Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 48 , Issue 10
Showing 1-50 articles out of 102 articles from the selected issue
  • Kazuo Tsutsumi, Haruo Emori, Hiroshi Takahashi
    1975 Volume 48 Issue 10 Pages 2613-2617
    Published: 1975
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The esterification of silica was performed by reactions with 2,2,2-trifluoroethanol vapor and ethanol vapor with and without basic catalysts, such as ammonia and pyridine. The esterification with ethanol was referred to as the control. The extents of the esterifications were observed by means of infrared spectroscopy. The reactivity of the silica with trifluoroethanol was higher than that with ethanol. This is presumably because trifluoroethanol is more acidic than ethanol. The esterification was accelerated by the addition of ammonia as a base catalyst. For example, in the reaction of the silica with trifluoroethanol of 10.7 Torr at 30 °C for 3 hr, 35% of the surface silanols were esterified without any catalyst, while with the ammonia (0.2 Torr) catalyst, 98% of them was esterified. This suggests that the extraction of the proton from the hydroxyl groups of alcohol by NH3 contributes to the esterification. The addition of pyridine influenced the reaction rate as well, but the esterification itself was disturbed by the addition of excess pyridine, because pyridine was adsorbed strongly on the surface silanol and its heterocyclic ring prevented the alcohols from adsorption. It is supposed that the physical adsorption of trifluoroethanol on the surface silanol is necessary in the first stage of the esterification. The esterified silica became hydrophobic, and it was hydrolyzed in the presence of water.
  • Teruo Takayanagi, Haruhiko Yamamoto, Takao Kwan
    1975 Volume 48 Issue 10 Pages 2618-2622
    Published: 1975
    Released: March 27, 2006
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    The coordination of phosphine derivatives and some other bases to the cobalt mesoporphyrin IX dimethyl ester in toluene has been spectrophotometrically investigated. The coordination equilibrium constants were determined for each base, and found to be of this sequence (25 °C) : P(C4H9)3>>P(OCH3)3>P(C6H5)3>S(CH3)2>As(C6H5)3. The reversible oxygenation of the penta-coordinate complexes formed as above was investigated at lower temperatures (−20–−80 °C): the corresponding equilibrium constants were found to be in the following sequence (−80 °C): P(C4H9)3>P(OCH3)3>S(CH3)2>P(C6H5)3>As(C6H5)3. These relations were discussed in terms of the σ-donating ability of a ligand coordinated trans to oxygen.
  • Saburo Moriwaki, Ken-ichi Okamoto, Shigekazu Kusabayashi, Hiroshi Mika ...
    1975 Volume 48 Issue 10 Pages 2623-2626
    Published: 1975
    Released: March 27, 2006
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    The dark- and photo-conductivities of poly-9-vinylacridine (PVAcr) were investigated in comparison with those of poly-N-vinylcarbazole (PVCz). The dark current was ohmic over the whole voltage region studied up to 150000 V/cm. The photocurrent showed a linear dependence on the applied voltage even in fairly high applied fields up to 130000 V/cm and a spectral dependence corresponding antibatically to the absorption spectrum. The magnitude of the photocurrent with positive electrode illumination (iph+) was only 1.5–2 times larger than that with negative electrode illumination (iph), the behavior differing entirely from that in a PVCz film. The magnitude of the photocurrent of PVAcr was smaller than that of PVCz by several times for iph and by a hundred times for iph+. The poor photoconductivity of PVAcr was attributed both to the high concentration of the excimer-forming site acting as an effective exciton trap and to the poor electron-donating character.
  • Fujito Nemoto, Fumio Shimoda, Kazuhiko Ishizu
    1975 Volume 48 Issue 10 Pages 2627-2633
    Published: 1975
    Released: March 27, 2006
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    ESR and ENDOR spectra were obtained for the anion radicals of 4,4′-diisopropylbiphenyl, 4,4′-dicyclohexylbiphenyl and 4,4′-dicyclopentylbiphenyl. Both the β- and γ-proton coupling constants of the alkyl groups were precisely determined. The temperature dependence of the β-proton splittings of the alkyl groups were investigated. According to the Heller-McConnell relationship for hyperconjugation, a4β=(B0+B2cos4π, the positive temperature dependence of the alkyl β-proton splitting was adequately interpreted utilizing a revised model with restricted rotation. The rotational potential barrier and the energy difference of the two equilibrium states obtained were 1.2 and 0.5, 1.2 and 0.6, and 1.2 and 0.6 kcal/mol for the 4,4′-diisopropyl-, 4,4′-dicyclohexyl-, and 4,4′-dicyclopentylbiphenyl anions, respectively. The energy difference of the non-bonding interatomic interaction was calculated in terms of the Lennard-Jones 6–12 potential. Excellent agreement is found between the experimentally-determined value of the potential barrier and that calculated theoretically. ENDOR observations carried out for 4,4′-dicyclohexyl- and 4,4′-dicyclopentylbiphenyl anion radicals in solution demonstrated that γ-protons revealed two different hyperfine coupling constants. These hyperfine coupling constants were assigned to the stereochemically different γ-protons. The ratio of these γ-protons splittings suggest that hyperconjugation plays an important role in producing a spin density of the γ-protons as has been proposed for explanations of the β-proton splittings.
  • Asahi Suzuki, Kuwako Ohkawa, Seiichi Kanda, Masanori Emoto, Shunichi W ...
    1975 Volume 48 Issue 10 Pages 2634-2638
    Published: 1975
    Released: March 27, 2006
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    N,N′-Disubstituted dithiooxamide-Cu(II) as compound semiconductors prepared by the usual method have been liable to be an isomeric mixture of coordination polymers. Syntheses of the stereospecific coordination polymers were attempted by an interfacial technique. The dithiooxamides with two hydrophobic substituents, R’s, on nitrogen atoms of a ligand molecule could be spread on a water surface to form the monomolecular film, where its possible structure is cis isomers of the ligands. Some coordination compounds, i.e. the stereospecific coordination polymers, between the cis isomers and Cu2+ ions were found to be produced at the air-water interface by employing the substrate solution containing Cu2+ ions. This was established by the surface pressure vs. area measurements for their ligand molecules with C6H5CH2–, C6H11–, C12H25–, and C12H25OCOCH2– as hydrophobic substituents, and by the effects of various spreading solvents, pH in substrate solutions and temperatures on their monolayers. Furthermore, built-up films of these polymers were examined for thickness.
