Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 40 , Issue 5
Showing 1-50 articles out of 73 articles from the selected issue
  • Kazuo Nakamura
    1967 Volume 40 Issue 5 Pages 1019-1026
    Published: 1967
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The behavior of the alkali metal ions, Li, Na, and K, in solutions of terephthalonitrile in ethereal solvents was studied by means of the electron spin resonance of the anion radical. The metal ions formed ion pairs by association with the anion in solution at one of the two cyano groups; the rate at which the cation is transferred between these two groups determines the detailed structure of the ESR spectrum. Within the limits of slow transfer, the spectrum was interpreted in terms of splittings due to two sets of proton pairs and two non-equivalent nitrogens. As the transfer rate increased, the spectrum exhibited an alternating line width, until finally the splittings were averaged within the limits of the fast transfer rate. The transfer rate of cations in the same solvent was found to increase in the order of the size of cations. It also depended on the solvating power for the cation. At low concentrations and low temperatures, the ion pair tended to dissociate, thus giving free anions. The hyperfine interactions with the nuclear spin of the cations were also observed.
  • Kenichiro Nakamura, Shinichi Kikuchi
    1967 Volume 40 Issue 5 Pages 1027-1030
    Published: 1967
    Released: March 27, 2006
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    The photo-isomerization and photo-dimerization of cinnamic acid are discussed from the standpoint of the electronic structures in the ground and excited states. State energies, charge densities, bond orders and free valences are calculated by using the Pariser-Parr-Pople method, including the configuration interaction. The computed transition energies are in good agreement with the experimental results. It is found that the bond order between the α- and β-carbons of cinnamic acid decreases, while the free valences of the α- and β-carbons increases, upon the lowest electronic excitation. It is concluded that the photo-isomerization is due to the smaller bond order, and that the photo-dimerization is due to the larger free valences in the excited state of cinnamic acid.
  • Masao Sato, Tohru Azumi, Hiroshi Azumi
    1967 Volume 40 Issue 5 Pages 1031-1034
    Published: 1967
    Released: March 27, 2006
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    A long-lived emission of acriflavine absorbed into a polyvinylalcohol sheet has been investigated. At higher concentrations, a new, previously-unobserved emission band has been observed. It has been shown that the newly-observed band can be interpreted by a mechanism in which the thermal excitation of the triplet state to the excimer state takes place, followed by an emission. The term “delayed thermal excimer fluorescence” has been given to specify the emission of this type.
  • Masae Nemoto, Yoshiharu Usui, Masao Koizumi
    1967 Volume 40 Issue 5 Pages 1035-1040
    Published: 1967
    Released: March 27, 2006
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    The occurrence of a D–D mechanism in which the photochemical reaction is initiated by the interaction of the triplet dye and the ground-state dye molecules, has been established for the ethanol solution of eosine. Chief evidence for it has been afforded by: 1) the predominance of the second-order reaction at high dye concentrations, 2) the dependence of the quantum yield of the photoreduction upon the dye concentration, and 3) the effect of the dye concentration on the photochemical oxygen absorption and on the oxydative photobleaching of dye. Assuming no simple deactivation between the triplet dye and allylthiourea, the quantum yield for the formation of the triplet dye has been evaluated as 0.056. Then the rate constants for the following elementary reactions, (Remark: Graphics omitted.) and DT+ATU→intermediate are, respectively, 1×108 M−1sec−1 and 1–2×105 M−1sec−1. It seems that the reaction between oxygen and the triplet dye is chiefly an eventual deactivation of the latter, with no appreciable decomposition of the dye or of ethanol.
  • Junko Kondo, Toshio Uchijima, Yukio Yoneda
    1967 Volume 40 Issue 5 Pages 1040-1044
    Published: 1967
    Released: March 27, 2006
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    The flash desorption method was applied to the carbon dioxide - nickel oxide system in order to investigate the surface heterogeneity of nickel oxide catalysts. It was found that there were two peaks in flash desorption chromatograms. The Arrhenius plots for carbon monoxide oxidation on nickel oxide were found to be composed of two straight lines. It was shown that the inflection of the Arrhenius plots was due to the existence of two kinds of active sites which differ in activation energy for the oxidation reaction and in the strength of interaction with carbon dioxide. The numbers of active sites for carbon monoxide oxidation were determined by the measurement of the amounts of desorbed carbon dioxide.
  • Tsutomu Kagiya, Masatsugu Izu, Kenichi Fukui
    1967 Volume 40 Issue 5 Pages 1045-1049
    Published: 1967
    Released: March 27, 2006
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    Polymerizations were classified from a kinetic point of view. The polymerizations were divided into those with a rapid initiation and those with a slow initiation, according to the magnitude of the initiation rate in relation to the propagation rate. Both of these groups were then divided into stationary and non-stationary polymerizations according to the change in the number of moles of the propagating species with the reaction time. The next sub-classification, into chain and successive polymerizations, was made by estimating the change, with the reaction time, in the number-average degree of the polymerization of the polymer formed. Each proposed class was shown to possess a characteristic kinetic feature. Several examples of each class were collected.
  • Tsutomu Kagiya, Masatsugu Izu, Sueo Machi, Kenichi Fukui
    1967 Volume 40 Issue 5 Pages 1049-1054
    Published: 1967
    Released: March 27, 2006
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    A graphical method for the interpretation of the kinetics of the non-stationary polymerization, and for the evaluation of the rate constants of elementary reactions, was proposed. It was shown that the rates of elementary reactions could be estimated with an extrapolating method using the kinetic data on the polymer yield and the number-average degree of polymerization of the polymer. The graphical method was then applied to some practical examples.
