Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 8
Showing 1-50 articles out of 88 articles from the selected issue
  • Kazuyoshi Iimura, Naoto Kawakami, Masatami Takeda
    1969 Volume 42 Issue 8 Pages 2091-2098
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The conformational equilibria of rotational isomers of meso- and racemic-2,3-dichlorobutanes were investigated in various solvents by an infrared method. The coexistence of three rotational isomers was found for each of the meso and racemic-2,3-dichlorobutanes. However, the equilibrium concentrations changed depending on the solvent dielectric constant. The equilibrium concentration of the less polar form of a rotational isomer, in which the conformation is extended trans with respect to the Cl–C–C–Cl linkage, decreased as the solvent dielectric constant increased. The energy differences between the rotational isomers in the gaseous state and in acetonitrile solvent were also discussed.
  • R. S. Krishnan, R. S. Katiyar
    1969 Volume 42 Issue 8 Pages 2098-2101
    Published: 1969
    Released: March 27, 2006
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    The Raman spectrum of β-alanine has been recorded in the single crystal form employing λ 2537 technique. The infrared spectra in Nujol mull and KBr pellet have been taken for the range 400–4000 cm−1. The spectra exhibit the characteristic lines of the zwitter ion and also hydrogen bond vibrations in the region 2400–3000 cm−1. The tentative assignments of the observed lines are given and compared with those of other amino acids.
  • Takashi Maekawa, Toshio Yokokawa, Kichizo Niwa
    1969 Volume 42 Issue 8 Pages 2102-2106
    Published: 1969
    Released: March 27, 2006
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    The optical spectra and the magnetic susceptibilities were obtained in sodium phosphate glasses containing transition metal ions. It was shown that the content of the transition metal ions of higher valency states increases with an increase in that of Na2O whenever an oxidation equilibrium occurs between two or more valency states. By combining the visible spectra analyzed from the viewpoint of the ligand field theory with the results of the magnetic susceptibility measurement, it was shown that most transition metals coordinate six oxygen atoms in the phosphates.
  • Kihei Morinaga
    1969 Volume 42 Issue 8 Pages 2106-2111
    Published: 1969
    Released: March 27, 2006
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    The ignition of hydrogen and oxygen could be induced by the so-called silent electric discharge, and the ignition delay time after the termination of the discharge was found to be proportional to a logarithm of the discharge intensity (pulse current). The proportionality constants in different diluents, argon and helium, were analyzed to yield the net effect of chain breaking in the reaction:
    H+O2+M\xrightarrowk4HO2+M
    and the rate coefficient, k1, for the reaction:
    H+O2\xrightarrowk1OH+O
    assuming a third-body efficiency of the diluent gases. It was inferred from the results that the radical reproducing from HO2 significantly lessened the effect of the above chain breaking reaction, the accumulation of radicals seemed to be persistent even in the low-temperature region, where the k1 value was observed not to be above the assumed value of k1[M]/2.
  • Tokio Yamabe, Kenichi Fukui
    1969 Volume 42 Issue 8 Pages 2112-2119
    Published: 1969
    Released: March 27, 2006
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    A theory of the molecular-size distribution of cross-linked polymers to be formed from a mixture of polyfunctional monomers and mono-functional monomers through step-by-step polymerizations by certain initiators is presented on the assumption that all unconverted functional groups are equireactive for both initiations and propagations, which proceed without termination, transfer, or cyclization. The distribution is obtained by applying the statistical theory of gel formation with multifunctional interunit junctions, which are, in this case, equivalent to cross-linking chains. Some noticeable theoretical results are obtained: (1) the distribution obtained is quite different from that obtained for branched-chain polymers by condensation polymerization; (2) the fraction of converted functional groups at the gel point is independent of the initial concentration of the monofunctional monomer, while it is in proportion to the ratio of the initial concentration of the initiator to that of polyfunctional monomers; (3) there is a certain condition under which the gelation will never take place, even at complete conversion, and (4) the state to be reached after the gel point is quite different from the results obtained previously. The case of a mixture of monomers with any distribution of functionalities is also briefly presented. An explanation of the validity of the distribution beyond the gel point is discussed in the Appendix.
  • Shizuo Fujiwara, Kayoko Sakioka
    1969 Volume 42 Issue 8 Pages 2120-2122
    Published: 1969
    Released: March 27, 2006
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    The mechanism of ESR relaxation in ·ON(SO3)22− is discussed. As the line width in an aqueous solution is plotted against the concentration, it is almost concentration independent in the range lower than 7×10−3 mol/l, but the dependence increases in the higher range. Powles and Moseley showed that the anisotropy of the g-value contributes to the line width in the lower concentration range, but the line width in the higher-concentration range, which is investigated in the present investigation, can not be accounted for by the g-tensor anisotropy. Hence, it is supposed that electron spin exchange or nuclear quadrupole interaction contributes in the higher-concentration range. The latter can, however, be eliminated by the line width measurement in a deuterium measurement in a deuterium oxide solution, and so it may be concluded that electron spin exchange is the main contribution to the line width in the higher-concentration range. This is in accordance with the proposal of Jones. Furthermore, we could show that, by calculation of the line shape for Bloch’s equation, including exchange interactions, the exchange frequency of 5.4×107 sec−1 can give a line fitting the observed line shape for the 7.8×10−2 mol/l solution. This result can be taken as another evidence showing that the electron spin exchange is the main source of the line width in the higher-concentration range.