  • Isao Ando, Naomi Jinno, Atsuo Nishioka
    1975 Volume 48 Issue 10 Pages 2639-2647
    Published: 1975
    Released: March 27, 2006
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    The concentration and temperature dependences of the 13C chemical shifts of N,N-dimethylacetamide (DMA) in CCl4, H2O, and H2SO4 solutions were measured by means of a 13C FT-NMR spectrometer at 25.15 MHz. From the temperature dependence of the chemical-shift difference between the cis- and trans-NCH3 carbons, the activation energy, Ea, for the hindered internal rotation about the C–N bond was obtained to be 10–17.5 kcal/mol; it was also found to be ca. 10 kcal/mol at an infinite dilution in a CCl4 solution. The chemical shift of each carbon in the DMA molecule was calculated using Pople’s expression under the average excitation-energy approximation by means of the CNDO/2 method. The calculated finding that each carbon in DMA appears in the order of carbonyl, trans-NCH3, cis-NCH3, and acetyl carbons from the low field agrees with the order assigned by McFarlane. Further, as for the molecular association in neat liquid, various models are discussed on the basis of quantum-chemical calculations, and a model is proposed which has antiparallel oriented carbonyl groups in associated states of the molecules of more than two. The observed differences between the chemical shifts of the carbonyl carbons at dilutions in CCl4 and H2O solutions, and between those in CCl4 and H2SO4 solutions, are found to agree well with the results calculated using the model in which the DMA molecules at dilutions in CCl4, H2O, and H2SO4 exist as monomer, hydrogen-bonded DMA with H2O, and protonated DMA respectively.
  • Keiichi Fukuyama, Tomitake Tsukihara, Yukiteru Katsube, Takashi Hamasa ...
    1975 Volume 48 Issue 10 Pages 2648-2652
    Published: 1975
    Released: March 27, 2006
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    The crystal structure of versicolorin C, C18H12O7, has been determined by the X-ray diffraction method. The crystals are monoclinic, with the space group P21/a, and with four molecules in a unit cell with dimensions of a=24.918(7), b=7.922(3), c=7.003(3) Å, and β=92.85(4)°. The structure was refined by the least-squares method to R=0.053 for 1693 non-zero reflections. There are two intramolecular hydrogen bonds. A pair of molecules related by a center of symmetry forms a dimer by means of intermolecular hydrogen bonds.
  • Satoshi Hirayama
    1975 Volume 48 Issue 10 Pages 2653-2659
    Published: 1975
    Released: March 27, 2006
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    The absorption, fluorescence, and excitation spectra of 2-methyl-1-aceanthrenone (I) were investigated in several solvents in the temperature range of 77–298 K. The results show that the hydrogen-bonded (fluorescent) and non-hydrogen-bonded (very weakly fluorescent) molecules of I coexist in ethanol to a comparable extent. This is the reason why its absorption spectra are very broad in alcoholic solvents. With a decrease in the temperature, the apparent fluorescence quantum yield in ethanol at first rises to a maximum (0.37) at 197 K and then decreases. Below ca. 113 K, a new fluorescence band due to the non-hydrogen-bonded molecule appears. In 2-methyltetrahydrofuran (MTHF), the temperature dependence of the fluorescence quantum yield of I is significant only at low temperatures. The yield varies monotonously from 0.014 at 132 K to 0.30 at 77 K. A behavior intermediate between those in ethanol and in MTHF is observed in EPA. The rise and fall of the fluorescence quantum yield in ethanol or in EPA may be interpreted in terms of the temperature-dependent concentration change in the hydrogen-bonded molecule. From the results in MTHF, the maximum rate constant of the intersystem crossing between the S1ππ* and T* states is estimated to be of the order of 1013 s−1.
  • Shukichi Sakuraba, Akio Kakuta, Ryoka Matsushima
    1975 Volume 48 Issue 10 Pages 2660-2662
    Published: 1975
    Released: March 27, 2006
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    Sensitized decomposition of the trioxalatocobaltate(III) ion was studied in deoxygenated aqueous solution at room temperature, using biacetyl as an n-π* triplet sensitizer and 9-carboxyanthracene as a π-π* triplet sensitizer. In the presence of one of these sensitizers the photodecomposition rate of the complex was increased, and the plot of the reciprocal of the sensitization quantum yield as a function of the concentration of the complex gave a straight line for each sensitization system. On the other hand, the complex quenched the phosphorescence without affecting the fluorescence of the sensitizers, indicating a triplet energy transfer mechanism. A photokinetic treatment of the data for both the sensitized photolysis and the quenching process gave a result in line with proposed mechanism for bimolecular triplet energy transfer.
  • Masakazu Anpo, Toshiaki Wada, Yutaka Kubokawa
    1975 Volume 48 Issue 10 Pages 2663-2666
    Published: 1975
    Released: March 27, 2006
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    The effects of surface pretreatment upon the photolysis as well as the absorption and phosphorescence spectra of 2-pentanone adsorbed on porous Vycor glass have been investigated. The rate of propane formation (Norrish type I reaction) passes through a maximum and then decreases at higher degassing temperatures, while that of ethylene formation (Norrish type II reaction) decreases with increasing degassing temperature. Simultaneously, the phosphorescence intensity increases while the blue shift of the (n,π*) band decreases. This suggests that with a rise in degassing temperature the triplet lifetime increases while the surface polarity decreases. Thus, the decrease in the rate of ethylene formation is attributed to destabilization of the 1,4-biradicals formed by the intramolecular hydrogen abstraction, and the decrease in the rate of propane formation to the decrease in the lifetime of the n-propyl radicals, the hydrogen abstraction efficiency, and the probability of α-cleavage.
