonated alcohols, acids, and esters were investigated by means of the INDO-MO theory and in connection with their proton and carbon-13 NMR results. The relative stability of the protonated conformers as detected by the NMR spectroscopy, had a good coincidence with the MO-theory and the experimental results. The proton or carbon-13 chemical shifts and coupling constants also showed satisfactory linear correlations between the theory and the experiment; the proton and isotropic (13C) chemical shifts could be well explained by the linear correlation between the diamagnetic shielding constant and the electron density on the proton of the O–H bond and between the calculated paramagnetic shielding effect and the observed isotropic chemical shifts. The observed coupling constants of the proton and carbon-13 NMR had good overall parallelisms with those evaluated by means of the Fermi contact effect.
  • Aritada Hatta, Yoshihiro Moriya, Wataru Suëtaka
    1975 Volume 48 Issue 12 Pages 3441-3445
    Published: 1975
    Released: March 27, 2006
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    The infrared absorption spectra of thin films of α-alanine formed on pure nickel and “Raney nickel” surfaces, modified with its aqueous solution, were measured by the high-sensitivity reflection method. From the infrared dichroism in the reflection spectra, the molecular orientations in the thin films were derived. In the thin film formed on pure nickel modified at 5 °C, the CO2 group of α-alanine is oriented nearly vertical to the metal surface and the O···O axis is inclined to the surface. On the other hand, when the “Raney nickel” film is modified at 5 °C, the Cα–Co(carboxylate) bond is oriented obliquely to the surface. When the “Raney nickel” film is modified at 100 °C, the Ni-alanine chelate is formed on the surface: the Cα–Co bond and the NH2 group are nearly parallel to the substrate surface, while the O···O axis is vertical to that surface.
  • Yoshihisa Matsui, Hiroshi Sawada, Kazuo Mochida, Yoshio Date
    1975 Volume 48 Issue 12 Pages 3446-3449
    Published: 1975
    Released: March 27, 2006
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    The adsorption of α- and β-cyclodextrins on the surface of the dropping mercury electrode was examined in a phosphate buffer solution by means of voltammetry with a triangular potential sweep. The α- and β-cyclodextrins gave two capacitive peaks corresponding to the adsorption and desorption processes respectively. The α-cyclodextrin additionally gave two cathodic peaks and an anodic peak, probably due to reorientation processes. The effects on the peak heights were investigated in terms of the sweep rate, the cyclodextrin concentration, the temperature, the ionic strength, and the pH. The adsorption of both cyclodextrins followed the Langmuir isotherm, and the equilibrium constants for the adsorption were evaluated to be 1.2×104 M−1 for α-cyclodextrin and 1.0×105 M−1 for β-cyclodextrin at 25°C and pH 6.5.
  • Tsing-Ko Lin, Niro Matsuura
    1975 Volume 48 Issue 12 Pages 3450-3455
    Published: 1975
    Released: March 27, 2006
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    Sodium metaphosphate glass, with a polymerization degree of 50–100, was used as target material for the study of the chemical effects of (n, γ) reaction. Mean oxidation number of 32P was introduced as a new parameter to elucidate the oxidation reaction brought on the recoil product. The mean oxidation number of 32P from (n, γ) recoil in such glassy polyphosphate was about +4. More than 90% of the 32P set free was reattached as an end group in the newly formed radioactive polyphosphate. The recoiled monoatomic 32P species (less than 10% of the total 32P) defficient in oxygen kept a low mean oxidation number ca. +3. Ionizing radiation produced color center (with λmax at 510 nm) which seemed partially to oxidize the 32P product. The effect was very weak, and could be suppressed by the hold scavengers. Thermal annealing showed that the mean oxidation number of 32P rapidly attained +5 (the valence of target) by 300 °C; however, it seems very difficult to raise the mean oxidation number of 32P to +5 by γ-ray annealing. The oxidation of 32P through thermal annealing is considered to be a diffusion process, with an activation energy of ca. 7×103 cal/mol. Possible reaction between the hot-zone and the radiation spurs is discussed.
  • Hideo Matsuzuru, Yoshiki Wadachi
    1975 Volume 48 Issue 12 Pages 3456-3459
    Published: 1975
    Released: March 27, 2006
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    The kinetics of ion exchanges of Ag+, Zn2+ and Cr3+ at extremely low concentrations on the chelating resin Dowex A-1 has been studied by means of finite volume method. The rate of exchanges for both Ag+ and Zn2+ is dependent on the ionic strength, particle size of the resin and reaction temperature. At higher ionic strength (0.1–0.05) the kinetics is controlled by particle diffusion, whereas at lower ionic one (0.01–0.001) film diffusion is predominant. The apparent activation energy obtained is 3.84 kcal/mol for Ag+ and 3.91 kcal/mol for Zn2+. The exchange rate of Cr3+ obeys a first-order rate equation independent of the ionic strength and particle size of the resin. The apparent activation energy is 15.5 kcal/mol. These results support the view that the ratedetermining step of this reaction is chelate formation reaction.
  • Tadashi Fukuzawa, Nozomu Ebara, Mikio Katayama, Hideaki Koizumi
    1975 Volume 48 Issue 12 Pages 3460-3463
    Published: 1975
    Released: March 27, 2006
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    The mechanism of enhancement of emission quantum yield of the methanol solution of tris(dibenzoylmethano) europium (III) by triethylamine has been investigated. Lifetime of Eu3+ resonance emission of the chelate did not change remarkably when triethylamine was added. The aspect of temperature dependence of the emission intensity was similar for both the chelate itself and the chelate-amine adduct under direct excitation of the metal level, but differed under excitation of the ligand. It was suggested that the sensitization is mainly due to a suppression of nonradiative process in the ligand triplet state.