  • Keishiro Shirahama, Makoto Hayashi, Ryohei Matuura
    1969 Volume 42 Issue 8 Pages 2123-2128
    Published: 1969
    Released: March 27, 2006
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    Solubilities and critical micelle concentrations (CMC) of potassium dodecyl sulfate (KDS) and hexadecyl sulfate (KHS) were measured in aqueous solutions to which dioxane, acetone, urea, or dimethyl sulfoxide had been added over the temperature range of 5–40°C. It was found that all additives mentioned above raised solubility and CMC with an exception for dioxane which showed a slight minimum on a CMC-additive concentration curve. Solvent effects on the alkyl and ionic groups of a surfactant molecule were separated by considering the difference of the standard free energy change for the solution process of KHS and that of KDS. It was deduced that a primary effect on the alkyl group is the one that a strongly cohesive solvent, water, is replaced by a less cohesive organic solvent and other mechamisms, such as an effect on the water structure, follow as the secondary. In terms of the above considerations, effects on the Krafft point were also referred to.
  • Kuniyasu Tanno, Shoji Shida
    1969 Volume 42 Issue 8 Pages 2128-2131
    Published: 1969
    Released: March 27, 2006
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    The reactions of ions, especially fragmentation of excited ions and the subsequent reactions of fragment ions in the radiolysis of liquid propane have been investigated by the use of charge scavengers such as sulfur hexafluoride (SF6) and ammonia (NH3). It has been confirmed that the fragment ions are produced by the dissociation of the excited parent ion prior to the parent ion-electron recombination. The yields of C2H5+ and C3H7+ have been measured by the use of the reaction, RH++ NH3→R+ NH4, with the results G≥0.28 and ∼1.1 respectively. These ions neutralize with electrons to form ethylene or propylene. The hydride ion transfer reaction between C2H5+ and propane may be competing with the neutralization of C2H5+ by electron in the absence of an additive. The yields of fragment ions are compared in the radiolysis of several saturated hydrocarbons.
  • Yukihiko Nakajima, Shin Sato, Shoji Shida
    1969 Volume 42 Issue 8 Pages 2132-2136
    Published: 1969
    Released: March 27, 2006
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    A series of monocarboxylic acids and esters have been γ-irradiated at 77°K, either pure or in the rigid matrix of 2-methyltetrahydrofuran, and the products have been examined by ESR spectroscopy. The spectra obtained in the pure state showed that the primary paramagnetic species in each case is the corresponding radical anion, (Remark: Graphics omitted.). In the rigid matrix, these characteristic spectra have been obtained after illuminating the γ-irradiated sample with visible light at the expense of the spectra of trapped electrons. When ultraviolet light was used for the illumination, the spectra of the radical anions disappeared, but instead appeared the spectra of the radicals produced by the decomposition of the radical anions. The latter spectra were almost the same as those obtained by the direct photolyses of acids and esters.
  • Hatsuho Uedaira, Hisashi Uedaira
    1969 Volume 42 Issue 8 Pages 2137-2140
    Published: 1969
    Released: March 27, 2006
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    Osmotic and activity coefficients of aqueous xylose and maltose solutions at 25°C are measured by the isopiestic vapor pressure method. Densities of these solutions are also determined at 25°C. The activity coefficients of water in these solutions show that both xylose and maltose solutions do not behave as regular solutions. Second virial coefficients for xylose and maltose are calculated from partial molar volumes of the solute and the solvent at infinite dilution and empirical equations of water activity coefficient. The coefficients calculated for xylose and maltose are 111 and 248 cc/mol, respectively. Second virial coefficients for these sugars and a few other sugars are approximately proportional to the molecular weight. This relation is explained by the van der Waals model.
  • Hisashi Ueadaira, Hatsuho Uedaira
    1969 Volume 42 Issue 8 Pages 2140-2142
    Published: 1969
    Released: March 27, 2006
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    Diffusion coefficients for the systems aqueous xylose solution and aqueous malotse solution at 25°C were measured by the Rayleigh interference method. Viscosities of these systems were also determined. The concentration dependence of diffusion coefficient for maltose solution is well described by the Gordon relation. For xylose solution, however, a small deviation from this relation is observed. The translational frictional coefficient of maltose was calculated by the shell model of Bloomfield et al. If the effect of the local viscosity around a molecule of the solute is corrected, the agreement between the calculated and the observed values is satifsactory.
  • Tasuku Nakai
    1969 Volume 42 Issue 8 Pages 2143-2148
    Published: 1969
    Released: March 27, 2006
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    A novel method for the estimation of the interfacial energy of an embryo from the solubility data in solid-liquid systems has been proposed. The distribution function of embryos in solutions derived thermodynamically has been used as the base for the present treatment. The interfacial energies were calculated numerically for three different combinations of solute and solvent, namely, water-inorganic salt, water-organic compound, and organic solvent-organic compound. A fairly good linear relationship was observed between the interfacial energies calculated and the temperatures over the whole temperature range of solubility data. The semiempirical equation describing the relationship between the interfacial energy of the embryo and the temperature in the solid-liquid system was found to be exactly the same as that between the surface energy of the liquid in contact with gas through a free surface and the temperature. The size dependence of the interfacial energy has also been briefly described.
  • Chuichi Kato, Shigehiro Konaka, Takao Iijima, Masao Kimura
    1969 Volume 42 Issue 8 Pages 2148-2158
    Published: 1969
    Released: March 27, 2006
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    The molecular structures of formaldehyde, acetaldehyde, and acetone have been investigated by the sector-microphotometer method of electron diffraction. Certain of the bonded interatomic distances, rg, were determined to be as follows: for formaldehyde, r(C–O)=1.2093±0.0033 Å and r(C-H)=1.0967±0.0535 Å; for acetaldehyde, r(C=O)=1.2085±0.0033 Å and r(C–C)=1.5142±0.0051 Å; for acetone, r(C=O)=1.2110±0.0041 Å and r(C–C)=1.5167±0.0048 Å. The value of rg(C=O) for formaldehyde was perfectly consistent wth the zero-point average distance, rz(C=O), determined by microwave spectroscopy.