  • Katsutoshi Ohkubo, Hiromichi Ikebe, Masahide Okada
    1975 Volume 48 Issue 10 Pages 2667-2672
    Published: 1975
    Released: March 27, 2006
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    The NOx(x=1 or 2)-catalyzed isomerization of cis-2-butene was investigated by means of the INDO-UHF theory, with a particular view to the energetic and conformational aspects of the reaction. The NO2-addition process to form the intermediate radical (R1) had no appreciable activation barrier, although the NO2-fission process from the intermediate radical (R2) had the C-NO2 dissociation energy of 44.6 kcal/mol. Some characteristic features of the stretched C-C bond in the intermediate radical (R1) were; (1) rcc=1.45 Å, which was roughly equal to the value (1.481 Å) in cis-2-butene at the transition state of its thermal isomerization; (2) a pseudo π-conjugation with a small π-character (about 13% of ECCR) in comparison with that (about 29% of ECCR) in cis-2-butene, and (3) approximately the same magnitude of the hfsc value (34.40–34.47 G) for the sp2-hydrid carbon as that (experimental value of 39.07 G) for the said atom in the ethyl radical. The calculated internal-rotation barrier of the intermediate radical (R1) around the C–C bond (1.75–3.01 kcal/mol in the two rotating directions) was smaller than that (around 4 kcal/mol) obtained from the thermodynamic estimations. The energetically most stable or unstable rotamer was found in the staggered or the eclipsed configuration respectively; a hydrogen-bonding effect on the stabilization was observed in staggered configuration, although a remarkable effect of the homoconjugation or the repulsive interaction of unpaired and lone-paired electrons can be disregarded in the present internal-rotamer.
  • Keishiro Shirahama
    1975 Volume 48 Issue 10 Pages 2673-2676
    Published: 1975
    Released: March 27, 2006
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    Reaction kinetics in the presence of micelles is formulated on the basis of a microheterogeneous reaction in accordance with a current model of micellar catalysis. The necessary molecular parameters are the radius of the hydrocarbon core of a spherical micelle, the thickness of a reaction surface layer, the surface and zeta potentials, and a distribution coefficient of a hydrophobic substrate. The derived expression was applied to the hydrolysis reaction of methylorthobenzoate in the presence of sodium dodecylsufate micelle to describe reaction properties such as a rate-surfactant concentration profile, inhibition by added electrolyte, and activation energy. The micellar effect on the reaction rate was explained by a simple concentration effect of the reactants; the stabilization of the transition state by the micellar surface potential need not be taken into consideration. Inhibition of the orthoester hydrolysis by a cationic surfactant is also predicted.
  • Takeshi Asai
    1975 Volume 48 Issue 10 Pages 2677-2679
    Published: 1975
    Released: March 27, 2006
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    The crystal structure of sodium hexahydroxoantimonate (V), NaSb(OH)6, has been refined. The previous structure given by Schrewelius was confirmed, but the positional parameters of oxygen atoms were shifted significantly. Both antimony and sodium atoms are surrounded by six oxygen atoms octahedrally. The interatomic distances are: Sb–O=1.972–1.999 Å (mean 1.98 Å), O–O=2.758–2.834 Å (2.80 Å) for an SbO6 octahedron, Na–O=2.375–2.406 Å (2.39 Å) and O–O=3.229–3.526 Å (3.38Å) for an NaO6 octahedron. Two types of sequences of hydrogen bonds were recognized. They were compared with the sequences of hydrogen bonds in In(OH)3 and MnSn(OH)6.
  • Yo-ichi Ishikawa, Ko-ichi Oka, Shin Sato
    1975 Volume 48 Issue 10 Pages 2680-2684
    Published: 1975
    Released: March 27, 2006
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    The rate of the photobleaching of the trapped electrons in the 3-methylhexane and methylcyclohexane matrices at 77 K was measured by means of ESR as a function of the concentration of the 3-methylhexyl or methylcyclohexyl radicals present in the matrices. The quantum yield of the photobleaching at the wavelength of 1300 nm increased with the increase in the radical concentration. The stable products such as olefins formed during the γ-irradiation did not affect the quantum efficiency. These results support the suggestion made by Willard et al. that the 3-methylhexyl and methylcyclohexyl radicals capture the electrons released from the trapping sites by the irradiation of the infrared light. A comparison showed that the radicals are comparable with sulfur hexafluoride in electron capture.
  • Tsuneki Ichikawa, Hiroshi Yoshida, Koichiro Hayashi
    1975 Volume 48 Issue 10 Pages 2685-2689
    Published: 1975
    Released: March 27, 2006
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    An approach was presented to elucidate the distribution of trapped electron-cation distance from isothermal decay of the trapped electron by numerically solving the Smoluchowski equation and was applied to the observed isothermal decay of trapped electron at 92.2–95.0 K in 2-methyltetrahydrofuran glass irradiated by γ-rays at 77 K. The distribution curve (the probability density of finding initially the electron at the distance r) thus obtained was close to a Gaussian function.
  • Masatoshi Hirayama, Michihiko Sato, Makoto Takeuchi, Makoto Saito
    1975 Volume 48 Issue 10 Pages 2690-2697
    Published: 1975
    Released: March 27, 2006
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    The paramagnetic proton chemical shifts induced by a series of Ln(FOD)3(Ln=Pr, Eu, Dy, Ho, Er, and Yb) were observed for aniline and m-toluidine in CCl4. In an attempt to separate the pseudo-contact(pcs) and contact shift(cs) contributions, the spin-density distributions of the π-cation radicals or the Ni(AcAc)2-induced shifts were used for the cs pattern in a molecule, as well as the geometric factors for the pcs pattern. The appropriate regions of the two geometric parameters were determined by the computer-search method for the least-squares fits of the observed to the calculated shifts. Thus, the intramolecular average value of the ratio of cs-to-pcs contributions was evaluated. The variation in this ratio with an Ln ion corresponds relatively well to that of the theoretical ratio, |⟨SZ⟩⁄|δ|, where ⟨Sz⟩ has been calculated by Golding et al. and where δ is the relative pcs predicted by Bleaney et al.