  • Kenji Fujiwara, Kohji Fukushi, Shun-ichi Ikawa, Masao Kimura
    1975 Volume 48 Issue 12 Pages 3464-3468
    Published: 1975
    Released: March 27, 2006
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    The infrared band shapes of the fundamental and overtone C–I stretching vibrations of methyl iodide in solutions are well approximated by the superposition of Lorentzian functions. From a comparison of the bandwidths of the ν3(→1), ν3(1→2), and ν3(0→2) transitions, it is pointed out that the vibrational relaxation of the translational-diffusion type proposed by Bratos et al. contributes to the band-widths, in addition to reorientational relaxation. A slight deviation from the Lorentzian function was observed in the low-frequency region of the fundamental band.
  • Mizuka Sano, Takatoshi Narisawa, Yasumasa J. I’haya
    1975 Volume 48 Issue 12 Pages 3469-3470
    Published: 1975
    Released: March 27, 2006
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    The origin peak for the lowest singlet-triplet absorption transition of acenaphthenequinone crystals has been observed at 17981.7 cm−1 at 4.2 K. From the direction of the polarization and the Zeeman intensity pattern at 50 kOe, the lowest triplet-state configuration is identified as 3B1(nπ*). The transition to the state from the ground state gains its intensity from the z-polarized 1A1(ππ*)–1A1 transition through the y-component in the spin-orbit interaction.
  • Tohr Yamanaka
    1975 Volume 48 Issue 12 Pages 3471-3474
    Published: 1975
    Released: March 27, 2006
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    The addition of acetic acid (AcOH) to limonene (IV) over 111–333 g/1 of solid acid catalysts, at 28–92 °C and in an excess of AcOH (19–100 times of IV in molarity), were studied in terms of the kinetic data, at a total conversion of IV less than 10 mol%, and in terms of acid strength distributions of the catalysts. In the reaction medium, a leveling of the acid strength on solids was observed. For the formation of α- and β-terpinyl acetates (I and II) and a mixture of the isomeric p-menthadienes (III) as by-products, (1) the rates are proportional to the square root of the initial concentrations of IV; (2) the apparent activation energies are 18.3 kcal/mol for all the catalysts, and (3) the pre-exponential factors are roughly proportional to the square root of the highest acidity (h0,max) of the catalyst surface in the medium. The effects of the acid properties of the catalyst on the catalytic activity and the selectivity are different from those in a homogeneous liquid acid-catalyst system.
  • Akihiko Yamagishi
    1975 Volume 48 Issue 12 Pages 3475-3479
    Published: 1975
    Released: March 27, 2006
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    The reversible one-electron-transfer reactions of the following cation radicals were studied by temperature-jump and stopped-flow methods: phenothiazine (PhZ)/N,N,N′,N′-tetramethyl-p-phenylenediamine cation (TMPD\underset.+), PhZ/N,N-dimethyl-p-phenylenediamine cation (DMPD\underset.+), DMPD/TMPD\underset.+ and DMPD/N,N,N′,N′-tetramethylbenzidine cation (TMBZ\underset.+). The solvent used was either 1 : 3 ethanol-water or acetonitrile. For PhZ/TMPD\underset.+, PhZ/DMPD\underset.+ in ethanol-water and also for DMPD/TMPD\underset.+ in acetonitrile, the backward reaction corresponding to the negative free energy change of reaction (ΔF°<0) proceeds almost at the diffusion controlled rate. The backward rate constant for DMPD/TMPD\underset.+ in ethanol-water, (6±1)×108 M−1 s−1, is slightly less than a diffusion controlled one even for ΔF°<0. The results are discussed as compared with the previous study on 7,7,8,8-tetracyanoquinodimethane/substituted-p-benzoquinone anions.
  • Tsutomu Okuda, Koji Yamada, Yoshihiro Furukawa, Hisao Negita
    1975 Volume 48 Issue 12 Pages 3480-3482
    Published: 1975
    Released: March 27, 2006
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    The nuclear quadrupole resonance (NQ R) of 127I in tellurium tetraiodide was observed, and the Zeeman effect on a single crystal was examined. Tellurium tetraiodide shows ten resonance lines in the frequency range from 195 to 260 MHz. From the analysis of the zero-splitting patterns, it has become apparent that tellurium tetraiodide crystals contain eight nonequivalent iodine atoms, two of which yield large asymmetry parameters (94.9% and 73.8%) and small quadrupole coupling constants (775.07 MHz and 929.55 MHz) at room temperature. These two may be assigned to the bridging iodine atoms, but they differ markedly from each other in the temperature dependences of e2Q q/h and η. The other six iodine atoms have small η values and coupling constants of about 1600 MHz; they are assigned to the terminal atoms. From these results, it may be concluded that each tellurium atom has three terminal and two bridging iodine atoms.
  • Masamoto Iwaizumi, Takashi Kishi, Fumio Watari, Taro Isobe
    1975 Volume 48 Issue 12 Pages 3483-3485
    Published: 1975
    Released: March 27, 2006
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    The triplet splittings due to protons were observed for the ESR of the dimeric cation radicals of P(CH3)3, P(CH2CH3)3, and PH(CH3)2; they were formed by the γ irradiation of the rigid CH2Cl2 solutions of these alkylphosphines at 77 K. The observed proton hyperfine splittings for the dimer-cation radicals, [(CH3)3P–P(CH3)3]+ and [(CH3CH2)3P–P(CH2CH3)3]+, were assigned to the hyperfine interaction with two of the methyl and with two of the methylene protons respectively, while those for the [(CH3)2HP–PH(CH3)2]+ radical were assigned to the hyperfine interaction with the two P–H protons. In the former two radicals, the rotations of the methyl and the ethyl groups are restricted. The conformations of the methyl and the ethyl groups have been estimated on the basis of the observed proton hyperfine splittings. The P–H protons of the [(CH3)2HP–PH(CH3)2]+ radical have an extremely large isotropic coupling constant of 58 G; it may be attributed to the direct interaction with the unpaired electron in the anti-bonding σ* orbital of the P–P bond.