  • Takashi Kajiwara, Hiroo Inokuchi, Shigeru Minomura
    1967 Volume 40 Issue 5 Pages 1055-1058
    Published: 1967
    Released: March 27, 2006
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    The charge mobilities of anthracene single crystals were measured under high pressures up to 7.4 kbar. An experimental apparatus like Kepler’s was used. A sample holder was attached in a Drickamer-type high-pressure photocell, with kerosene employed as the pressure-transmitting fluid. The electron mobilities along the a and b crystal axes increased as the pressure applied increased; the values of the charge drift mobility at 7 kbar were 1.7 times as large as those at atmospheric pressure. The electron mobility along the c′ axis was nearly constant. The hole mobility, however, could not be measured, because the tail of the pulse signal, observed on the oscilloscope, was deformed.
  • Kisaburo Umemoto
    1967 Volume 40 Issue 5 Pages 1058-1065
    Published: 1967
    Released: March 27, 2006
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    The electrochemical reduction mechanism of anthracene, benzophenone and anthraquinone was studied in N,N′-dimethylformamide (DMF) and/or its water mixture by means of polarography and electron spin resonance spectroscopy (ESR). The polarograms of these compounds consisted of two well-defined waves in anhydrous DMF: the first wave corresponds to the formation of the anion radical and the second wave to the reduction of the anion radical to the dinegative anion. When water was added, the limiting current of the first wave increased at the expense of the second wave. In order to elucidate the reduction mechanism of these molecules in DMF-water mixture, the kinetic behavior of the anion radical was studied by the ESR method. It has been found that the reduction of anthracene is understood by the protonation mechanism, but that of anthraquinone is not explained by the protonation mechanism at all; the disproportionation of the anion radical must be considered. For the reduction of benzophenone both the protonation and the disproportionation mechanism must be taken into consideration.
  • Takuya Hamamura, Genzo Tomita
    1967 Volume 40 Issue 5 Pages 1066-1070
    Published: 1967
    Released: March 27, 2006
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    The rate of the reaction of oxygen with a rhenium filament under a filament temperature of (1500–2100)°K and an oxygen pressure of (2×10−4–4×10−6)mmHg have been measured with a flow method. The reaction rate increases with an increase in the temperature, reaches zu maximum at about 1800°K, and then decreases with a further increase in the temperature. The reaction rate is proportional to the 0.9th power of the oxygen pressure below 1700°K, whereas it is proportional to the 1.8th power above 1900°K. The apparent compositions of the rhenium oxides produced in the reaction have been determined from the weight change of the filament, and the oxides in the formulas of Re2O7 and ReO3 have been found. For purposes of comparison, the reaction rates of oxygen with a tungsten filament have also been measured by the same method.
  • Teijiro Yonezawa, Hiroshi Kato, Hideyuki Konishi
    1967 Volume 40 Issue 5 Pages 1071-1076
    Published: 1967
    Released: March 27, 2006
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    Familiar small ionic intermediates are treated by the semi-empirical SCF method previously proposed for all valence electron systems by the present authors. The calculated orbital energies are compared with the results of other full SCF calculations and the experiments. The agreements between them are satisfactory. Utilizing the calculated orbital charge distributions and the atomic dipole values, the reactivities and the most reactive centers of these ions are discussed. The calculated results on the proton affinities and the excitation energies of various compounds are also presented.
  • Mitsunori Sukigara, Shin-ichi Kikuchi
    1967 Volume 40 Issue 5 Pages 1077-1081
    Published: 1967
    Released: March 27, 2006
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    The electronic structures and electronic absorption spectra of p-fluoro-, p-chloro-, p-bromo-, p-iodo, p-methoxy-, and p-dimethylaminobenzenediazonium cations were studied by making molecular orbital calculations and by measuring the visible and near-ultraviolet absorption spectra. From the calculations it is understood that when an electron-donating group is introduced at the p-position of the benzenediazonium cation, the 1A1-1A1 transition shows a very large shift to longer wavelengths, while the 1A1-1B1 transition is not so much affected; at the same time, the N–N bond order in the ground state decreases. It is shown that there is a linear relationship between the N–N bond order and the wave number of the N–N stretching of the p-substituted benzenediazonium salt. It is concluded from the calculations that the electron affinity of the nonsubstituted benzenediazonium cation has a large value, such as 2.40 eV.
  • Mitsunori Sukigara, Shin-ichi Kikuchi
    1967 Volume 40 Issue 5 Pages 1082-1086
    Published: 1967
    Released: March 27, 2006
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    The electronic structures and electronic absorption spectra of m-fluoro-, m-chloro-, m-bromo-, and m-methoxybenzenediazonium cations were studied by making molecular orbital calculations, and by measuring the near-ultraviolet absorption spectra. From the calculations it is understood that when an electron-donating group is introduced at the m-position of the benzenediazonium cation, a mixing of the lowest locally-excited 1B1 state within the benzenediazonium cation and the intramolecular charge-transfer state arising from the electron transfer from the electron-donating group at the m-position to the lowest unoccupied molecular orbital of the benzenediazonium framework comes to show a large contribution of the substituted cation in the lowest excited state while at the same time the energy of the corresponding state is lowered. The ground and the excited 1A1 states of the nonsubstituted cation are not so greatly affected by the m-substitution as is the 1B1 state. The degree of the mixing of the 1A1 and 1B1 state of the benzenediazonium cation by the m-substitution is not so impotant in the ground and lower excited states of the m-substituted benzenediazonium cation.