  • Takashi Fujikawa, Tomoo Aoyama, Toshiaki Ohta, Haruo Kuroda
    1975 Volume 48 Issue 10 Pages 2698-2703
    Published: 1975
    Released: March 27, 2006
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    One-center-expansion ab initio calculations with STO basis set were carried out on H2O, NH3, CH4 and BH3, to estimate the energies and probabilities of shake-up processes accompanying the photoionization of a core level. A method based on equivalent-core approximation and that based on configuration interaction procedure were applied to obtain wave functions of core-hole ions. It is shown that the calculations by the former method yield very satisfactory results, not only for the core ionization potential, but also for the energies and intensities of shake-up satellites.
  • Yoshiyuki Mido, Tamotsu Gohda
    1975 Volume 48 Issue 10 Pages 2704-2707
    Published: 1975
    Released: March 27, 2006
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    The free N–H stretching vibrations of various trialkylureas, R2UR′, in dilute solutions were studied in order to resolve our questions concerning the rotational isomerism of dialkylureas. In the infrared spectrum of R2UR′, where R is isopropyl or cyclohexyl, an additional N–H band appears on the higher-frequency side of the trans N–H band. It was also observed that the larger the effective size of the R′ group on R2UR′ is, the stronger the intensity of the additional band becomes. It was concluded, in connection with the rotational isomerism of dialkylureas, that the additional band arises from a form in which the N–H group is out of the skeletal plane.
  • Haruhiko Yokoyama, Hideo Yamatera
    1975 Volume 48 Issue 10 Pages 2708-2718
    Published: 1975
    Released: March 27, 2006
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    The osmotic coefficients of aqueous solutions of magnesium, calcium, manganese, and tris(1,10-phenanthroline)ruthenium(II) sulfates were measured at 25 °C by means of a vapor-pressure osmometer. Then the ionassociation constants of these electrolytes were obtained as a function of the closest distance of approach of ions from the measured osmotic coefficients as well as from the available conductivity and cryoscopy data. The best values of the closest distance of approach and the ion-association constant (given in Table 6) were estimated with the help of theories of ion association. The formation of triple-ions and quadrupoles and the hydration of ions are also discussed in connection with the ion-association constant.
  • Haruhiko Yokoyama, Hideo Yamatera
    1975 Volume 48 Issue 10 Pages 2719-2726
    Published: 1975
    Released: March 27, 2006
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    Simple and mixed aqueous solutions of copper, magnesium, calcium, manganese, and zinc sulfates were spectrophotometrically studied in order to obtain the ion-association constants of the divalent metal ions with the sulfate ion. The ion-association constant of copper sulfate was obtained from the measured absorbances of copper sulfate solutions at 250 nm as a function of the closest distance of approach of ions. For the other metal sulfates which show a negligible absorption at 250 nm, absorbances were measured on the mixed solutions with copper sulfate, and the results were analyzed by the use of the results on copper sulfate in order to obtain the ion-association constants. The best values of the ion-association constant and the closest distance of approach were determined for each metal sulfate with the help of the theory of ion association. The results were compared with those obtained from the measurements of osmotic coefficients and electric conductivities. The numerical results are summarized in Table 6 of the text.
  • Noriaki Funasaki, Masayuki Nakagaki
    1975 Volume 48 Issue 10 Pages 2727-2731
    Published: 1975
    Released: March 27, 2006
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    Collapse pressure, equilibrium spreading pressure, and melting points of binary mixtures of hexadecanol and octadecanol were measured in order to study the phase equilibrium among a monolayer, a solid, and a liquid and to apply the result to evaporation control of water by monolayers. Collapse pressure and equilibrium spreading pressure of solid mixtures have a maximum at a given composition, while the equilibrium spreading pressure of a liquid mixture has not a maximum. Melting points have a minimum at a given composition. From thermodynamic analysis of these phase equilibriums, it was concluded that the mixed monolayer and liquid mixture were ideal solutions, while the solid mixture was a lattice-distorted solid solution. That is, when the two components of different molecular volumes form a solid solution, the solid solution has high energy due to the distortion of the crystal lattice and consequently, it becomes easier to spread and the mixed monolayer becomes more stable against collapse. From these results, the relations between the composition of solid solution and the surface pressure, composition, and specific evaporation resistance of the mixed monolayer in equilibrium with the solid solution, were obtained.
  • Jiro Hiraishi, Takako Shinoda
    1975 Volume 48 Issue 10 Pages 2732-2735
    Published: 1975
    Released: March 27, 2006
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    The lattice vibrations of 1,2-C2H4Br2 and 1,2-C2D4Br2 were measured by means of Raman spectroscopy. The temperature dependence of the frequencies and the half widths of the lattice vibrations indicates that the phase transition of the crystal is associated with the rotation of the molecule around the Br–Br axis.
  • Katsumi Kimura, Shunji Katsumata, Kazuteru Osafune
    1975 Volume 48 Issue 10 Pages 2736-2738
    Published: 1975
    Released: March 27, 2006
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    The He I photoelectron spectra of unsymmetric hydrazines CH3HNNH2 and (CH3)2NNH2 have been measured and CNDO/2calculations have been carried out, in which gauche (outer- and inner-skew) forms and trans form were taken into account for CH3HNNH2. It has been found that nonbonding splittings in the photoelectron spectra are well reproduced by CNDO/2 calculations with gauch forms. The present result of conformation are supported by available conformational studies. The following conclusions have been obtained on orbital assignments of the photoelectron spectra: 1) The first and second bands are due to the methylated and unmethylated nitrogen lone pairs, respectively. 2) The third bands are attributed to the N–N bonding orbitals. 3) The rest of the photoelectron spectra up to 18 eV can be explained in terms of other p-type orbitals (C–N bonding, CH3 pseudo π, and NH2 pseudo π).