  • Katsumi Nakamaru, Kazuo Jin, Atsuko Tazawa, Masaru Kanno
    1975 Volume 48 Issue 12 Pages 3486-3490
    Published: 1975
    Released: March 27, 2006
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    The photoreactions of hexacyanocobaltate(III) in non-aqueous solvents (methanol, ethanol, acetonitrile, DMF, pyridine) caused by irradiation at 365 nm or 313 nm are found to be the photosolvation
    [Co(CN)_6]^3- + Solv. \oversethν→ [Co(CN)_5(Solv.)]^2- + CN^-
    In pyridine, in addition to the photosolvation product, a fluorescent substance which is perhaps an aromatic compound is also formed by the irradiation at 365 nm. The quantum yields are almost the same as that in aqueous solution. In ethanol, the quantum yields irradiated at both 313 nm and 365 nm are the same, indicating that the quantum yield is independent of the exciting wavelength. The sensitized photosolvation using several donors failed to occur because of the solubility limitation. Interesting spectral results are also reported.
  • Masao Sakurai, Tsuyoshi Komatsu, Tsurutaro Nakagawa
    1975 Volume 48 Issue 12 Pages 3491-3495
    Published: 1975
    Released: March 27, 2006
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    The densities of dilute aqueous solutions of two homologous organic salts, RNH3Cl and RCOONa, where R varies from H to n-octyl, have been measured at 5, 25, and 45 °C using a buoyancy technique. The apparent molal volumes, φv, of the salts and the limiting partial molal volumes, \barV°, of the individual ions have been evaluated. The contributions of a methylene group to the partial molal volume, \barV°(CH2), as estimated from the \barV° data for longer-chain salts, are nearly the same for both series: approximately 15.3, 15.9, and 16.5 ml/mol at 5, 25, and 45 °C respectively. Compared to these values, on the other hand, the \barV°(CH2) estimated for shorterchain RNH3Cl is larger and that for shorter-chain RCOONa is smaller. The second derivative of the \barV° with respect to the temperature, ∂2\barV°⁄∂T2, which is often regarded as a useful measure of structural effects, is almost independent of the chain length for longer-chain homologues. The concentration dependence of φv does not always vary in a regular manner with the chain length. The present results suggest that the volumetric behavior of aqueous organic electrolyte solutions is more complicated than has previously been believed.
  • Haruo Mizuno, Takahide Saito, Naomichi Iso
    1975 Volume 48 Issue 12 Pages 3496-3499
    Published: 1975
    Released: March 27, 2006
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    The dissociation-association behavior of phycocyanin has been studied by sedimentation-equilibrium measurements under various pH and ionic-strength conditions. The weight-average molecular weight of phycocyanin changed according to the changes in concentration of the solute. From the concentration dependence of the molecular weight, it has been claimed that the dissociation-association equilibrium system of phycocyanin is trimer\ ightleftharpoonsmonomer at pH 6.8 in the relatively low concentration region and hexamer\ ightleftharpoonsmonomer at pH 5.4. However, the coexistence of the trimer\ ightleftharpoonsmonomer and hexamer\ ightleftharpoonsmonomer systems is in evidence in the concentration region larger than 0.06 g/dl. This dissociation-association behavior of phycocyanin is supported by the experimental results obtained from sedimentation-transportation and osmotic-pressure measurements.
  • Tokio Yamabe, Kazuyoshi Tanaka, Hiroshi Ueno, Kenichi Fukui
    1975 Volume 48 Issue 12 Pages 3500-3505
    Published: 1975
    Released: March 27, 2006
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    The long-range force between a hydrogen atom and a hydride ion has been studied by means of the second-order perturbation theory. This H–H system has been chosen as the simplest example of a system composed of a neutral atom and an anion. The results seem to suggest that the analytical closed form of the second-order energy is desirable for any discussion of the long-range interaction between H and H in place of the usual multipole expansion. According to the multipole expansion until the R−12 term, the nature of the long-range interaction operating in this system seems to be dispersive, and it seems to become inductive at a much larger R because of the existence of the leading R−4 term.
  • Kazuko Sasaki Kunihisa, Takako Shinoda
    1975 Volume 48 Issue 12 Pages 3506-3511
    Published: 1975
    Released: March 27, 2006
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    An improved DTA furnace and sample cell have been used for accurate DTA measurements and clear polarizing microscopic photographs. The photographs, DTA and TTA curves were obtained simultaneously at different heating or cooling rates for solid-smectic, smectic-cholesteric and cholesteric-isotropic liquid phase transitions in cholesteryl myristate.
  • Haruo Hosoya, Miyuki Murakami
    1975 Volume 48 Issue 12 Pages 3512-3517
    Published: 1975
    Released: March 27, 2006
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    Topological bond order plT is proposed to be defined for a bond l in the graph corresponding to the carbon atom skeleton of a hydrocarbon. This quantity is obtained by hand calculation of the topological indices of the graph and its subgraphs. The plT value is linearly correlated well with the Coulson bond order plC for both the chain and cyclic compounds. If the bonds with the same Pauling bond order plP are compared this linear relationship is greatly improved and one gets an empirical relation as
    p_l^C=A  p_l^T + B  p_l^P.
  • Masamichi Akimoto, Etsuro Echigoya
    1975 Volume 48 Issue 12 Pages 3518-3522
    Published: 1975
    Released: March 27, 2006
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    Vapor-phase oxidation of butadiene, 2,5-dihydrofuran and furan over supported molybdena catalysts has been investigated with reference to the reaction mechanism and the rate-determining step of maleic anhydride formation from butadiene. Formation of maleic anhydride during the oxidation of butadiene was found to follow two reaction mechanisms, (a) via 2,5-dihydrofuran and furan, and (b) via 2,5-dihydrofuran but not via furan. The energy barrier for the addition of oxygen species to adsorbed butadiene or furan is very high, i.e., 28.9 or 21.9kcal/g-mol, respectively, as compared to that for the oxidative dehydrogenation of the intermediate compounds such as 2,5-dihydrofuran. Formation of 2,5-dihydrofuran is rate-determining in these mechanisms during the oxidation of butadiene to maleic anhydride. The second mechanism plays a more important role in maleic anhydride formation at low temperatures, the role of the first mechanism increasing with a rise in the reaction temperature.