  • Takao Iijima, Masao Kimura
    1969 Volume 42 Issue 8 Pages 2159-2164
    Published: 1969
    Released: March 27, 2006
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    The zero-point average structure of acetaldehyde has been determined by the use of the moments of inertia and the average distances, obtained by microwave spectroscopy and electron diffraction respectively. The following rz parameters have been determined: 1.515±0.005 Å for C–C, 1.207±0.004 Å for C=O, 1.073±0.002 Å for C–H(methyl), 123°48′±9′ for ∠CCO, and 108°52′±17′ for ∠HCH of the methyl top.
  • Tatsuya Yasunaga, Shoji Harada
    1969 Volume 42 Issue 8 Pages 2165-2169
    Published: 1969
    Released: March 27, 2006
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    The temperature-jump method was used to study the kinetics of FeCl2+ and FeBr2+ complex formations in aqueous solutions. Complex formation is composed of two paths. In the acid-independent path, the rate-determining step of complex formation may be the reaction between Fe(H2O)53+ and X (X=Cl, Br). The other path is that via the hydrolysis of ferric ions, and the rate-determining step is the loss of a water molecule from the inner coordination sphere of the metal ion. The kinetic values obtained are in good agreement with the results obtained by the flow method.
  • Yoshio Matsunaga
    1969 Volume 42 Issue 8 Pages 2170-2173
    Published: 1969
    Released: March 27, 2006
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    The orbital electronegativities in the nine aromatic hydrocarbons were estimated on the basis of the ionization potentials and the appearance potentials of the doubly-charged ions. Then, by applying the principle of electronegativity equalization to molecular complexes, the orbital electronegativities in typical electron acceptors were evaluated. The ionic character in single and crystal complexes were discussed in terms of the electronegativities of the component molecules. Consideration of neither the ionization potential of the donor molecule, the electron affinity of the acceptor molecule, nor the orbital electronegativities appeared to be enough to define the ionic character in a complex.
  • Masayasu Kurahashi, Makoto Fukuyo, Akira Shimada, Akio Furusaki, Isamu ...
    1969 Volume 42 Issue 8 Pages 2174-2179
    Published: 1969
    Released: March 27, 2006
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    The crystal structure of carbazole has been refined with three-dimensional X-ray data. Single crystals obtained from the melt are orthorhombic with four molecules in a unit cell of the dimensions a=7.772, b=19.182 and c=5.725 Å; space group is Pnma. Positional and thermal parameters were obtained by the least-squares method. The final discrepancy index R is 10.9% excluding zero intensity data. The e.s.d.’s in bond lengths not involving hydrogen atoms are 0.006–0.010 Å, and the corresponding errors in bond angles are about 0.5°. The molecule is planar within the deviation of 0.03 Å. A crystallographic mirror plane normal to the b-axis passes through the nitrogen atom and is perpendicular to the molecular plane. Comparison of the observed and theoretical bond lengths is made with discussion thereof. Some physical properties related to the crystal structure are also discussed by comparing its structure with that of fluorene. With the help of thermodynamical data, it has been argued that the hydrogen bond of N–H···N between molecules is not formed not only in the crystalline state but also in the liquid state.
  • Taro Tachibana, Toshie Ohya, Tohru Yoshioka, Junji Koezuka, Hiroko Iko ...
    1969 Volume 42 Issue 8 Pages 2180-2183
    Published: 1969
    Released: March 27, 2006
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    Mössbauer spectral studies were made of samples of α-Fe2O3 highly dispersed on silica gel before and after activation, which consisted of evacuated heating at 475°C. The spectra gave Ividence that Fe2+ ions were produced from α-Fe2O3 during the activation process. Reduction was impossible after the activation and oxidation had been repeated three times. However, the inactivated sample came to be again reduced by activation after having been exposed to water vapor at room temperature. In order to explain these facts, a working hypothesis was advanced that the hydroxyl groups near the surface of the particles play a principal role in reacting with organic contamination from the vacuum system, as a result bringing about the partial reduction of α-Fe2O3.
  • Masao Suzuki, Kunio Kozima
    1969 Volume 42 Issue 8 Pages 2183-2186
    Published: 1969
    Released: March 27, 2006
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    The microwave spectrum of trans-crotonaldehyde has been measured in the frequency region from 8.2 to 36 kMc/sec. The R-branches for the a-type and the R- and Q-branches for the b-type have been assigned. The low J transitions of the a-type and all of the b-type transitions are split into the A-level and the E-level by the internal rotation of the methyl group. The apparent rotational constants for the A- and E-levels have been obtained from the pseudo-rigid rotor approximation as AA=32636.58 Mc/sec, AE=32627.57 Mc/sec, B=2183.30 Mc/sec, and C=2073.32 Mc/sec. From these values it can be concluded that this molecule is of the s-trans form. The barrier height of the hindering rotation of the methyl group is 1730±10 cal/mol. The value of the total dipole moment is 3.72±0.28 D.