  • Kiwamu Yamaoka, Mineo Takatsuki, Masaji Miura
    1975 Volume 48 Issue 10 Pages 2739-2744
    Published: 1975
    Released: March 27, 2006
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    The interaction of trypaflavine with sodium polyphosphate in aqueous solutions in the pH range 6–7 has been investigated by means of light absorption spectroscopy, conductometric titration and ultrafiltration. The metachromatic behavior of the bound dye was characterized in terms of hypso- and hypochromic effects in both visible and UV regions where no pronounced metachromasy band was observed. The effects were studied by varying the mixing ratio of polymer residue to dye, P/D, from 0.1 to 10000. They were found to be maximum in the P/D range 2–10. The effect of the chain length of polyphosphate on metachromasy was determined by use of fourteen refractionated samples with the degree of polymerization, \barn, ranging from 8 to 158. No metachromasy appeared in samples with \barn<7. It fully developed for those with \barn>20, sharply depending on the chain length between 7 and 20. By conductometric titration and ultrafiltration, it was verified that the dye binds to the ionized phosphate almost at 1 : 1, and that the disappearance of metachromasy with the increase in P/D values or with the addition of salts results from two entirely different processes. The results were compared with the data for other dyes.
  • Isao Kanesaka, Kiyoyasu Kawai
    1975 Volume 48 Issue 10 Pages 2745-2750
    Published: 1975
    Released: March 27, 2006
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    An advanced method for the calculation of the Franck-Gondon factor is reported. It is realized on the assumption of the neglect of the zero-point motions except for the three normal coordinates whose vectors are three-dimensionally orthogonal to each other. The overlap integral is given by the Cartesian displacement coordinate system in order to consider precisely the molecular structures of the ground and excited states. This coordinate system does not cause any conflicts with the above assumption. Thus, the overlap integral is defined every nucleus with one- to three-dimensional formulae to satisfy sufficiently the Franck principle, which has been considered precisely only in the case of the diatomic molecule. The method is applied to acetylene and dideuteroacetylene with very good results. The intensity factors obtained are discussed, along with the effects of the force constants and anharmonicity.
  • Masayasu Sugisaki
    1975 Volume 48 Issue 10 Pages 2751-2754
    Published: 1975
    Released: March 27, 2006
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    The Soret coefficients of aqueous electrolytes were measured by the conductometric method for salts of K2SO4, Na2SO4, ZnSO4, and CdSO4 in the concentration range from 0.001 to 0.01 M at 25 °C and 35 °C. The heats of transport were calculated from the Soret coefficients. The concentration dependence of the heat of transport was ascertained to be proportional to the square root of the ionic strength, and the slopes for Na2SO4 and K2SO4 salts at 25 °C were found to be larger than those reported by Snowdon and Turner. The temperature dependence of the heat of transport was examined based on the data at 25 °C and 35 °C. The heat capacities concerning the transported entropy were found to be negative for the four salts examined.
  • Masakatsu Koshinuma, Tsunetaka Sasaki
    1975 Volume 48 Issue 10 Pages 2755-2759
    Published: 1975
    Released: March 27, 2006
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    A concentration cell using an ion-exchange semipermeable membrane as a septum for the measurement of the activities of ionic surfactants has been constructed, the method of measurement is here in described. The membranes used proved each to be exclusively permeable to one ion. The activities of both the tetradecyl sulfate ion (TS) and the counterion (Na+) were determined. In the concentration region from 4.0×10−4 mol/1 to CMC, logf±=−(0.070logC+0.283) held for the mean activity coefficient, f±. The f± value at the CMC was found to be 0.81, considerably smaller than the value, 0.978, calculated by the Debye-Hückel equation taking account of the ionic size, 5.5 Å. Above the CMC the activity of the TS ion decreased, that of the Na+ ion increased, and the mean activity slightly increased with the NaTS concentration. The Gibbs adsorption isotherm was applied for the adsorption of NaTS, using exclusively the observed data of the amount of adsorption, the surface tension, and the activities. A satisfactory agreement was obtained between the amount of adsorption observed and that calculated. The observed decrease in the surface tension above the CMC was confirmed by calculations using the Gibbs adsorption iostherm, the observed data of activity, and the amount of adsorption. The charged-phase separation model was verified as the mechanism of the micelle formation, and the degree of counterion attachment was calculated to be 0.81.
  • Hironobu Umemoto, Shunzo Yamamoto, Shin Sato
    1975 Volume 48 Issue 10 Pages 2760-2763
    Published: 1975
    Released: March 27, 2006
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    The ratio of the collison-broadening cross-section of ammonia to that of argon for the cadmium-resonance line at 326.1 nm has been estimated to be 2.1 by comparing the experimental data of the transmission measurement with the theoretically calculated numerical table. The table shows the relation between the transmission of a resonance line passing through the system containing absorbing atoms and the ratio of the Lorentz half-breadth to the Doppler half-breadth at different values of two parameters; the optical density, and the ratio of the Doppler half-breadth of the emission line to that of the absorption line. This table may have universal importance for the study of the absorption of atomic spectra.
  • Fumio Nozaki, Fumio Matsukawa, Yoshikazu Mano
    1975 Volume 48 Issue 10 Pages 2764-2768
    Published: 1975
    Released: March 27, 2006
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    The reduction of NO with CO over the uranium oxide catalyst and its mixed catalysts with alkali metal oxide or alkaline earth metal oxide has been investigated using conventional flow and pulse reactors at temperatures of 250 to 450 °C under atmospheric pressure. The activity of the uranium oxide catalyst without any additive was higher than that of the Fe2O3 catalyst, although it was inferior to that of the CuO–Cr2O3 catalyst. The addition of alkali metal oxide or alkaline earth metal oxide to uranium oxide, particularly in the case of Cs2O or K2O, was effective in enhancing the catalyst activity. The W/F-conversion curves revealed that the reduction of NO to N2 proceeds consecutively, passing through N2O as a gas-phase intermediate. The reaction rates were formulated as r=kPCO1.0PNO0.4. The kinetic study suggested a redox reaction sequence. The oxidation states of the catalysts were discussed on the basis of X-ray diffractograms.
  • Gernot Frenking, Hiroshi Kato, Kimihiko Hirao, Kenichi Fukui
    1975 Volume 48 Issue 10 Pages 2769-2774
    Published: 1975
    Released: March 27, 2006
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    Localized MO calculations have been carried out by the “energy localization” method of Edmiston and Ruedenberg, based upon the INDO MO’s, for 3-, 4-, and 5-membered cycloalkanes and their heterocycles containing one oxygen or nitrogen atom. Furthermore, LMO calculations were performed for the protonated three-membered heterocyclic compounds. The s-nature of the LMO’s is discussed and correlated with the bond angle, the bond moment, the bond energy, and the bond polarity. Some LMO density maps are shown.