  • Susumu Tsuchiya, Tadao Shiba
    1967 Volume 40 Issue 5 Pages 1086-1089
    Published: 1967
    Released: March 27, 2006
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    The relative reactivity of the adsorbed species during a catalytic methanol synthesis reaction on a ternary-component catalyst was investigated. Abrupt changes in the ambient pressure of a component in the gas phase, at a nearly equilibrium condition, were correlated with the corresponding changes in the amounts of the adsorption and in the total ambient pressure. The data collected from such dynamical treatments indicate that the species adsorbed on the catalyst surface, in a nearly equilibrated system of the simultaneous adsorption of hydrogen and carbon monoxide, is mostly the surface intermediate complex formed from both of them. Furthermore, the results obtained suggest an order for the reaction speed of each elementary step in the methanol synthesis reaction.
  • Itiro Omura, Hiroshi Doi
    1967 Volume 40 Issue 5 Pages 1090-1094
    Published: 1967
    Released: March 27, 2006
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    An emission line of He II was generated at 304 Å (40.80 eV) from a microwave plasma light source operated in the standing wave mode. On the other hand, the plasma without the standing wave mode emits only the resonance line of He I at 584 Å (21.21 eV). A resonance line of Ar I was emitted at 1048 Å (11.82 eV) by argon carrier gas flowing through a capillary tube. The mass spectra of propane, n-butane, propylene, benzene, and isoamyl acetate obtained by the use of the emission line of He II at 304 Å were not very different from those of the electron impact method at 50 eV. The positive-charge distribution on each atom of the ionized molecules is estimated from the total ion yield of the molecule. In the fragmentation processes of isoamyl acetate, the intensity of the fragment ion (CH3CO+) including carbonyl group rose rapidly with the increase in the photon energies obtained by the resonance lines of Ar I, He I, and He II. At these photon energies, the ratios of the fragment ion, CH3CO+ , to that of C5H10+ were 0.17, 0.43 and 2.0 respectively.
  • Yonezo Morino, Chi Matsumura
    1967 Volume 40 Issue 5 Pages 1095-1100
    Published: 1967
    Released: March 27, 2006
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    Microwave spectra have been measured for various vibrationally excited states of the OCS molecule. The l-type doubling constants obtained for the excited states of the bending vibration, ν2, have led to the determination of the zero-order coupling constant, qe. It has been shown that the qe value thus obtained is useful for the evaluation of the harmonic force constants. The Fermi resonances have been discussed; they lead to the conclusion that the effect due to the cubic constant, k223, cannot be ignored, nor can that due to k122 With due consideration for this situation, the equilibrium structure has been found to be:
    re(O–C)=1.1572±0.002 Å and re(C–S)=1.5606±0.002 Å.
  • Yonezo Morino, Chi Matsumura
    1967 Volume 40 Issue 5 Pages 1101-1104
    Published: 1967
    Released: March 27, 2006
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    The microwave spectra of the OCSe molecule have been measured for the ground and vibrationally excited states of a number of isotopic species under the natural abundance ratio. It was concluded from the results that the rs-structure is given by r(O–C)=1.157 Å and rs(C–Se)=1.708 Å, and that the general quadratic force field is represented by fR(CSe)=5.42, fr(CO)=15.38, fRr=0.68, and fα=0.286 md/Å.
  • Hiromitu Naono
    1967 Volume 40 Issue 5 Pages 1104-1110
    Published: 1967
    Released: March 27, 2006
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    The inhibiting action of triphosphate on the crystallization of strontium sulfate has been investigated conductometrically. The crystallization of strontium sulfate is remarkably inhibited by a minute amount of triphosphate. A supersaturated solution of 0.02 M strontium sulfate is, in practice, completely stabilized in the presence of 3×10−5 M triphosphate. In this stabilized solution, the growth of the seed crystal of strontium sulfate has been examined. The growth of the seed suggests that, in the stabilized solution, the formation of the critical nucleus of strontium sulfate is inhibited by the action of triphosphate. By utilizing the relation between the nucleation rate of strontium sulfate and the concentration of triphosophate, it has been shown that triphosphate increases the energy of formation of the critical nucleus. On the other hand, the adsorption of triphosphate on the crystal surface of strontium sulfate is endothermic; the heat of adsorption is estimated to be 3kT per triphosphate from the temperature dependence on the adsorption isotherm. The heat of adsorption of triphosphate increases the energy of formation of the critical nucleus of strontium sulfate. It may, therefore, be concluded that the nucleation of strontium sulfate is inhibited by the adsorption of triphosphate. From the calculation of the collision between triphosphate and the embryo of strontium sulfate, it may be deduced that the adsorption of triphosphate is predominant in the initial stage of the formation of the embryo of strontium sulfate.
  • Takashi Kawamura, Shoichi Matsunami, Teijiro Yonezawa
    1967 Volume 40 Issue 5 Pages 1111-1115
    Published: 1967
    Released: March 27, 2006
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    The effects of solvents on the g-value of di-t-butyl nitric oxide (DTBNO) have been examined. Plots of the g-value vs. the hyperfine coupling constant of 14N of DTBNO in various solvents formed two different straight lines, for aprotic solvents and for protic solvents. An analysis of the solvent effects on the g-value has also been attempted. The solvent-dependent shifts of the g-value may be divided into three terms, resulting from the blue-shift of the n–π* transition, from the redistribution of the odd electron, and from the delocalization of the lone-pair orbital on the oxygen atom of DTBNO. The first term is calculated from the observed shift of the n–π* absorption in the visible ray spectrum, while the seond one is evaluated from the solvent shift of the g-value of DTBNO in aprotic solvents, where the delocalization of the lone-pair is excepted to be negligible The last term, the difference between the observed shift in the g-value and the sum of the former two terms, is estimated to be in the range from −4×10−5 to −10×10−5, which corresponds to the from 2% to 5% delocalization of the lone-pair electron.