  • Kiyoshi Okazaki, Shin Sato
    1975 Volume 48 Issue 12 Pages 3523-3528
    Published: 1975
    Released: March 27, 2006
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    The binary-encounter collision theory has been applied to the calculation of the G-values for the ionization and excitations of diatomic molecules irradiated by 100 keV electrons. The obtained G-values of electrons are as follows, in the order of H2, N2, CO, NO, and O2: 2.83, 2.55, 2.68, 3.61, and 2.98. These values are in fair agreement with the experimental ones. The present non-empirical method is compared with the semi-empirical ones proposed by other investigators. The G-values of some other products were also calculated: the excited hydrogen atoms in the radiolysis of H2 (0.9) and the ozone formation in the radiolysis of O2 (12.6). These G-values are also in fair agreement with the experimental ones.
  • Nobuaki Yoshimizu, Chiaki Hirose, Shiro Maeda
    1975 Volume 48 Issue 12 Pages 3529-3532
    Published: 1975
    Released: March 27, 2006
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    In the rotational spectrum of ethylene oxide, the five lowest-lying vibrational states are assigned and the vibration-rotation constants and the centrifugal distortion constants are derived. The vibrational frequencies are estimated from relative intensity measurements at νa=803±18 cm−1 and νb=814±23 cm−1 for the antisymmetric species (with respect to the C2 operation) and at νc=872±34 cm−1, νd=1020±33 cm−1, and νe=1109±42 cm−1 for the symmetric species. The intensity measurements of the remaining spectral lines showed that these lines belong to vibrational states at frequencies above about 1000 cm−1. The νa, νb, and νc states are tentatively assigned to ν15, ν12, and ν5, respectively, by taking into account the Goriolis interactions.
  • Koichi Kobayashi, Hiroshi Sato, Kosei Kachi, Masao Nakamura, Tsunetaka ...
    1975 Volume 48 Issue 12 Pages 3533-3539
    Published: 1975
    Released: March 27, 2006
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    The regions of dispersion, coagulation precipitation, coagulation flotation, and redispersion were determined for aqueous bentonite-cationic surfactant and bentonite-cationic surfactant-polyacrylamide(PAA) systems. The region of coagulation flotation was markedly extended by the addition of PAA to both the lower and higher concentration regions of the cationic surfactant, hexadecyldimethylbenzylammonium chloride(HDBAC), and to the lower concentration region of bentonite. The phenomenon of coagulation flotation was investigated in detail and was applied to the removal of Co2+ ions and nuclear fission products, 144Ce and 155Eu, from an aqueous solution. The composition of the reagents for the maximum efficiency of bentonite flotation corresponded to that of the maximum efficiency of Co2+-ion flotation. The effect of the pH on the flotation efficiency was studied in particular. The maximum flotation efficiency of 96% was obtained at pH 11 for Co2+ ions, 86% at pH 9.7 for 144Ce, and 93% at pH 10.5 for 155Eu. These radioactive elements were almost completely adsorbed on the surface of bentonite particles and were floated with them in the pH region of the maximum flotation efficiency. It was confirmed that Co2+ ions could be floated also from an extremely low concentration (10−9 mol/l) of Co2+ ions with nearly the same efficiency of flotation and with the additives in the same condition. Co2+ ions could also be effectively removed by using the step-by-step flotation, showing as high a flotation efficiency as 99.8%.
  • Katsuo Takahashi, Reita Tamamushi
    1975 Volume 48 Issue 12 Pages 3540-3544
    Published: 1975
    Released: March 27, 2006
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    The electrochemical properties of the interfacial layer between a DME and dilute aqueous solutions of MCl (M: alkali-metal) at the cathodic limiting current plateau were studied by means of impedance measurements at relatively low frequencies (≤250 Hz). From the frequency and potential dependence of the capacitive and the resistive components of the electrode impedance, the following conclusions were obtained concerning the properties of the interfacial layer under the above condition: (i) when the concentration of cations is extremely low in the vicinity of the electrode surface, the impedance behaves as if the conventional double-layer were absent: (ii) the impedance behavior of the present system can be explained by assuming an equivalent circuit which is given by a series combination of the Warburg impedance for the reduction of M+ and the resistance of solution; and (iii) such an interfacial layer is conventionally called “the Nernst double-layer” and its formation is determined by the mass-transport of the reacting species M+.
  • Katsuo Takahashi, Kiyoshi Matsuda, Reita Tamamushi
    1975 Volume 48 Issue 12 Pages 3545-3552
    Published: 1975
    Released: March 27, 2006
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    The admittance of various electrodes/dilute aqueous electrolyte solution systems was measured at far negative potentials in the frequency range of 22–500 Hz, and the experimental results were discussed in terms of the mechanism of the electrochemical reduction of water molecules. The frequency dependence of the conductance- and susceptance-components was analyzed by assuming possible equivalent circuits. It was concluded that, in the systems which give inductive susceptances at low frequencies, the reduction of water proceeds according to the electrochemical mechanisms;
    H_2O+e→H_ad+OH^-, H_ad+H_2O+e→H_2+OH^-
    where the current density due to the second reaction path is proportional to the product of θ and (1–θ), θ being the coverage of the electrode surface by adsorbed hydrogen atoms, Had. At some metal electrodes in solutions of alkali-metal cations, no inductive susceptance was observed; this suggests that the hydrogen evolution proceeds according to other mechanisms.
  • Masahiro Manabe, Masaharu Koda, Keishiro Shirahama
    1975 Volume 48 Issue 12 Pages 3553-3556
    Published: 1975
    Released: March 27, 2006
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    The partition coefficients of normal alkanols (RmOH, m=2 to 6) and a number of polyoxyethylene normal alkyl ethers (RmEnOH, n=1,2 m=2 to 5; n=3, 4m=4,5) in the dodecane-water system have been determined at a high dilution at 25 °C. From the finding that the standard free energies of the transfer of the solutes from water to the dodecane phase show a linear relation with the number of methylene and oxyethylene groups, the contribution of the groups to the free energy was obtained as −0.858 for alkanols and −0.808 kcal/mol methylene group for ethers, and 0.655 kcal/mol oxyethylene group respectively. Extrapolation to zero oxyethylene in the linear relationship for the normal alkylethers gave standard free energies of transfer less than those for normal alkanols with the same alkyl chain length. Thus, the alkanol is more hydrophilic than the hypothetical “ether” with no oxyethylene group. The difference in the free energies is discussed from the viewpoint of intramolecular hydrogen-bond formation in the polyoxyethylene chain in the dodecane phase.