  • Hiroshi Yokoi, Taro Isobe
    1969 Volume 42 Issue 8 Pages 2187-2193
    Published: 1969
    Released: March 27, 2006
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    The ESR and the optical absorption of the copper(II) complexes of ethylenediamine and a series of alkylated ethylenediamines have been investigated in order to estimate the character of the chemical bonding in the copper(II) complex. The covalency of the bonding of the copper atom to the ligand nitrogen atoms in the complexes has been discussed in connection with the chemical and physical properties of the complexes or of their ligand molecules themselves. The ESR results indicate that the σ bonding of the complexes becomes more covalent as the number of alkyl groups in their ligand molecules increases; furthermore, the tendency toward the σ bonding becomes more pronounced when the alkyl groups are ethyl rather than methyl and when they are N-substituted alkyl groups rather than C-substituted ones. It is also indicated that there is a linear relationship between the energies of the ultraviolet absorption band for the complexes and the relative ionization potentials estimated for their ligand molecules, and that absorption band can be assigned to an electron transfer from a ligand σ orbital to an antibonding orbital associated with the copper atom. From these results, it may be concluded that, as the σ bonding becomes more covalent, this charge transfer band shifts to a longer wavelength.
  • Toshihide Tsuji, Kazuo Fueki, Takashi Mukaibo
    1969 Volume 42 Issue 8 Pages 2193-2198
    Published: 1969
    Released: March 27, 2006
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    Activity, and partial molal free energy, enthalpy and entropy of AgBr in AgBr-NaBr solid solutions have been obtained at 350 and 400°C from the e.m.f. data of galvanic cells of the type Ag/AgBr-NaBr/Br2. It has been found that the solid solution forms a regular solution defined by Hildebrand. A miscibility gap has been found by the study of galvanic cells and confirmed by high temperature X-ray diffraction. A new phase diagram of the AgBr-NaBr system is presented.
  • Teiji Omori, Junichiro Imai, Mahiko Nagao, Tetsuo Morimoto
    1969 Volume 42 Issue 8 Pages 2198-2202
    Published: 1969
    Released: March 27, 2006
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    Two kinds of anatase samples which have very large specific surface areas and low crystallinities were prepared, and the interaction between the solid surface and the water molecule was investigated by measuring the water content, the heat of immersion in water, and the infrared spectrum of each sample. Two characteristic features were found in these samples: first, the plot of the heat of immersion vs. the pretreatment temperature did not reveal such a maximum as had been found previously with the crystalline anatase, and second, the heat of surface hydration as calculated from the plot of the heat of immersion vs. the water content was found to be remarkably smaller than with the crystalline anatase. These facts have led us to conclude that, with the anatase samples of a low crystallinity, not only does the rehydration reaction of a surface oxide structure produced at an elevated temperature proceed more easily on immersion in water, but also the heat of rehydration is smaller, than in a sample of a high crystallinity. Moreover, it was found from an infrared spectroscopic investigation that the water molecules physisorbed on the surfaces of large-area samples could be desorbed more gradually than those on small-area samples and remained small in quantity up to near 300°C in vacuo.
  • Tohru Azumi, Saburo Nagakura
    1969 Volume 42 Issue 8 Pages 2203-2208
    Published: 1969
    Released: March 27, 2006
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    General equations applicable to photoselection experiments for Zeeman split phosphorescence are derived. The general equations are also extended to the cases where excitation and observation are effected with unpolarized light, and expressions for the ratio of phosphorescence intensities of the three split subcomponents are obtained. Some comments on experimentation are made.
  • Takahisa Ichikawa, Keiji Kuwata
    1969 Volume 42 Issue 8 Pages 2208-2211
    Published: 1969
    Released: March 27, 2006
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    ESR studies on the UV irradiated α,β-unsaturated aldehyde - hydrogen peroxide mixtures have been done at low temperature in order to examine the reactions of an OH radical with aldehyde: formyl hydrogen-abstraction, methyl hydrogen-abstraction, and addition to an olefinic bond. It has been shown that abstraction of a methyl hydrogen by an OH radical occurs in croton-aldehyde, whereas β-addition of an OH radical to an olefinic bond takes place in methacrolein and acrolein. A formyl hydrogen is unreactive with an OH radical in any case. The distribution of unpaired electron in the radicals was also discussed.
  • Toru Nakagawa, Yonezo Morino
    1969 Volume 42 Issue 8 Pages 2212-2219
    Published: 1969
    Released: March 27, 2006
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    The general fourth-order potential constants, f, for hydrogen cyanide were determined by a least-squares analysis applied to the observed values of the vibrational energies and the rotational constants for six isotopic species, H12C14N, H13C14N, H12C15N, D12C14N, D13C14N, and D12C15N. The normal frequencies, ωi, the cubic and quartic potential constants, kijk and kijkl, the anharmonicity constants, xij, the vibration-rotation interaction constants, αi, and the Coriolis coupling constants, ζijx were calculated for the six isotopic species.
  • Katsutoshi Ohkubo, Tokio Yamabe, Kenichi Fukui
    1969 Volume 42 Issue 8 Pages 2220-2227
    Published: 1969
    Released: March 27, 2006
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    The low-temperature liquid-phase oxidation of cumene using triphenylsulfonium chloride was-studied in order to establish the nature of the activity of sulfonium catalysts and the oxidation mechanism. The oxidation occurs in an autocatalytic fashion below 70°C, while it proceeds in an-auto-retarding fashion above 85°C. This is a characteristic feature of this oxidation. The cause of the deactivation at higher temperatures is mainly the deoxygenation of the assumed complex (Cat.···O2). The decomposition of cumene hydroperoxide and the subsequent formation of α-cumyl alcohol, acetophenone, and dicumyl peroxide were seriously affected by the presence of sulfonium salts. The formation of acetophenone was accelerated thermally, while that of a-cumyl alcohol was not accelerated much, though it was accelerated by the catalyst-oxygen complex. Dicumyl peroxide, once formed in an appreciable amount, was gradually decomposed, both thermally and catalytically. The catalyst was deactivated by the product formed. This phenomenon was attributed to the masking action of oxygen-containing products. The mechanism oxidation was discussed on the basis of these observations.