  • Masashi Imamura, Hiroshi Seki
    1967 Volume 40 Issue 5 Pages 1116-1118
    Published: 1967
    Released: March 27, 2006
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    Liquid methanol containing trimethyl borate and nitrous oxide was irradiated with thermal neutrons from a nuclear reactor. In contrast to the marked effect on the γ-radiolysis yields, nitrous oxide had a little effect on the recoil radiolysis yields from methanol, and nitrogen yield was as low as 0.2 in G unit. These results indicate that the yield of the solvated electron in the recoil radiolysis of methanol is about one tenth of that in the γ-radiolysis.
  • Kazuko Ogino (née Ebata), Nobuyuki Tanaka
    1967 Volume 40 Issue 5 Pages 1119-1123
    Published: 1967
    Released: March 27, 2006
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    The current-potential curves of some substitution-inert complex ions are affected by the change in the composition of the supporting electrolyte. The change in the one-electron reduction wave of hexaquochromium(III) ions with the increase in the concentration of sodium perchlorate and sodium iodide is analyzed in terms of the effect of the structure of the electrical double layer. The addition of sodium sulfate at a constant ionic strength of 0.1 shifts the half-wave potentials of hexaquochromium(III), hexamminechromium(III) and hexamminecobalt(III) ions to more negative potentials. In the case of hexamminecobalt(III), the shift is much greater than in the cases of the former two complex ions. These phenomena are interpreted to be due to the effects of the double layer structure and of the ion association.
  • Eizi Hirota, Chi Matsumura, Yonezo Morino
    1967 Volume 40 Issue 5 Pages 1124-1130
    Published: 1967
    Released: March 27, 2006
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    The microwave spectrum of propane was observed in the first-excited states of the CH3torsion. Each transition was split into a symmetric triplet; the splittings were 14–19% larger for the (−) state than for the (+) state. The top-top interaction and its effect on the rotational spectra were treated by the perturbation theory, and the results were applied to the analysis of the triplet splittings. The two barrier parameters, V3 and V3″, were thus determined to be 3325±20 and −170±30 cal/mol respectively.
  • Agnes Paul, Pandarinath B. Janardhan
    1967 Volume 40 Issue 5 Pages 1131-1136
    Published: 1967
    Released: March 27, 2006
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    The mechanism of paper chromatography consists of three stages: i) adsorption; ii) desorption; iii) migration due to solvation. Solvation depends on the physical properties of the solvent. The present paper will attempt to correlate the Rf values of metal ions with such physical properties of the solvent as (a) surface tension, (b) viscosity, (c) solubilisation, and (d) the dielectric constant. Experiments have been conducted with pure and mixed solvents of the aliphatic alcohol series. As a result, it may be reported that the Rf values of cations (silver, copper, nickel and ferric ions) bear almost a linear relationship to the dielectric constant/viscosity quotient.
  • Fumiaki Kai
    1967 Volume 40 Issue 5 Pages 1136-1139
    Published: 1967
    Released: March 27, 2006
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    The composition of the complex formed with L-histidine and mercury(II) in a solution has been investigated spectroscopically. The complex formation in an aqueous solution was not observed, but in an alcoholic solution (1 : 1), there appeared about 274 mμ an absorption maximum which can be attributed to the complex formation. By the spectroscopic measurements of this alcoholic solution containing two components in various proportions, it was shown that only one kind of complex with a 1 : 1 composition was formed in a 50% ethanol-water solution at pH 3.25–3.75 and at 20°C. Accordingly, the composition of the complex may be considered to be as follows:
    (Remark: Graphics omitted.)
  • Yasuaki Shimoishi, Tadashi Hayami
    1967 Volume 40 Issue 5 Pages 1139-1141
    Published: 1967
    Released: March 27, 2006
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    The method of determining micro amounts of fluorine is based on the bleaching of the thorium complex of 2-(1, 8-dihydroxy-3, 6-disulfo-2-naphthylazo)-phenoxyacetic acid (PAC) by fluoride ions, which are strongly coordinated to the thorium in the complex and with thus liberate the free PAC. The complex is composed of thorium and PAC in a 1 : 1 molar ratio. PAC has an absorption maximum at 525 mμ, while the thorium complex shows a maximum at 555 mμ. The determination is based on the decrease in the absorbance at 610 mμ. Beer’s law holds up to 30 μg fluoride ions per 25 ml. The optimum pH range is from 2.5 to 3.5. The apparent molar extinction coefficient is calculated to be 20000.
  • Kyoji Tôei, Haruo Miyata, Takuji Harada
    1967 Volume 40 Issue 5 Pages 1141-1145
    Published: 1967
    Released: March 27, 2006
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    o-Carboxyphenyl-azo-chromotropic acid was synthesized as a colorimetric reagent for thorium. The acid dissociation constants of the reagent have been determined spectrophotometrically at 25°C and μ=0.1 (NaClO4). The pK1 (for the dissociation of the carboxyl group) and the pK2 (for the dissociation of the naphtholic hydroxyl groups) were 3.20 and 10.17 respectively. The reagent forms a violet 1 : 1 complex with thorium, showing an absorption maximum at 565 mμ in an acidic solution. The apparent stability constant of the thorium complex was measured spectrophotometrically.