  • Tadayoshi Yoshida, Shin-ichiro Ogura, Masataka Okuyama
    1975 Volume 48 Issue 10 Pages 2775-2778
    Published: 1975
    Released: March 27, 2006
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    The ultra-thin layer of glycerol α-cis-9-octadecenate (glycerol α-monooleate:GMO) could be formed by impregnating nitrocellulose (NC) film with GMO and by then filling microscopically the interstices of the network structure of NC with microdrops of GMO. The dielectric dispersion characteristic of this film was found to be similar to that observed for bimolecular films. In a concentrated KCl solution (100 mM), however, an anomalous dielectric dispersion phenomenon was observed below 10 kHz. The low-frequency dispersion was attributed to surface conductance along the planes of contact between the GMO microdrops and the NC network. The ultra-thin film of di(cis-9-octadecenyl)phosphate (dioleyl phosphate: DOPH) could also be formed by this method. When a constant DC voltage (50 mV) was applied across the film in a 20 mM KCl solution, the electric current through the whole system changed periodically.
  • Hiroyasu Nomura, Yutaka Miyahara
    1975 Volume 48 Issue 10 Pages 2779-2781
    Published: 1975
    Released: March 27, 2006
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    The reorientational correlation times of the benzene molecule in mixtures of benzene with carbon tetrachloride were measured by the method of the Raman line shape analysis. The reorientational relaxation times τor of C6H6 in solutions increased with increasing mole fraction of CCl4. Information was also obtained on an intermolecular vibration-vibration energy transfer process which primarily affects the mean life time of the first excited vibrational state ν2 (a1g) in benzene in solutions.
  • Jai Shanker Jha, Sudha Singh, Ram Gopal
    1975 Volume 48 Issue 10 Pages 2782-2784
    Published: 1975
    Released: March 27, 2006
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    Ion-solvent interaction of some tetraalkylammonium ions in dimethyl sulphoxide has been studied in this communication from the point of view of electrolytic conductivity and the derived Walden product. The R4N+ ions do not appear to interact strongly with this solvent; further, the salts examined appear to be completely dissociated in the concentration range studied here.
  • H. D. Purohit, H. S. Sharma, A. D. Vyas
    1975 Volume 48 Issue 10 Pages 2785-2788
    Published: 1975
    Released: March 27, 2006
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    The dielectric permittivity ε′ and dielectric loss ε″ have been measured at 9.83 GHz for the solutions of four trihalogenated esters in six non-polar solvents having wide range of viscosities at 35 °C. The static permittivity ε0 at 1 MHz and high frequency limiting permittivity ε=nD2 have also been measured at 35 °C. The normalized plots of logτ vs. logη for these esters are linear for non-interacting solvents only. The anomalous behaviour of these solutes in other solvents has been explained in terms of solute-solvent interactions. The distribution parameter α, the free energies of activation ΔFτ, ΔFη and the dipole moment μ of these esters have also been reported.
  • Hiroko Yokobayashi, Kenzo Nagase, Kazuo Muraishi
    1975 Volume 48 Issue 10 Pages 2789-2792
    Published: 1975
    Released: March 27, 2006
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    The thermal decomposition reactions of MC4H4O4 (M : Mg(II), Co(II), Ni(II), Cu(II), Zn(II), and Pb(II)) in nitrogen or helium were investigated by means of TG-DTA, X-ray diffraction measurements, gas chromatography, and combustion analysis for carbon. The decomposition residues of the Mg and Zn salts were composed of the corresponding metal oxides and some carbon, while those of the Co, Ni, Cu, and Pb salts were composed of the corresponding metals and some carbon. H2, O2, CO, CO2, H2O, CH4, C2H2, C2H4, HCOOCH3, HCOOC2H5, CH3COOC2H5, C2H5COOC2H5, and (CH2CO)2O were identified as the gaseous decomposition products; the compositions of the gaseous mixtures varied a great deal with the metals. Possible reaction mechanisms were discussed mainly on the basis of the decomposition products.
  • Yoshio Shijo
    1975 Volume 48 Issue 10 Pages 2793-2796
    Published: 1975
    Released: March 27, 2006
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    A sensitive spectrophotometric procedure for the determination of iron(III) has been developed, utilising the ternary complex system of iron–Eriochrome Cyanin R–Tridodecylethylammonium. The iron–Eriochrome Cyanin R chelate anion was extracted with tridodecylethylammonium bromide in xylene. The extracted species had an absorption maximum at 613 nm in the organic layer. The optimum pH range for the extraction was 5.8–6.5. Beer’s law held for 0.2–2 μg of iron(III) in 5 ml of the organic layer. The molar absorptivity of the extracted species was 1.73×105 cm−1·l mol−1·1 at 613 nm. The composition of the ternary complex was assumed to be (Remark: Graphics omitted.) Lead, mercury, tin, chromium, beryllium, thorium, uranium, nitrate, iodide, thiocyanate, and perchlorate interfered with the determination of iron(III).
  • Yasuaki Shimoishi
    1975 Volume 48 Issue 10 Pages 2797-2800
    Published: 1975
    Released: March 27, 2006
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    The gas-chromatographic method using an electron-capture detector has a high sensitivity for the determination of selenium. Moreover, as the reaction of selenium(IV) with 4-nitro-o-phenylenediamine is scarcely disturbed by other elements, the chemical separation from the matrix element is not necessary. The direct determination of very small amounts of selenium in copper and copper salts has been investigated. A mixture of equal volumes of nitric acid, hydrochloric acid, and perchloric acid dissolves the copper sample and also oxidizes the selenium to the quadrivalent state quantitatively. No loss of selenium was observed upon this treatment. The proposed method can determine the selenium in copper samples in amounts as low as 0.005 μg/g.