  • Tsunenari Saito, Shin Sato
    1969 Volume 42 Issue 8 Pages 2228-2232
    Published: 1969
    Released: March 27, 2006
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    The luminescence from a benzene solution containing p-terphenyl induced by γ-ray irradiation has been compared with that induced by UV irradiation at 2500 Å in the presence of various quenchers. The quenching efficiencies of electron and positive ion scavengers (SF6, N2O, CO2 and NH3) were found to be greater for the γ-ray excitation than for the UV excitation, while 1,3-butadiene, which is known as a quencher for excited benzene, (1B2u), showed almost the same efficiency for both modes of excitation. These results suggest that, even in a benzene solution, a series of ionic reactions is partly responsible for the formation of the scintillating state of p-terphenyl, and that the apparent quenching effect of ion scavengers is mainly due to their interference in the formation of the excited state of the benzene which is produced by the recombination reaction between the benzene cation and an electron. It was estimated that more than 30% of the excited state of benzene is formed by the recombination reaction.
  • Hiroshi Yokoi, Mitsuru Sai, Taro Isobe
    1969 Volume 42 Issue 8 Pages 2232-2238
    Published: 1969
    Released: March 27, 2006
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    The ESR of bis-(N,N-diethylethylenediamine)copper(II) perchlorate has been examined in the polycrystalline state at three temperatures corresponding to the color change in the copper (II) complex due to thermochromism, in the glassy state of an aqueous solution at the temperature of liquid nitrogen, and in the magnetically-diluted state in diamagnetic bis-(N,N-diethylethylenediamine)nickel(II) perchlorate powder at three temperatures corresponding to the color change of the diluent due to thermochromism. The g and A values for square planar copper(II) complexes have been discussed in connection with the strength of the axial ligand field. The ESR results indicate that the structure of bis-(N,N-diethylethylenediamine)copper(II) perchlorate changes remarkably according to its circumstances, and possible mechanisms for the thermochromism have been suggested.
  • Yoshimi Kurimura, Hideo Kuriyama
    1969 Volume 42 Issue 8 Pages 2238-2242
    Published: 1969
    Released: March 27, 2006
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    The kinetics of the autoxidation of ferrous ions in tripolyphosphate solutions (pH 2–8) at an ionic strength of 0.20 M NaClO4 was studied using a spectrophotometric technique. The rate expression for the oxidation reaction is given by:
    d[Fe(III)]⁄dt=4kI[FeII(Htpp4−)][O2]+4kII[FeII(Htpp4−)2][O2],
    and 4kII found is to be 1.0×102 M−1 sec−1 at 15°C. The simultaneous reaction paths of
    FeII(Htpp4−)+O2\xrightarrowkIFeIII(Htpp4−)+O2- and FeII(Htpp4−)2+O2\xrightarrowkIIFeIII(Htpp4−)2+O2-
    are consistent with the results obtained. When there is an excess of the triphosphate solution in the pH range from 6 to 8, the latter may be the rate-determining step. The acceleration of the oxidation of the ferrous ions in the triphosphate solution may be due to the fact that the stabilization of the oxidation products, FeIII(Htpp4−) and FeIII(Htpp4−)2, is greater than that of the corresponding ferrous triphosphate complexes. As the activation parameters for the latter reaction, the experiments gave the values of ΔH\ eweq∼10 kcal mol−1 and ΔS\ eweq∼−25 cal mol−1. deg−1. The negative and relatively small value of the entropy of activation suggests that the activated complex is more extensively hydrated than is the ferrous complex of FeII(Htpp4−)2.
  • Akio Iwase, Chieko Yokoyama
    1969 Volume 42 Issue 8 Pages 2243-2246
    Published: 1969
    Released: March 27, 2006
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    The oscillopolarographic behaviour of lanthanide ions at the dropping mercury electrode and hanging-drop mercury electrode was discussed. The variations of incision depth on the oscillopolarograms with a dropping mercury electrode in KSGN, KCl, KBr and NaClO4 at pH 3.65 and 4.65 were found to depend on the first ionization potentials and the basicity of the lanthanide. On the basis of the results obtained it can therefore be presumed that the electrode reaction rate increases with the increase of the first ionization potentials.
  • Goro Yamaguchi, Masataro Okumiya, Shuichiro Ono
    1969 Volume 42 Issue 8 Pages 2247-2249
    Published: 1969
    Released: March 27, 2006
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    The structure of tohdite, 5Al2O3·H2O, was determined by Yamaguchi Yanagida, and Ono (1964). Least-squares refinements based on their structure have been carried out using X-ray-powder data. The final R factor of the reflection intensity reduced to 0.08 from the initial value of 0.26.
  • Fumiaki Kai
    1969 Volume 42 Issue 8 Pages 2250-2254
    Published: 1969
    Released: March 27, 2006
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    The formation constants of the complex formed between o-(2-thiazolylazo)-4-chlorophenol TACL, and mercury(II) in 2% v/v dioxane-water were logKHgR+=6.21 and logKHgR2=6.10 at μ=0.1 and at room temperature. TACL was suggested as a suitable metallochromic indicator for the direct titrimetric determination of mercury(II) ions at pH 6.7–8.7 with an EDTA titrant. This optimum pH range was rather wide compared with that of the other metallochromic indicators, such as Cu-PAN, XO, and MTB. There were marked colour changes from deep blue to reddish-yellow or to violet at equivalence points. The mercury(II) ions up to 210 mg in 100 ml can be determined within an error of ±0.3% by this method.