  • Kyoji Toei, Haruo Miyata, Susumu Nakashima, Sachiaki Kiguchi
    1967 Volume 40 Issue 5 Pages 1145-1147
    Published: 1967
    Released: March 27, 2006
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    o-Hydroxyphenyl-azo-chromotropic acid was used as a colorimetrie reagent for thorium. The acid dissociation constants of the reagent have been determined by the pH titration method. The pK1 (for the dissociation of the phenolic hydroxyl group) and pK2 (for that of the naphtholic hydroxyl group) were found to be 7.60 and 10.60 respectively at 25°C and μ=0.1. The reagent forms a violet 1 : 1 complex in an acidic solution, and its apparent stability constant is measured spectrophotometrically.
  • K. Lal, R. P. Agarwal
    1967 Volume 40 Issue 5 Pages 1148-1152
    Published: 1967
    Released: March 27, 2006
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    A quantitative study of the interaction of vanadyl ions with catechol (H2A) has been carried out by means of potentiometric titrations of vanadyl sulphate with potassium hydroxide in the presence of varying concentrations of catechol. The formation of 1 : 1 and 1 : 2 complexes has been indicated. The equilibrium constants for the VO2++H2A\ ightleftarrowsVOA+2H+ and VOA+H2A\ ightleftarrowsVOA22−+2H+ reactions have been found to be 1.41×10−6 and 7.76×10−9 respectively, giving the values of 1.90×1015 and 1.05×1013 for the formation constants of 1 : 1 and 1 : 2 chelates respectively. Above pH 4, the 1 : 1 complex has been shown to hydrolyze, and the equilibrium constant for the VOA+H2O\ ightleftarrowsVO(OH)A+H+ reaction has been found to be 7.94×10−6.
  • Ryoei Ishida, Norio Hasegawa
    1967 Volume 40 Issue 5 Pages 1153-1158
    Published: 1967
    Released: March 27, 2006
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    Chromazurol S reacts with scandium(III) in a weakly acidic medium to form one of two kinds of complexes according to the pH value of the medium. Their compositions were confirmed; one had a 1 : 2 combining ratio of scandium (III) and chromazurol S at pH 5.2 or higher, and the other, a 1 : 1 ratio at pH below 4.0. The color development of the 1 : 2 complex is more sensitive than the other. Therefore, it was applied to the determination of scandium(III). Several conditions for the color development were investigated, a calibration curve was made under the optimum conditions, and the influences of coexisting ions were investigated. The maximum absorption wavelength of the complex is 550 mμ against the reagent blank. The optimum pH for the color development is about 5.6. By adding a reagent in an amount four times the scandium concentration, the maximum color intensity is given. The color intensity decreases gradually during the first 1.5 hr, and then it remains constant for several hours. A linear relationship between the absorbance and the scandium concentration is obtained in the concentration range from 4 to 27 μg per 10 ml. The value of the molar extinction coefficient of the complex at 550 mμ is 27000, and the sensitivity of the color reaction is 0.0017 μg/cm2 for log I0/I=0.001. The formation constant, K, of the complex is calculated to be 9.5×1011 under these conditions. Anions such as fluoride, phosphate, oxalate, tartrate, citrate, and EDTA interfere with the color development of the complex. Cations such as Al(III), Be(II), U(VI), Fe(II), Th(IV), Cu(II), Y(III), Fe(III), Zr(IV), and W(VI) interfere, too.
  • Reiko Hirota, Nobufusa Saito
    1967 Volume 40 Issue 5 Pages 1159-1162
    Published: 1967
    Released: March 27, 2006
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    The rate of isotopic exchange reaction between bis(α-benzildioximato)nickel(II) and nickel ions in pyridine greatly increases in the presence of water. When the water content in pyridine is lower than 3 M, the reaction takes place according to the rate equation:
    Rate=k1(complex)+k2(complex)(Ni2+)(H2O)
    For the catalyzed step, a mechanism is proposed.
  • Ichiro Shimizu, Ryokichi Tsuchiya, Eishin Kyuno
    1967 Volume 40 Issue 5 Pages 1162-1166
    Published: 1967
    Released: March 27, 2006
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    Three copper(II) complexes with phthalic acid, [Cuph(H2O)] (I) (ph=C6H4(COO)2), [Cu(Hph)2(H2O)2] (II), and [Cuph]2 (III), were prepared. Compound I was prepared from an aqueous solution of copper sulfate and phthalic acid within the temperature range of 60–79°C. It was a light blue crystal forming a hexagonal unit, the parameters being a=13.07 Å and c=13.98 Å and with the chemical unit Z equalling 8. II was prepared at a temperature below 60°C. It was a blue crystal having a hexagonal unit of a=11.42 Å, c=13.68 Å, and Z=4. The magnetic moments of I and II were 1.87 B. M. and 1.96 B. M. (both 21.5°C) respectively, showing I and II to have a monomer structure with respect to the two copper atoms. III could be prepared at temperatures above 79°C. It was a bluish-green crystal containing a hexagonal unit of a=12.77 Å, c=13.02 Å, and Z=4. The magnetic moment of III was found to be 1.54 B. M. (18.4°C), suggesting that complex III consisted of a dimer structure with respect to the copper atoms. The appearance of a shoulder near 370 mμ. in the reflection spectra of the copper complex III in the powdered crystalline state confirmed the suggestion of a dimer structure.
  • Bunji Iwasaki, Takashi Katsura
    1967 Volume 40 Issue 5 Pages 1167-1170
    Published: 1967
    Released: March 27, 2006
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    An attempt was made to make clear the manner of the vaporization of chlorine compounds from basaltic rocks at a series of temperatures ranging from 1000 to 1300°C, in atmospheres of air and of a mixed gas (CO2–H2), and on cooling from 1200 to 800°C in air, neglecting the effect of water vapor. The vaporization of chlorine compounds was found to take place from the surface of a melt and through the interstices of rock grains. When crystals began to separate from the melt, they suddently prevented the vaporization. From the results of cooling experiments on the basaltic melt, it was concluded that the chlorine compounds in the liquid basaltic lava extruded at approximately 1200°C are continously vaporized until the liquid lava is covered with thin films including crystals and glassy materials. The temperature at which the vaporization of chlorine compounds ceases is 1100°C at the highest.