  • Fuyuhiko Inagaki, Masaaki Sakakibara, Issei Harada, Takehiko Shimanouc ...
    1975 Volume 48 Issue 12 Pages 3557-3560
    Published: 1975
    Released: March 27, 2006
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    Rotational isomerism of 1,4-pentadiene has been studied. Normal frequencies have been calculated for the low frequency vibrations of four possible rotational isomers. From the change in the spectra in the gaseous, liquid, glassy, and solid states, it has been concluded that the two skew-skew forms (SS and SS′) and the cis-skew form (CS) are stable in the liquid and gaseous states, the SS and SS′ forms coexist in the glassy state, and only the SS form remains in the solid state. It has also been found that the energy difference among the three isomers in liquid state is not appreciably large.
  • Shun’ichi Tsukiyama, Akira Takamura, Yasuko Fukuda, Masumi Koish ...
    1975 Volume 48 Issue 12 Pages 3561-3564
    Published: 1975
    Released: March 27, 2006
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    The object of this paper is to investigate the effect of the ratio of the viscosities of dispersed and continuous phases, μd⁄μc, on the particle-size distribution in o/w-type emulsions. The viscosity ratios (μd⁄μc) used were 0.836 : 1, 0.271 : 1, 0.0992 : 1, 0.0280 : 1, and 0.00133 : 1. The size of the dispersed liquid droplets was measured by the microphotographic method. The mean diameter and the particle-size distribution were determined, and, further, the specific interfacial energy was evaluated. When the viscosity ratio was much smaller than unity, the particle-size distribution showed a skewed curve. On the contrary, the specific interfacial energy increased remarkably as the viscosity ratio approached unity.
  • Isao Suzuki
    1975 Volume 48 Issue 12 Pages 3565-3572
    Published: 1975
    Released: March 27, 2006
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    A general formalism is presented for the calculation of the vibration-rotation energy levels of linear symmetrical XY2 type molecules through direct numerical diagonalization of the vibrational hamiltonian matrix. This method is applied to the CO2 and CS2 molecules, of which the general quartic force fields have been known accurately. The results are compared with those obtained by an ordinary perturbation treatment, and the truncation effects of the matrix sizes as well as of the expansions of the potential functions are discussed. Special attention is paid to the peculiarities in the potential function of CO2 for which very strong mixings of the basis harmonic oscillator wave functions are observed. The general formula for evaluating the matrix elements of the transition moment are also discussed and its applicability to the problems of vibrational intensities and the dipole moment functions is discussed.
  • Norimasa Nogami, Hiromu Sugeta, Tatsuo Miyazawa
    1975 Volume 48 Issue 12 Pages 3573-3575
    Published: 1975
    Released: March 27, 2006
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    The Raman spectra of the liquid, unannealed solid and annealed solid, and the infrared spectra of the gas, liquid, and annealed solid of ethyl methyl sulfide were measured. Normal vibrations were treated of the trans and gauche isomers. C–S stretching, CH2 rocking and skeletal deformation vibrations were discussed in relation with molecular structures. Only the gauche isomer was found to exist in the annealed solid. In the liquid state, the gauche isomer was found to be more stable, by 0.14±0.05 kcal/mol, than the trans isomer. The vibrational assignment made of ethyl methyl sulfide is consistent with those of related sulfides and disulfides.
  • Kazuo Tsutsumi, Hong Qui Koh, Seiichi Hagiwara, Hiroshi Takahashi
    1975 Volume 48 Issue 12 Pages 3576-3580
    Published: 1975
    Released: March 27, 2006
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    The differential heat of adsorption of ammonia on synthetic zeolites was calorimetrically measured and the distribution of the surface acidity was discussed in relation to the catalytic activity for cumene-cracking as a function of zeolite compositions. A newly designed apparatus, a twin-conduction-type calorimeter equipped with a semiconductor thermoelement and an adsorption apparatus, was used for the direct measurement of the differential heat of adsorption. The differential heat of adsorption of ammonia decreased with the increase in surface coverage, the acid site on the surface becoming stronger up to 27 kcal/mol for ammonia-adsorption when the ratio of silica to alumina was higher and the content of exchanged ammonium ions was higher. The cumene-cracking reaction was effectively catalyzed by zeolites having such sites with heat of adsorption of ammonia exceeding 25 kcal/mol.
  • Tetsuo Katsuyama, Toshihiko Kumai
    1975 Volume 48 Issue 12 Pages 3581-3584
    Published: 1975
    Released: March 27, 2006
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    The kinetics and the mechanism of the ligand substitution reaction between ethylenediaminetetraacetatocuprate-(II)(CuY2−) and triethylenetetraminezinc(II)(ZnT2+) were studied spectrophotometrically in the pH range 7.0–10.5 at I=0.2(NaClO4) and 25.0 °C. The exchange reaction was accelerated by traces of either EDTA or triethylenetetramine(Trien). The exchange reaction was shown to proceed by the chain reaction mechanism where the chain-propagating steps are the reaction of CuY2− with Trien and the reaction of ZnT2+ with EDTA. Each chain-propagating step was investigated. The apparent rate constant of the reaction of CuY2− with Trien increases with pH, while that of ZnT2+ with EDTA decreases with pH.
  • Yo Ueda, Yukio Ono
    1975 Volume 48 Issue 12 Pages 3585-3592
    Published: 1975
    Released: March 27, 2006
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    Activated complexes of the polarographic reductions of unsaturated organic compounds were assumed to be formed by the interaction of the π-molecular orbital of each compound with a hypothetical atomic orbital of the electrode employed. Linear correlations were obtained between the mutual differences in the polarographic half-wave reduction potentials of a series of unsaturated organic compounds and the respective differences in the π-stabilization energies calculated on the basis of the presumed structures of activated complexes. These linear relationships were considered to lend experimental support to the propriety of the presumed structures of the activated complexes of the polarographic reductions of unsaturated organic compounds.