  • Yu Yokoyama, Shigero Ikeda
    1969 Volume 42 Issue 8 Pages 2254-2258
    Published: 1969
    Released: March 27, 2006
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    Photonometric titration of thallic ion is described, in which uranous ion, the titrant, is generated by photoreduction of uranyl ion in a sulfuric acid solution containing sodium lactate. Uranyl ion could be reduced with the light at wavelengths longer than 300 mμ, whereas thallic ion could not be reduced with the light in this wavelength range. Selective photoreduction of uranyl ion was accomplished by eliminating wavelengths below 300 mμ with a filter. In this photonometric titration, reaction solutions were irradiated without stirring at 29.5±0.5°C. The absorbance of uranous ion produced was measured at 655 mμ, every fixed irradiation time, and the absorbance was plotted against the irradiation time. Induction period, which means the period during which the absorbance remains actually zero, was in a linear relation with thallic concentration. Thus the titration of thallic ion was satisfactorily carried out in the concentration range from 0.01 to 0.1 mM. The results proved the feasibility of titration in a completely sealed container and suggest a possibility of titration on a microvolume of reaction solution.
  • Akira Ouchi, Hiroshi Eguchi, Toshio Takeuchi, Akiko Furuhashi
    1969 Volume 42 Issue 8 Pages 2259-2263
    Published: 1969
    Released: March 27, 2006
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    The bromo-3-methyl-5-phenyl-1,2-dithiol-1-ium complexes were obtained from metal benzoylacetonate, using hydrogen sulfide and bromine with a catalyst of hydrogen bromide. These complexes resemble bromo-bis(3,5-dimethyl-1,2-dithiol-1-ium) complexes and many of them are of the high-spin type. The Zn(II) and Cd(II) complexes are of the ML2Br4 type (where M=metal and L=3-methyl-5-phenyl-1,2-dithiol-1-ium), like 3,5-dimethyl-1,2-dithiol-1-ium complexes, while Cu(I) is of the MLBr2 type. However the analytical results shows that the Mn(II), Fe(II) and Co(II) complexes are of the ML2Br3 type. Infrared spectra as well as electronic spectra are shown and discussed.
  • Yasuo Torii, Takanori Yazaki, Youkoh Kaizu, Shigetaka Murasato, Hirosh ...
    1969 Volume 42 Issue 8 Pages 2264-2267
    Published: 1969
    Released: March 27, 2006
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    Electronic absorption spectra of the alkali metal complexes with 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine or 5,5′-dimethyl-2,2′-bipyridine have been observed in tetrahydrofuran solutions. Each spectrum has four major bands in the near infrared, visible and near ultraviolet regions, and is essentially due to the π–π*transitions in the negative ion (extra π electron trapping state) of bipyridine or its dimethyl derivatives coordinating to a metal ion. The band about 18000 cm−1 is the most sensitive to the metal ion species involved and assigned to a transition with the polarization parallel to the short axis of the bipyridine molecule. Each absorption band of the bipyrdine negative ion shows characteristic spectral shift upon CH3-substitutions in its peripheral positions. This CH3-substitution effect on the absorption spectra of bipyridine negative ion is quite different from that of complexes including neutral bipyridines and gives a basis of the criterion to determine whether the coordinating bipyridine in a certain bipyridine complex do exist in negative ion (π electron trapping state) or not.
  • Mutsuo Kodama, Yayoe Tominaga
    1969 Volume 42 Issue 8 Pages 2267-2272
    Published: 1969
    Released: March 27, 2006
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    The d.c. polarographic behavior of the cadmium(II) ion in ethylenediaminetetrapropionate (EDTP) was studied in the pH range from 8.30 to 10.30. Over the entire range of experimental conditions employed, the cadmium(II)ion invariably gave a single well-defined wave corresponding to the following reversible two-electron reduction:
    (Remark: Graphics omitted.)
    Even in the presence of ammonia or the alaninate ion, the cadmium(II) ion in the EDTP solution also behaves reversibly in a polarographic electrolysis. However, the half-wave potential was found to be shifted to the more negative potentials by the addition of ammonia or alaninate. This was ascribed to the formation of a mixed ligand chelate involving ammonia or the alaninate ion. From the relation between the shift of the half-wave potential and the concentration of ammonia or alaninate, the composition and the stability constant of the mixed ligand chelate were determined and the electrode reaction was established as:
    (Remark: Graphics omitted.)
    where A means the ammonia or the alaninate ion. The K2, KNH3, and Kala values determined were 5.5×102, 1.38×102, and 2.61×104 respectively.
  • Takayoshi Sakai, Yûko Funaki
    1969 Volume 42 Issue 8 Pages 2272-2275
    Published: 1969
    Released: March 27, 2006
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    Zirconium(IV) reacts with an excess of bromopyrogallol red to form a violet complex. The constant absorbance of a solution containing the complex is obtained in the pH range from 5.0 to 5.4 at 670 mμ. About 25 min is required to complete the chelate formation in a boiling water bath. The complex thus formed is stable for at least 3 hr. The color system obeys Beer’s law in the range from 4 to 35 μg zirconium in 25 ml. The sensitivity of the reaction is 0.002 μg per cm2 for an absorbance of 0.001. In composition the complex has a metal-to-ligand ratio of 1:2. The molar absorptivity and the apparent formation constant of the complex are calculated to be 7.01×104 at 670 mμ and 1.11×109 at pH 5.2 respectively. The effect of diverse ions on the determination is examined.