  • Tetsuya Ogura, Nobuo Furuno, Shinichi Kawaguchi
    1967 Volume 40 Issue 5 Pages 1171-1174
    Published: 1967
    Released: March 27, 2006
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    A colorless crystalline complex of allyl alcohol with copper(I) chloride, (CH2=CHCH2OH)-CuCl, was synthesized at room temperature in a vacuum system. A similar complex with calcium chloride was also prepared for the sake of comparison. The equilibrium vapor pressure of the copper (I) chloride complex was determined at vairous temperatures, and ΔH=−12.0 kcal/mol was obtained as the heat of formation from solid copper (I) chloride and gaseous allyl alcohol. The C=C stretching frequency of allyl alcohol is shifted by 95 cm−1 to the lower frequency side by ligation to copper (I). The C–O stretching band shows a very minor shift of 15 cm−1. This value is almost the same as in the calcium chloride complex. Thus, in the copper (I) chloride complex, allyl alcohol coordinates to the metal mainly through the double bond, but the OH group also participates in the coordination. By measuring the decrease in vapor pressure, copper(I) chloride was found to exist as a dimer in allyl alcohol at 23–43°C, but as a monomer at 97°C.
  • Toschitake Iwamoto, Tadahiko Miyoshi, Takeshi Miyamoto, Yukiyoshi Sasa ...
    1967 Volume 40 Issue 5 Pages 1174-1178
    Published: 1967
    Released: March 27, 2006
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    Benzene and aniline clathrates of metal-complex host lattices with a general formula of M(II)(NH3)2Ni(CN)4·2G, in which M(II) was nickel, copper, or cadmium, and G, benzene or aniline as the guest molecule, were prepared. The stoichiometry was established through the analytical data and the structural information obtained from the powder X-ray diffractometric data. They are tetragonal with reasonable lattice parameters except for Cu(NH3)2Ni(CN)4·2C6H5NH2, which may be estimated to be orthorhombic or monoclinic. The host lattices of all the compounds have almost the same space character. The occupation of divalent metal M(II) at the octahedral site of the metal-complex host lattice was proved through the magnetic data.
  • Yukio Nakamura, Shinichi Kawaguchi
    1967 Volume 40 Issue 5 Pages 1179-1182
    Published: 1967
    Released: March 27, 2006
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    The main product in the reaction of bis (acetylacetonato) beryllium with bromine in the mole ratio of one to two was found to be bis(3-bromoacetylacetonato)beryllium. The mass-spectrometric analysis of the product of the same reaction in the mole ratio of one to one revealed the coexistence of mono- and dibrominated chelates, but the quantitative information concerning the product distribution has not been obtained. In this reaction a small amount of white precipitate was produced as a minor product. The same compound was obtained in the reaction of bis-(acetylacetonato) beryllium with hydrogen bromide in dichloromethane containing water, and identified as diaquoacetylacetonatoberyIlium bromide on the bases of the elemental analysis, the anion exchange experiment and the infrared assay.
  • Toshikazu Nagai, Katsuhiko Nishitomi, Niichiro Tokura
    1967 Volume 40 Issue 5 Pages 1183-1188
    Published: 1967
    Released: March 27, 2006
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    The photochemical sulfonation of propionic-α, α-d2-acid-d1 (83% isotopic purity at the α-position) with sulfuryl chloride to form the cyclic anhydride of the deuterated β-sulfopropionic acid was carried out. The isotopic purity of the resulting anhydride decreased to 55±2% at the α-position. This result indicates that an α-hydrogen is abstracted in a ratio of 67.5±5%, followed by the rearrangement of a β-hydrogen prior to the sulfonation at the β-carbon atom. The mechanism is somewhat different from that proposed by Kharasch et al. [M. S. Kharasch, T. H. Chao and H. C. Brown, J. Am. Chem. Soc., 62, 2393 (1940)] for the photosulfonation of propionic acid. The present paper will also study the thermal decomposition of the cyclic anhydride to produce acrylic acid; its mechanistic aspects will be considered.
  • Kousuke Kusuda, Koichi Mano, Akira Fujino, Takeo Sakan
    1967 Volume 40 Issue 5 Pages 1188-1194
    Published: 1967
    Released: March 27, 2006
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    The reaction of perchloro-(3, 4-dimethylenecyclobutene) (I) with molecular oxygen in the solutions of carbon tetrachloride, benzene and ether was investigated. The identified products were phosgene, perchloro-(dimethylenesuccinic) acid (IIa), its dichloride, its anhydride, perchloro-(2, 3-dimethylenecyclobutanone) (IV) and 2, 2, 3′, 3′, 4-pentachloro-3-methyleneglutaric acid (VIII) in carbon tetrachloride. In benzene the products were the same as in carbon tetrachloride except VIII. Phosgene, oxalic acid, IIa and perchloro-(3-cyclobutene)-1, 2-dicarboxylic acid were obtained in ether. A radical chain mechanism is suggested for the degradations in the former two solvents on the basis of the similar reaction of I with oxygen in tetrachloro-ethylene yielding phosgene, IV, VIII and trichloroacetyl chloride. A possibility that I could be a chlorine radical source for the chain initiation by forming an unstable adduct with oxygen in the solution is also discussed.