  • Masaaki Kojima, Hiromi Funaki, Yuzo Yoshikawa, Kazuo Yamasaki
    1975 Volume 48 Issue 10 Pages 2801-2804
    Published: 1975
    Released: March 27, 2006
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    The tris(meso-2,3-butanediamine)cobalt(III) complex was prepared, and four possible isomers, mer-Λ, mer-Δ, facial-Λ, facial-Δ, were isolated by column chromatography on SP-Sephadex in the formation ratio of 1.4 : 1.4 : 1.0 : 1.0. The configurations and conformations of these isomers were proposed on the basis of the electronic, the circular dichorism, and the PMR spectra.
  • Ryokichi Tsuchiya, Katsuhide Manzaki, Shigeru Sekiya, Akira Uehara, Ei ...
    1975 Volume 48 Issue 10 Pages 2805-2808
    Published: 1975
    Released: March 27, 2006
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    Thermal chelation of the following two types of complexes in solid phase was investigated by means of derivatography: Na[CoX(Hedta or Hpdta)] and [CoX(Hgly)en2]X2 (X=Cl or Br), where Hedta or Hpdta and Hgly designate quinquedentate ethylenediaminehydrogentetraacetate or propylenediaminehydrogentetraacetate ion and unidentate glycine molecule, respectively. The results show that all the complexes undergo characteristic thermal chelation through the dehydrohalogenation, giving an increase in ligand denticity from five to six in Na[CoX(Hedta or Hpdta)] and one to two in Na[CoX(Hgly)en2]X2. The reaction mechanism in the thermal chelation of each complex in solid phase was discussed in terms of the thermochemical data.
  • Takashi Uehiro, Iwao Taminaga, Yukichi Yoshino
    1975 Volume 48 Issue 10 Pages 2809-2812
    Published: 1975
    Released: March 27, 2006
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    The spontaneous decomposition of the oxalato complex of manganese(IV), [Mn2IVO2(C2O4)4]4−, in oxalate buffer solutions is investigated photometrically. It is found that the reaction proceeds in two steps, the first step being [Mn2IVO2(C2O4)4]4−→[MnIII(C2O4)3]3− and the second, [MnIII(C2O4)3]3−→manganese(II) complexes. The experimental rate at pH 3.9 is written as:
    rate & =-d[Mn_2^IV]/dt
     & =α[Mn^III]+β[Mn_2^IV]^1/2[Mn^III]+γ[Mn_2^IV]^1/2,
    where Mn2IV and MnIII denote [Mn2IVO2(C2O4)4]−4 and [MnIII(C2O4)3]3− respectively. Compared with α and β terms, the contribution of the γ term is much smaller. A mechanism involving the CO2 radical is postulated for the reaction.
  • Mutsuo Kodama
    1975 Volume 48 Issue 10 Pages 2813-2815
    Published: 1975
    Released: March 27, 2006
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    The kinetics of the substitution reactions of TTHA with nickel(II) complexes of diethylenetriamine (Dien), ethylenediaminemonoacetate (EDMA), and nitrilotriacetate (NTA) were studied systematically by employing the polarographic technique. All the substitution reactions were found to have a common reaction mechanism. They were first-order with respect to TTHA and also first-order with respect to a 1:1-ratio nickel(II) complex of Dien, EDMA, or NTA. In all the substitution reactions, the rate constants for the reactions involving a com-pletely-deprotonated TTHA anion were nearly identical to those for the corresponding DTPA (diethylenetriaminepentaacetate) reactions, suggesting that the TTHA reaction has the same reaction mechanism as the DTPA reaction. In the Dien system, the rate constant for the reaction of the quadrivalent TTHA anion is nearly identical to that of the quinquivalent TTHA anion, whereas, in the reactions of NTA and EDMA complexes, the reaction of the quadrivalent TTHA anion is drastically slower than that of the quinquivalent TTHA anion. These facts suggest that the proton transfer from the entering group to the leaving group plays an important role in determining the rate of the multidentate ligand-substitution reaction.
  • Hidetoshi Kita, Koji Tanaka, Toshio Tanaka
    1975 Volume 48 Issue 10 Pages 2816-2819
    Published: 1975
    Released: March 27, 2006
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    The reactions of Me2SnL(S2CNEt2) (L=S2CNEt2 (1) and I (2)) with iodine in cyclohexane were investigated employing a stopped-flow technique. The kinetic data indicate that the reaction in the presence of a large excess of 1 or 2 proceeds via a charge-transfer complex of Me2SnL(S2CNEt2)·I2, which decomposes in the ratedetermining step to yield Me2SnI(L) and unstable I(S2CNEt2). This unstable intermediate reacts with the excess 1 or 2 to afford Me2SnI(L) and tetraethylthiuramdisulfide (3). The reaction of 1 with a large excess of I2was also kinetically studied to reveal the formation of the 1 : 2 complex, Me2Sn(S2CNEt2)2·2I2, as an intermediate; this intermediate then undergoes a simultaneous degradation to afford Me2SnI2 and 3. The transition state in the reaction is discussed.
  • Yoichi Demura, Toshio Kawato, Hajime Kanatomi, Ichiro Murase
    1975 Volume 48 Issue 10 Pages 2820-2824
    Published: 1975
    Released: March 27, 2006
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    Metal chelates of 9-hydroxy-1-phenalenone(9-hydroxyperinaphthenone) have been prepared. Metalligand compositions were 1:2 for Cu(II), Ni(II), Co(II), Mn(II), Zn(II), Mg(II), UO2(II), and Be(II) chelates and 1 : 3 for Fe(III) and Al(III) chelates. The structure of the Cu(II) chelate was determined to be squareplanar by the spectral analogy to copper(II) acetylacetonate. The Ni(II), Co(II), Mn(II), Zn(II), and Mg(II) chelates were octahedral with further coordination of two moles of water. The structure determination dealt at first with the Ni(II) chelate by means of its electronic spectrum and magnetic property; the others were studied using the similarity of their X-ray diffraction diagrams to that of the Ni(II) chelate. The Fe(III) and Al(III) chelates were also octahedral and probably have D3 symmetry. Infrared spectra were studied for the free ligand and the metal chelates and the assignment of the carbonyl and metal-oxygen stretching vibrations was discussed by comparison with those of metal acetylacetonates.