  • Nobufumi Maki
    1969 Volume 42 Issue 8 Pages 2275-2281
    Published: 1969
    Released: March 27, 2006
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    The bis(2,2′-dipyridyl) and bis(1,10-phenanthroline) cobalt(III) complexes of the [CoX2N4]-type, including the following new compounds, have been prepared: [Co(CN)2dip2]NO3·7H2O, [Co-(CN)2dip2]2SO4·12H2O, Na[Co(SO3)2dip2]·5H2O, Na[Co(S2O3)2dip2]·7H2O [Co(N3)2dip2]N3·2H2O, [Co(N3)2dip2]ClO4, [Co(N3)2dip2]2SO4·5H2O, [Co(N3)2dip2]NO3·2H2O, [Co(N3)2dip2]Cl·3H2O, [Co(SCN)2dip2]NCS·\frac52H2O, [Co(SCN)2dip2]ClO4·2H2O, [Co(SCN)2dip2]Cl·3H2O, K[Co(SO3)2phen2]·5H2O, [Co(NO2)2phen2]Cl·4H2O, Na[Co(S2O3)2phen2], [Co(N3)2phen2]N3[Co(CN)2phen2]NO3·6H2O, [Co(CN)2phen2]Cl·4H2O. The known compounds, including the cobalt(II) and cobalt(III) complexes of the luteo type, have also been prepared by methods other than those described hitherto in the literature. The absorption spectra in the visible and ultraviolet regions have been measured and compared with those of the bis(ethylenediamine)cobalt-(III) complexes. The rhodanato-cobalt(III) complexes, [Co(SCN)2dip2]ClO4·2H2O and [Co-(SCN)2phen2]NCS, have been ascertained to be the sulfur-bonded thiocyanato complexes on the evidence of the absorption spectra in the visible and infrared regions.
  • Yoshiro Ogata, Yoshio Kosugi
    1969 Volume 42 Issue 8 Pages 2282-2286
    Published: 1969
    Released: March 27, 2006
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    A novel quantitative determination of L-ascorbic acid by UV spectrophotometry in a HCl-KCl buffer has been developed. Ascorbic acid (λmax 244 mμ) of over 2×10−5 M can quantitatively be determined by this method. Several oxidizing, reducing, acidic or basic reagents and other organic compounds which may be present together with ascorbic acid in ordinary drugs and drinks do not interfere the determination.
  • Masaru Noguchi, Akashi Yoshifuji, Zenzi Hagiwara
    1969 Volume 42 Issue 8 Pages 2286-2291
    Published: 1969
    Released: March 27, 2006
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    In order to find the accurate separation factors of two adjacent rare earths between the aqueous and resin phases, measurements were performed at 30°C in the presence of EDTA and using Dowex 50W, X-8, 50–100 mesh. The following results were obtained under the same experimental conditions as were employed in ion-exchange system for the isolation of the rare earth series. The separation factors were 2.05 for Er-Tm, 1.88 for Dy-Ho, 1.61 for Y-Dy, 1.76 for Tb-Y, 1.30 for Eu-Gd, and 3.77 for Sm-Nd. In the Er-Tm separation factor, a fairly large discrepancy was observed between the calculated and experimental values. It is concluded from the experimental results that the separation factors of pairs of lanthanons should be directly measured.
  • Takako Inazu, Hisashi Okawa, Takahiko Inazu, Tamotsu Yoshino
    1969 Volume 42 Issue 8 Pages 2291-2295
    Published: 1969
    Released: March 27, 2006
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    In this paper, the syntheses of copper(II) complexes of 3-alkylsalicylaldehydes, B, as well as the syntheses and properties of dimeric copper(II) complexes, C, with bridged alkoxy groups are reported.
  • Isao Masuda, Mitsuhiro Sakano, Koichiro Shinra
    1969 Volume 42 Issue 8 Pages 2296-2300
    Published: 1969
    Released: March 27, 2006
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    Dimethylglyoxime-Co(III) complexes with the formula [Co(dmgH)2A2]n (I), where dmgH is dimethylglyoximato mono-anion, A is an axial ligand such as aniline, p-anisidine, pyridine, γ-picoline, imidazole, NH3, CN, and NO2, and n is −1, 0, or +1, were found to change their electronic absorption spectra reversibly depending on the pH of the solution. These changes have been attributed to the dissociation of the proton from the intramolecular hydrogen bridges of the complex; the changes are accompanied by the formation of the complex [Co(dmgH)(dmg)A2]n−1, where dmg represents the dimethylglyoximato di-anion. The proton dissociation constants (pKa) obtained by the spectrophotometric method indicated that the complex I is generally a weak acid of pKa=7.7–12.6. With the exception of the pyridine and the γ-picoline ligand, axial ligands do not appreciably affect the pKa values. However, axial pyridine and the γ-picoline ligand increase the tendency of the hydrogen bridges to dissociate the proton.
  • Nobuyuki Tanaka, Tadashi Fujisawa
    1969 Volume 42 Issue 8 Pages 2300-2302
    Published: 1969
    Released: March 27, 2006
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    The electrochemical behavior of platinum in solutions of ethylenediaminetetraacetate(EDTA) has been investigated by the measurements of current-potential and current-time curves and by the controlled-potential electrolysis. EDTA gives the anodic limiting current, which is much smaller than that of one-electron transfer obtained for the ordinary diffusion-controlled electrode reaction. Platinum was detected by the spectrophotometric method in the solution which was subjected to the electrolysis at controlled potential. The results suggest that the anodic current is due to the electrolytic dissolution of the platinum electrode by the reactions,
    Pt+2H2O→Pt(OH)2+2H+2e (1)
    Pt(OH)2+H2Y2→PtY2−+2H2O (2)
    where Y4− represents a quadrivalent anion of EDTA.