  • Yûkichi Takashi
    1967 Volume 40 Issue 5 Pages 1194-1201
    Published: 1967
    Released: March 27, 2006
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    The reactions of various alkylantimony compounds with titanium chlorides have been investigated. Tetraethylstibonium chloride was found to react with titanium tetrachloride to give the complex salts [SbEt4]2TiCl6 (I), [SbEt4]TiCl5 (II) and [SbEt4]Ti2Cl9 (III), and with titanium trichloride to give the complex salts [SbEt4]2TiCl5 (VI) and [SbEt4]TiCl4 (V). Titanium dichloride was oxidized by tetraethylstibonium chloride to form the complex salts of tervalent titanium, IV and V. Triethylantimony dichloride made addition with titanium tetrachloride and afforded two or more ionic complexes, SbEt3Cl2·TiCl4 and (SbEt3Cl2)m(TiCl4)n. Titanium dichloride was oxidized by triethylantimony dichloride to give a complex of tervalent titanium, SbEt3·nTiCl3. Triethylstibine reduced titanium tetrachloride and formed an adduct of tervalent titanium, SbEt3Cl2·2TiCl3, when an excess of titanium tetrachloride was allowed to react. An excess of triethylstibine gave rise to complicated reactions with titanium tetrachloride, and formed TiCl3·mSbEt3Cl2·nSbt3 complexes.
  • Yûkichi Takashi
    1967 Volume 40 Issue 5 Pages 1201-1204
    Published: 1967
    Released: March 27, 2006
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    The reactions of the three-component polyolefin catalysts consisting of titanium trichloride (α-type), triethylaluminum, and various electron donor compounds have been investigated. Electron donors in a certain range of reactant ratios were found to accelerate the alkylation of the titanium ion remarkably at a temperature suitable for the polymerization of α-olenns. The roles of the electron donors have been discussed on the basis of the reaction behavior of the catalyst components and of the properties of the complexes which are thought to be the reaction intermediates.
  • Tadao Hayakawa, Yukihiko Fujiwara, Junzo Noguchi
    1967 Volume 40 Issue 5 Pages 1205-1208
    Published: 1967
    Released: March 27, 2006
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    With stannous chloride in formic acid, nitroarginine can be reduced to L-arginine hydrochloride quantitatively. This new method for the removal of the nitro group was applied successfully in the synthesis of poly-L-arginine hydrochloride from poly-L-nitroarginine, which had been prepared by the polymerization of N-carbothiophenyl-L-nitroarginine in dimethylsulfoxide at 120°C for 14 hr. The infrared absorption spectra of these polymers showed absorptions at 1708 cm−1 and 1766 cm−1, these absorptions might correspond to the C=O group in the hydantoin of the N-terminal. The poly-L-arginine hydrochloride showed positive Biuret and Sakaguchi reactions.
  • Yojiro Tsuzuki, Katsumi Tanaka
    1967 Volume 40 Issue 5 Pages 1208-1211
    Published: 1967
    Released: March 27, 2006
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    We have measured the nuclear magnetic resonance spectra (NMR) of some anomers of aryl 2,3,4,6-tetra-O-acetyl-D-glucopyranosides and found that the signal of the anomeric proton in the α-anomers could be separated from the signals due to the other protons, and that the chemical shift in fact distinctly appeared in a lower mangetic field (δ=5.95 ppm, J=3.0 to 3.5 cps) than those in alkyl 2,3,4,6-tetra-O-acetyl-D-glucopyranosides. Lower field shifts have also been observed in β-anomers, but it was impossible to determine the chemical shift exactly possibly because of the overlapping with the signals due to the other protons attached to the pyranose ring.
  • Shozo Furuyama
    1967 Volume 40 Issue 5 Pages 1212-1217
    Published: 1967
    Released: March 27, 2006
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    The thermal rearrangements and the disproportionation of potassium benzenecarboxylates have been investigated at 350–460°C using potassium deuterophthalate, deuterobenzoate, benzoate-1-14C and benzoate-7-14C. The following results were obtained: (1) Hydrogen atoms of potassium phthalate and benzoate transfer intermolecularly during the conversion. The hydrogen atoms seem to exchange many times. (2) The intermolecular transfer of hydrogen atoms also takes place between different benzenecarboxylates. (3) The hydrogen atoms transfer intermolecularly many times, irrespective of either the reaction temperature, the kinds of catalysts, and the kinds of potassium carboxylates. (4) The hydrogen exchange takes place only during the conversion. (5) Many of the carboxyl groups of potassium benzoate are replaced by carbon dioxide in the gas phase and by carbon dioxide from potassium carbonate. A possible mechanism is presented.
  • Yasuhiko Dozen
    1967 Volume 40 Issue 5 Pages 1218-1223
    Published: 1967
    Released: March 27, 2006
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    The cadmium halides-catalyzed thermal transformation of potassium and sodium salts of isomeric methyl- and phenylbenzoic acids has been investigated. Potassium o-toluate gave toluene, 3-methylphthalic, and 4-methylisophthalic acids, whereas sodium o-toluate gave toluene, 3-, and 4-methylphthalic acids, as the main products. In the reaction of potassium m- and p-toluates, both of them gave toluene, 5-methylisophthalic, and 4-methylphthalic acids, whereas the sodium salt of these acids gave toluene and 4-methylphthalic acid, as the main products. Potassium and sodium isomeric dimethylbenzoates gave xylenes and dimethylphthalic acids, e. g., 3, 4- and 4, 5-dimethylphthalic acids from 2, 3- or 3, 4-dimethylbenzoates, 3, 5-dimethylphthalic acid from 2, 4-dimethylbenzoate, and 3, 6-dimethylphthalic acid from 2, 5-dimethylbenzoate. In the case of o-phenylbenzoate, potassium salt gave biphenyl, m- and p-phenylbenzoic, and biphenyl-p-p′-dicarboxylic acids, but sodium salt gave biphenyl, m- and p-phenylbenzoic, and 4-phenyl-phthalic acids. Sodium p-phenylbenzoate gave biphenyl and 4-phenylphthalic acid, but potassium p-phenylbenzoate was stable under the conditions used. These results may be interpreted by the ortho-, meta-, and para-directed disproportionation for the potassium salts and ortho-di-rected one for the sodium salts. These dibasic acid salts produced were decarboxylated to mono-carboxylates, which then underwent further disproportionation.