  • Michio Hirota, Shizuo Fujiwara
    1975 Volume 48 Issue 10 Pages 2825-2828
    Published: 1975
    Released: March 27, 2006
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    Palladium(I) species were produced by the polarographic reduction of palladium(II)–oxinate and –acetylacetonate complexes in a N,N-dimethylformamide solution. These species were unstable and decomposed into electro-inactive species through an irreversible following chemical reaction. The rate constants were obtained from the fundamental and second harmonic AC polarograms, which were obtained at two different frequencies of the AC potential, 55.8 and 173.6 Hz, at 22.5 °C as 5.5±1.0 s−1 for the oxinate complex and as 50±10 s−1 for the acetylacetonate complex.
  • Kunio Ohzeki, Tooru Tamura, Tomihito Kambara
    1975 Volume 48 Issue 10 Pages 2829-2831
    Published: 1975
    Released: March 27, 2006
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    The reaction of nickel ions fixed on the ion exchange resin with 2-thenoyltrifluoroacetone was investigated in various organic solvents. In the presence of pyridine, nickel ions were quantitatively extracted from the resin into the organic phase in the form of the adducts of nickel(II) chelate with pyridine. The synergistic effect of a series of pyridine bases on the removal of the metal ions from the resin decreased in the order : pyridine >γ-picoline>β-picoline>α-picoline.
  • David J. Cookson, Thomas D. Smith, John R. Pilbrow
    1975 Volume 48 Issue 10 Pages 2832-2836
    Published: 1975
    Released: March 27, 2006
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    The X-band ESR spectra of a series of quadridentate Schiff base complexes of copper(II) have been examined in frozen xylene and chloroform solutions. Well resolved triplet state spectra were observed both at g ca. 2 and g ca. 4 due to dimeric forms of these complexes which exist in frozen solution. Magnetic and structural parameters have been determined by computer simulation of the triplet state spectra based on a lower than axial symmetry model for the copper(II) pair system.
  • N. Ray Chaudhuri, S. Mitra
    1975 Volume 48 Issue 10 Pages 2837-2841
    Published: 1975
    Released: March 27, 2006
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    Non-isothermal studies of some adduct molecules of metallic halides with ethylene glycol dimethyl ether of the type MX2(EGDME)y in solid state were carried out with a derivatograph, where M=Mn(II), Co(II), Ni(II), Cu(II) or Cd(II), X=Cl or Br, EGDME=ethylene glycol dimethyl ether and y=0.5–1. These adduct molecules lost ethylene glycol dimethyl ether in single or multiple steps upon heating. Thermally stable intermediate products were isolated and characterised by elemental analysis and IR spectral measurement. The activation energy for each step of decomposition of the adduct was evaluated from the analysis of TG, DTG and DTA curves of the respective derivatograms. Enthalpy change was evaluated from the DTA peak area and the order of reaction was found to be unity for each step of decomposition. Thermal parameters for the above adducts were compared with those for the corresponding type of adducts with oxo-compounds like dioxane or tetrahydrofuran.
  • Yasuhiko Dozen, Masato Hatta
    1975 Volume 48 Issue 10 Pages 2842-2847
    Published: 1975
    Released: March 27, 2006
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    2,3,6,7-Tetramethylnaphthalene (7b) was prepared from 2,3-dimethylsuccinic anhydride (1) and o-xylene in five steps, and the configurations of their intermediates were studied. The higher-melting isomer (threo form) of 1 gave higher-melting products in each step, while the lower-melting isomer (erythro form) of 1 gave lowermelting ones. The configurations of the intermediates were confirmed by the MNR spectral data of tetramethyltetralines (6b). Similar reactions were carried out with 3-benzoyl-2,3-dimethylpropionic acid (2a) in order to learn the configurations of the intermediates. 3-Aroyl-2,3-dimethylpropionic acids (2) gave 2,3-dimethyl-4-aryl-3-buten-4-oildes (3) upon heating with hydrochloric acid.
  • Masatsugu Kajitani, Yoshio Watanabe, Yutaka Iimura, Akira Sugimori
    1975 Volume 48 Issue 10 Pages 2848-2851
    Published: 1975
    Released: March 27, 2006
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    The selective hydrogenation of 2-naphthol (NL) was investigated with Ni (U-Ni-B, U-Ni-A, and R-Ni) and Co (U-Co-B, U-Co-A, and R-Co) catalysts in various solvents at elevated temperatures and pressure (50 kg/cm2). U-Ni-B and U-Ni-A exhibited a high selectivity for the formation of 1,2,3,4-tetrahydro-2-naphthol (ac-TL), expecially in alcoholic solvents, while the hydrogenation with R-Ni in Et2O, i-PrOH, and benzene solvents gave preferentially 5,6,7,8-tetrahydro-2-naphthol (ar-TL). The ar-TL formation over Ni catalysts decreased in the following order, irrespective of the catalysts. i-PrOH>EtOH>MeOH and Et2O> benzene. However, the selectivity over Co catalyst was influenced to a lesser extent by the solvents. The addition of amines promoted the hydrogenation of NL to ar-TL in the following order: prim->sec->tert-amine in EtOH over Ni and Co catalysts. In general, Ni catalysts are more susceptible to the effects of solvents and added amines than Co catalysts.
  • Shigeo Nishimura, Tomio Ichino, Akira Akimoto, Kiyoshi Tsuneda, Hiromu ...
    1975 Volume 48 Issue 10 Pages 2852-2854
    Published: 1975
    Released: March 27, 2006
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    Hydrogenation of 1,4-androstadiene-2,17-dione (1) with RuCl2(Ph3P)3 gives some saturated 5α-ketone together with 4-androstene-3,17-dione (2). The ratio of 2 to the saturated ketone formed increases almost in proportion to hydrogen pressure. The rate dependence upon hydrogen pressure has been shown to be first-order for formation of 2 and zero-order for formation of the saturated ketone. A mechanism which involves a 1,5-hydride shift at an intermediate species is proposed for the stereoselective formation of the 5α-ketone.
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