  • Akira Misono, Yasuzo Uchida, Ken-ichi Furuhata, Shohei Yoshida
    1969 Volume 42 Issue 8 Pages 2303-2307
    Published: 1969
    Released: March 27, 2006
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    The oligomerization of isoprene by catalyst systems consisting of a zirconium compound and an organoaluminum compound was studied. Isoprene was dimerized to 2,6-dimethyl-1,trans-3,6-octatriene by a catalyst system consisting of zirconium(IV) n-butoxide and diethylaluminum chloride. The selectivity for this dimer was increased to more than 90% by adding triphenylphosphine or tetrahydrofuran to this catalyst system. The effects of the molar ratio of the catalyst components and those of catalyst species were studied.
  • Keisuke Murayama, Takao Yoshioka
    1969 Volume 42 Issue 8 Pages 2307-2309
    Published: 1969
    Released: March 27, 2006
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    Decomposition studies of extremely stable free radicals such as 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (I), 2,2,6,6-tetramethylpiperidine-1-oxyl (VIII) and 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl (IX) were carried out: although radical I decomposed to give 1-hydroxy-2,2,6,6-tetramethyl-4-oxopiperidine (IV) both in the light and dark, radicals VIII and IX were more stable under these reaction conditions. Therefore it was confirmed that i) a source of hydrogen was the ketonic α-methyene hydrogens, ii) a radical which could give a thermodynamically stable conjugated product by a cycloelimination was easily decomposed and iii) the decomposition of radical I was only accelerated by heating and was independent of the action of light.
  • Akiko Chinone, Shigeru Sato, Toshiyasu Mase, Masaki Ohta
    1969 Volume 42 Issue 8 Pages 2310-2312
    Published: 1969
    Released: March 27, 2006
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    For the purpose of synthesizing new mesoionic compounds of oxazole ring system having oxo group at 4 position, reaction of N-phenylbenzimidoyl chloride with glycolic acid was examined. Only an unexpected rearranged product was obtained. The reaction of N-phenylbenzimidoyl chloride with glycolonitrile successfully afforded the intermediate, which was treated with hydrogen chloride or with picric acid or with acetyl perchlorate to give 4-imino-3,4-dihydro-1,3-oxazole derivatives. Condensation of N-phenylbenzimidoyl chloride with mandelonitrile followed by treatment with acetyl perchlorate gave 4-imino-3,4-dihydro-1,3-oxazole derivative.
  • Etsuo Niki, Yoshio Kamiya, Nobuto Ohta
    1969 Volume 42 Issue 8 Pages 2312-2318
    Published: 1969
    Released: March 27, 2006
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    Cooxidation of all the combinations of two hydrocarbons among styrene, α-methylstyrene, tetralin and cumene was studied at 70° C in the presence of azobisisobutyronitrile as a thermal initiator. The reactivity ratios for each binary mixture were determined by several appropriate methods. The relative reactivities of styrene, α-methylstyrene, tetralin and cumene toward the peroxy radicals were approximately in the ratio 15 : 10 : 5 : 1. It was also concluded that the secondary peroxy radicals were more reactive than the tertiary peroxy radicals and that the polymeric peroxy radicals were more reactive than the normal alkylperoxy radicals.
  • Kikumasa Sato, Masao Ohashi, Takeshi Amakasu, Katsuhiko Takeda
    1969 Volume 42 Issue 8 Pages 2319-2323
    Published: 1969
    Released: March 27, 2006
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    A new synthesis of 4-methylcoumarins has been developed by means of the acid-catalyzed condensation of phenols with β-aminocrotononitrile. Such monohydric phenols as phenol or cresols reacted with β-aminocrotononitrile in polyphosphoric acid (PPA) to give 4-methylcoumarins in poor yields, along with a good yield of 6-amino-3-cyano-2,4-lutidine (III). In contrast, 7-substituted-4-methylcoumarins were obtained in 23–44% yields from resorcinol and its monomethyl ether. On the other hand, when β-aminocrotononitrile was heated in PPA, the lutidine (III) was obtained in a high yield. Its precursor, 4-amino-1,3-dicyano-2-methylpenta-1,3-diene (XI), was isolated under mild conditions. These results suggest that β-aminocrotononitrile may undergo the preferential self-dimerization to the lutidine (III) rather than the intermolecular condensation with phenols.
  • Teijiro Yonezawa, Masakatsu Matsumoto, Yoichi Matsumura, Hiroshi Kato
    1969 Volume 42 Issue 8 Pages 2323-2326
    Published: 1969
    Released: March 27, 2006
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    1,3-Disubstituted thioparabanates (I) were reduced with ethanol under the action of light to yield 2-mercaptoimidazolidine-4,5-diones (II) with or without 2-(1-hydroxyethyl)-2-mercapto-imidazolidine-4,5-dione (III). It seems that these reactions may be initiated by the n–π* transition of the lone pair in the 2-thiocarbonyl group. When dimethylthioparabanate (Ic) was irradiated with a high-pressure mercury arc in a chloroform solution of amylene, a photocycloaddition product, a trimethylene sulfide (IVa), was obtained.
  • Kenji Fukui, Mitsuru Nakayama, Tokunaru Horie
    1969 Volume 42 Issue 8 Pages 2327-2330
    Published: 1969
    Released: March 27, 2006
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    The partial benzylation of 3-methoxy-2,4,6-trihydroxyacetophenone gave a mixture of 2,4-dibenzyloxy-6-hydroxy- and 4,6-dibenzyloxy-2-hydroxy-3-methoxyacetophenone. The latter was esterified with 4-benzyloxy-3-methoxybenzoyl chloride, and the resulting ester was converted into 8,3′-dimethoxy-5,7,4′-tribenzyloxyflavone via the corresponding diketone. The catalytic debenzylation of the flavone gave 8,3′-dimethoxy-5,7,4′-trihydroxyflavone. Its diethyl ether was also prepared from 3,6-dimethoxy-4-ethoxy-2-hydroxyacetophenone by an unambiguous method.
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