  • Makoto Watanabe, Shoji Sato, Hajime Saito
    1975 Volume 48 Issue 12 Pages 3593-3597
    Published: 1975
    Released: March 27, 2006
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    The hydrolysis of sodium trimeta- and tetrametaphosphates was run in water, dioxane–water, and formic acid–water solvents with an initial concentration of 0.025 mol/l at various pH values and temperatures. The hydrolysis of both the metaphosphates followed first-order kinetics with respect to the concentration of the phosphate under all the conditions studied and was an acid- and base-catalyzed reaction. In acidic solutions, the rate of hydrolysis of both the metaphosphates in water is faster than that in formic acid–water and slower than that in dioxane-water. Therefore, it is concluded that, in the formic acid–water solvent, the nucleophilicity of the water molecule may decrease on account of the solvation of the water molecule with the acid, while, in the dioxane–water solvent, since the scission of the hydrogen bond between water molecules may occur by the interaction of dioxane and water molecules, the nucleophilicity of the water molecule may increase. The hydrolysis of both metaphosphates in acidic solutions is considered to be an SN2 reaction, because the overall-reaction rate is highly dependent upon the nucleophilicity of the water molecule. In basic solutions, the rate of hydrolysis of sodium trimeta- and tetrametaphosphates in water is faster than or almost the same as that in dioxane-water. Consequently, the mechanism of the hydrolysis of both the metaphosphates in basic solutions seems to differ from that in acidic solutions. The increase in the rate of hydrolysis of small-ring phosphates in acidic solutions depends upon the activation energy and frequency factor, while that in basic solutions depends significantly upon the frequency factor. This may cause the difference in the solvent effect on the rate of hydrolysis of small-ring phosphates between acidic and basic solutions. The activation energy of the hydrolysis of both ring phosphates was 20–40 kcal/mol in the pH range of 1.0–12.5. The rate of hydrolysis of the metaphosphates in an aqueous sodium hydroxide solution is faster than that in an aqueous tetramethyl ammonium hydroxide solution and this can be attributed to catalysis by a sodium ion. The hydrolysis of sodium tripolyphosphate was also carried out in basic water and dioxane–water solvents. The solvent effect on the rate of hydrolysis of tripolyphosphate in basic solutions was the same as that in acidic solutions.
  • Mutsuo Kodama
    1975 Volume 48 Issue 12 Pages 3598-3602
    Published: 1975
    Released: March 27, 2006
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    The use of CyDTA in the amperometric determination of metal-ion mixtures was studied systematically. Because of the sluggishness of the nickel(II)-EDMA∼CyDTA substitution reaction, the nickel(II) ion in the EDMA solution could be masked completely in respect to the CyDTA. Therefore, even in the presence of an excess of nickel(II)ions, the copper(II), lead(II), cobalt(II), cadmium(II), and zinc(II) ions in the EDMA solution at about pH=6.50 could be determined accurately with CyDTA. In the amperometric titration of binary mixture of copper(II) and zinc(II), lead(II), cadmium(II), or cobalt(II) ions in the EDMA solution, titration curves with two sharp breaks could be obtained by following the change in the diffusion current due to the reduction of the copper(II)–EDMA complex. The first and second breaks correspond, respectively, to the equivalence point of zinc(II), lead(II), cadmium(II), or cobalt(II) and to that of copper(II).
  • Masumitsu Kubota
    1975 Volume 48 Issue 12 Pages 3603-3607
    Published: 1975
    Released: March 27, 2006
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    The elution behavior of lutetium from a cation-exchange column with α-hydroxyisobutyric acid solution (pH 3.77) was studied as a function of column distribution ratio of lutetium, flow rate, temperature and amount of lutetium. The elution curve fitted the normal distribution when the flow rate was smaller than 40 cm hr−1 for 0.14 M of the eluant, 60 cm h−1 for 0.12 M and 120 cm h−1 for 0.10 M. However, the normal distribution and constancy of the peak position could not be maintained when the amount of lutetium exceeded 200 μg cm−2. Within the range 15–35 °C, the peak position appeared late and the elution curve became sharper with temperature rise, but the diffusion coefficients remained constant. The value of the height equivalent to the theoretical plate was determined from the position and width of the elution peak which varied as a function of the flow rate. The diffusion coefficients of lutetium ions in the ion-exchange resin and the solution were calculated to be 2.6×10−7−6.4×10−9λ″ cm2s−1 and 4.2×10−5λ″ cm2s−1, respectively, according to Glueckauf’s theoretical equation, where λ″ is the column distribution ratio of lutetium ions. The experimental results make it possible to construct an elution curve for any column distribution ratio of lutetium in the range 2–20, temperature and flow rate.
  • Shunji Utsuno
    1975 Volume 48 Issue 12 Pages 3608-3610
    Published: 1975
    Released: March 27, 2006
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    Nine new cobalt(II) complexes were prepared which contained N,N-bis[2-(dimethylamino)ethyl]methylamine (dienMe) and some unidentate or bidentate ligands, such as acetonitrile, ammonia, ethylenediamine (en), trimethylenediamine (tn), the acetylacetonate ion (acac), or the oxalate ion. The solid-reflectance spectra revealed that six complexes of the [Co(XX)dienMe](ClO4)n formula (XX=2CH3CN, 2NH3, en, tn, acac, or 1/2C2O4; n=1 or 2) are five-coordinated, whereas three complexes, [Co(C2O4)(H2O)dienMe] and Co(C2O4)1⁄2 (solv)(dienMe)ClO4 (solv=CH3CN or CH3OH), are six-coordinated. On the basis of their electronic spectra, most of the five-coordinated complexes were supposed to have a trigonal-bipyramidal structure in the solid state and in solution. The IR spectra of three hemioxalato complexes revealed the presence of quadridentate oxalateion bridging between two cobalt ions, regardless of their coordination number.
  • Sumio Kaizaki, Yoichi Shimura
    1975 Volume 48 Issue 12 Pages 3611-3621
    Published: 1975
    Released: March 27, 2006
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    Nine chromium(III) complexes of trans-[CrX2(N)4] type with three kinds of optically active diamines (R-propylenediamine, S,S-stilbenediamine and S,S-2,4-pentanediamine) were prepared and the absorption and circular dichroism spectra were measured in the region of their d–d transitions. The CD behaviors in the spinallowed transitions were discussed in comparison with the corresponding cobalt(III) complexes and their bands were assigned to the tetragonal components. On the basis of the theoretical correlation between the rotational strengths for the spin-forbidden transitions and for the spin-allowed transitions, the CD peaks in the spin-forbidden transitions were discussed and assigned.
  • Yukito Murakami, Kazunori Sakata, Yasuhiro Tanaka, Tadashi Matsuo
    1975 Volume 48 Issue 12 Pages 3622-3630
    Published: 1975
    Released: March 27, 2006
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    The cobalt(II) and nickel(II) complexes of 1,19-dimethyl- and 1,19-diethoxycarbonyltetradehydrocorrins were prepared by the template reaction as functioned by metal ions from the corresponding 1,19-disubstituted 1,19-dideoxybiladiene-ac’s. The absorption bands appearing in the energy region greater than 15000 cm−1 were attributed to the π→π* transitions within a ligand molecule. The ligand-field bands were observed in the lower energy region (<15000 cm−1) for the cobalt(II) complexes in which cobalt(II) assumes the C2v coordination symmetry: 2A12A1, 2A22A1,2B22A1, and 2B12A1 in an increasing order of energy. The vibrational spectra provided evidences for the formation of the tetradehydrocorrin complexes with perchlorate ion as the counter ion. The angular methyl groups placed at the 1- and 19-positions of tetradehydrocorrins showed the abnormally large up-field shift (2.0 ppm) of their proton signal relative to the parent biladiene-ac’s due to the magnetic anisotropy of the adjacent pyrrole rings A and D. For a 1,19-diethyoxycarbonyltetradehydrocorrin complex, the 1,19-substituents were also placed in the shielding zone of the neighboring pyrrole rings. In the case of the cyclized 2,8,12,18-tetra(2-ethoxycarbonylethyl) derivative, the ethyl ester groups of the 2,18-substituents were presumably placed in a conformational space different from that occupied by those of the 8,12-substituents according to the proton NMR behaviors. The parent biladiene-ac which carries ethoxycarbonyl groups at the 1,19-positions caused a up-field shift of its methine (at bridge positions) proton signal upon cyclization due to the loss of electronic conjugation of carbonyl groups with pyrrole rings, in consistent with the vibrational data. The ESR spectra were measured in chloroform-benzene (2 : 1) at 77 K in the presence and absence of pyridine. The cobalt(II) complexes were identified as of low-spin square-planar type with the unpaired electron in the cobalt dz2 orbital. The coordination capability of 2-ethoxycarbonylethyl groups, which are directly bound to the pyrrole rings in the cyclized metal complex system, was also suggested.
  • Kazuo Kashiwabara, Toshimasa Yamanaka, Kazuo Saito, Naoto Komatsu, Nob ...
    1975 Volume 48 Issue 12 Pages 3631-3636
    Published: 1975
    Released: March 27, 2006
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    Three isomers of trans- and cis-[Co(CN)2{(R,R)-1,2-cyclohexanediamine}2]+ and five isomers of the corresponding (S)-propylenediamine complexes have been isolated by chromatography with Dowex 50W-X8 and SP-Sephadex columns, their geometrical structures being assigned on the basis of the ligand field absorption and PMR spectra. Isomers of cis-[Co(CN)2{(S)-propylenediamine}2]Cl, which have different placement of methyl groups of (S) -propylenediamine, gave different methyl PMR resonances with different chemical shifts. The absolute configuration of the isomers was determined from the circular dichroism in the first spin-allowed d-d and the charge transfer band region. The configurational and the vicinal effect have been discussed.
  • Jun-ichi Aihara
    1975 Volume 48 Issue 12 Pages 3637-3640
    Published: 1975
    Released: March 27, 2006
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    The resonance energies of polyacenes were determined on the basis of the additive principle of π-bond energies in nonaromatic compounds. The additive components in the total π-energies for these compounds were reasonably estimated from the infinitely large polyacene. The calculated resonance energies appear to be much improved as compared with those calculated by Hess and Schaad.
  • Kazuyoshi Seguchi, Akira Sera, Yoshinobu Otsuki, Kazuhiro Maruyama
    1975 Volume 48 Issue 12 Pages 3641-3644
    Published: 1975
    Released: March 27, 2006
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    The Diels-Alder reactions of cyclopentadienes with a variety of substituted ethylenes were carried out, and their reaction rates and the endo : exo isomer ratios of the products were determined. It was shown that the faster reaction is characterized by a higher endo isomer distribution and the existence of a linear correlation between the reaction rate and the endo isomer distribution. The results were interpreted in terms of the concept of secondary orbital interaction in the transition state.
  • Yoshihisa Matsui, Kazuo Mochida, Osamu Fukumoto, Yoshio Date
    1975 Volume 48 Issue 12 Pages 3645-3647
    Published: 1975
    Released: March 27, 2006
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    The benzidine rearrangement of hydrazobenzene is retarded by the addition of α-, β-, and γ-cyclodextrins. The effects on the rate of the cyclodextrins are decreased by the addition of cyclohexanol. The deceleration of the reaction by the cyclodextrins was attributed to the equilibrium complexation of the substrate in the cavities of the cyclodextrins, which may either restrict the large conformational change of the substrate necessary for reaching a sandwich-type transition state or lower the concentration of the diprotonated hydrazobenzene by means of the space alkalinity of cyclodextrins.
  • Shigeo Nishimura, Takeaki Takaoka, Yoshihiro Maekawa
    1975 Volume 48 Issue 12 Pages 3648-3654
    Published: 1975
    Released: March 27, 2006
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    m-Anisidine was hydrogenolyzed to an extent of 92.5% in hydrogenation with a palladium catalyst in acetic acid at 60 °C and 90 kg/cm2. The amount of hydrogenolysis in o- and p-anisidine was only 2.1 and 2.5%, respectively. This great difference in hydrogenolysis between the isomers was not observed with rhodium and platinum catalysts. With m- and p-anisidines, selectivity at the initiation of hydrogenation was studied for the formation of N-cyclohexylanisidine intermediates and for other products by an extrapolation method. Extensive hydrogenolysis of m-anisidine and slight hydrogenolysis of o- and p-anisidines over palladium result from a high selectivity in the formation of the enamine or imine intermediates. The hydrogenation pathways leading to hydrogenolysis and secondary amine formation over the three platinum metals are discussed.
  • Tadashi Suehiro, Shozo Yamazaki
    1975 Volume 48 Issue 12 Pages 3655-3659
    Published: 1975
    Released: March 27, 2006
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    3,4-Dimethyl-4-äthoxycarbonyl-cyclohexa-2,5-dienon-4-14C (9) lagert sich bei 60–70 °C in 60% Schwefelsäure zu 2,3-Dimethyl-5-hydroxybenzoesäure-äthylester-2-14C (10, 99.8%) und -1-14C (10b, 0.2%) insgesammt in ca. 50% Ausbeute um, unter Nebenbildung von 3,4-Xylenol (11, 12%) und 2,3-Dimethyl-5-hydroxybenzoesäure (12, 5%). Dass 10 die Struktur von 2,3-Dimethylbenzoesäure-Derivat hat, wurde durch Mischprobe mit der authentischen Verbindung festgestellt.
  • Taku Matsuo, Satoru Mihara
    1975 Volume 48 Issue 12 Pages 3660-3664
    Published: 1975
    Released: March 27, 2006
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    With the irradiation of dibromomaleic anhydride and N-phenylpyrrole, photosubstitution and photocyclization took place in succession to yield pyrrolo[1,2-a]quinoline-4,5-dicarboxylic anhydride as the final product. On the basis of energy-transfer experiments, both of the reactions were concluded to proceed via triplet species. Solvent effects were carefully examined and the presence of polar reaction intermediates was proposed to account for the solvent-dependent deactivation process.
  • Sotaro Miyano, Harukichi Hashimoto
    1975 Volume 48 Issue 12 Pages 3665-3668
    Published: 1975
    Released: March 27, 2006
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    Oxygen greatly accelerates the generation of the bromocarbenoid reagent of zinc from diethylzinc and bromoform. Olefins, including cyclohexene, cyclooctene, 1-hexene, cis- and trans-2-butene, isobutene, and 2-methyl-2-butene were bromocyclopropanated in yields of ca. 60–85% using a diethylzinc-bromoform-oxygen system. The bromocarbenoid showed high syn-selectivity for the addition to cyclooctene and cis-2-butene. 9-Bromo-9-deutero[6.1.0]nonane was obtained from cyclooctene using CDBr3. Styrene inhibited the formation of the bromocarbenoid reagent and polymerized under the reaction conditions, suggesting a free radical chain mechanism for the formation of the carbenoid reagent.
  • Teruo Matsuura, Yoshikatsu Ito
    1975 Volume 48 Issue 12 Pages 3669-3674
    Published: 1975
    Released: March 27, 2006
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    Irradiation of cis- (amarine; I) and trans- (isoamarine; II) 2,4,5-triphenylimidazolines in acetonitrile or benzene gave a photostationary mixture of cis- and trans-isomers, the latter predominating over the former. On irradiation in a dilute acetone solution under the conditions that acetone absorbed most of the incident light, cis-trans isomerization occurred only with isoamarine but not with amarine. In acetone, 2,4,5-triphenylimidazole (III) was also formed. Two kinds of intermediate species for the cis-trans isomerization were proposed; imidazolinyl radicals IV and/or V formed by hydrogen abstraction with the excited state of acetone (in acetone) and a biradical or a zwitterionic species VIa formed by cleavage from the excited state of I or II (in acetonitrile or benzene). Evidences for the intermediacy of VIa are presented.
  • Itsuo Matsuda, Keiichi Akiyama, Takaaki Toyoshima, Shinji Kato, Masate ...
    1975 Volume 48 Issue 12 Pages 3675-3677
    Published: 1975
    Released: March 27, 2006
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    It was found that benzenesulfinic acid reacted with N-substituted maleimides in aqueous ethanol to give sulfoneimides in good yields. The rate for the reaction was determined by the use of the neutralization titration, the effect of a substituent in N-substituted maleimides on the rate was studied, and the reaction route of benzenesulfinic acid with N-substituted maleimide was deduced.
  • Manabu Sen\={o}, Shinsaku Shiraishi, Koji Araki, Hideo Kise
    1975 Volume 48 Issue 12 Pages 3678-3681
    Published: 1975
    Released: March 27, 2006
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    The nonenzymatic hydrolysis of adenosine 5′-triphosphate (ATP) in micellar and reversed micellar system was examined as an approach to elucidate the function of ATPase. In aqueous micellar systems an anionic surfactant does not affect the hydrolysis rate, but a cationic surfactant, cetyltrimethylammonium bromide(CTAB), retards the hydrolysis. This deceleration effect is interpreted to be owing to the pH change or accumulation of hydroxide ions at the cationic micellar-water interface which serves as reaction site. In the reversed micellar system where aqueous ATP phase is solubilized in n-hexane by dodecylammonium propionate(DAP), the hydrolysis rate of ATP is enhanced by several times as compared with that in an aqueous system. Addition of Mg2+ or Ca2+ enhances the hydrolysis rate markedly only in the DAP reversed micellar system. The catalytic effect of the DAP reversed micellar system is discussed with respect to the polarity of water phase solubilized in the core of reversed micelles.
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