  • Yoshiyuki Kawase, Matsuko Takashima
    1967 Volume 40 Issue 5 Pages 1224-1231
    Published: 1967
    Released: March 27, 2006
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    Acetyl derivatives of 2, 3-dimethylbenzofuran and their methyl homologs were derived into the corresponding carboxylic acids by the haloform reaction, and the acetylation of thier esters by the Friedel-Crafts reaction was studied. The keto-esters obtained were hydrolyzed to give keto-acids, which were then further oxidized into dicarboxylic acids by the haloform reaction and decarboxylated to acetylbenzofurans. On the other hand, the dicarboxylic acids were also obtained by the oxidation of diacetylbenzofurans. By the haloform reaction of hindered acetyl compounds, we obtained only halogenated ketones, which it was difficult to hydrolyze to give carboxylic acids. After the structures of these products had been determined and compared, it became clear that the acetylation of 5-alkoxycarbonyl-2, 3-dimethylbenzofurans furnished the 6-acetylated compounds, while that of 6-alkoxycarbonyl compounds and their methyl homologs furnished the 4-acetylated compounds.
  • Toshitsugu Ozeki, Masakatsu Kusaka
    1967 Volume 40 Issue 5 Pages 1232-1239
    Published: 1967
    Released: March 27, 2006
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    The effects of the amine, the alcohol, the solvent, and the reaction temperature on the isomerization esterification of crotonyl chloride to the vinylacetic acid ester were investigated. Amines can be divided into three groups. The first group includes the amines with pka-values as high as 10; they give the isomerized product, ethyl vinylacetate (IEt), in a ca. 90% yield. The second includes the amines with pKa-values lower than 7.2; they give the normal product, ethyl trans-crotonsite (IIIEt). The third includes the remaining amines with intermediate pKa-values; they give various amounts of the two products. Ethyl cis-crotonate (IIEt) is always formed in only a small quantity. Alcohols favored the product ratio of IEt in the order:
    MeOH<EtOH<i-BuOH<i-PrOH<t-BuOH.
    Various aliphatic and aromatic solvents gave almost identical product ratios, regardless of their polarities. Below room temperature, the formation of IEt was predominant (ca. 95—97%), but above that temperature IIEt and IIIEt increased. It was understood that the steric factors of amine and alcohol influenced the extent of the double-bond shift and that the reaction proceeded via the ketene intermediate. The course of the reaction has been discussed.
  • Heinosuke Yasuda
    1967 Volume 40 Issue 5 Pages 1239-1244
    Published: 1967
    Released: March 27, 2006
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    The spectra of forty-five 2-pyrazolin-5-one dyes in the ultraviolet and visible regions are discussed on the basis of their hydrazone-keto structures. In particular, the effects of sterically-sensitive ortho-substitutions in the 1- and 4-positions on the pyrazolinone ring are investigated. The bathochromic effects on the visible absorption band of pyrazolinone dyes are caused by electron-attracting substituents in the 3-position, not by 1- and 4-substituents.
  • Naoki Toshima, Ichiro Moritani, Shinya Nishida
    1967 Volume 40 Issue 5 Pages 1245-1248
    Published: 1967
    Released: March 27, 2006
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    The reaction of diphenylcyclopropenone with cyclopentadienylmagnesium bromide did not give the expected tertiary carbinol, but resulted in the formation of tetraphenylcyclopenta-dienone, tetraphenyl-p-benzoquinone, and tetraphenylpyrocatechol in 1%, 2%, and 8% yields respectively. When diphenylcyclopropenone was treated with a mixture of metallic magnesium and iodine, the same products were obtained in increased yields. Similarly, the treatment of diphenylcyclopropenone with sodium amalgam in isopropyl alcohol - acetic acid gave tetraphenyl-p-benzoquinone and tetraphenylpyrocatechol in 4% and 20% yields respectively. These results suggest that diphenylcyclopropenone gives pinacol, 1, l′-dihydroxy-2, 2′, 3, 3′-tetraphenyl-l, l′-bi-cyclopropenyl, under the reaction conditions, but the pinacol is too unstable to be isolated and rearranges to the benzene derivatives.
  • Kiroku Yamazaki, Harusuke Tokui
    1967 Volume 40 Issue 5 Pages 1249-1253
    Published: 1967
    Released: March 27, 2006
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    The control of the burning rate is one of the important aspects in the extension of the capability of a solid propellant. The burning rate of a composite propellant was found to be increased remarkably by the proper impregnation of metallic foil, and upon the addition of a few percent of aluminum, silver and copper (in weight), the burning rate jumped up to several times that of the original one, providing there had been suitable processing. The impregnation of metallic foil was performed by mixing a predetermined amount of finely-cut strips of foil into propellant dough or by laminating the latter with foils. The propellant grain impregnated at random with strips of foil increased the burning rate considerably, but the one laminated with metallic foils which were oriented perpendicular to the burning surface showed the highest burning rate. The increment of the burning rate evidently depended upon the thickness of the foil used; the distance between adjacent foils for lamination showed no remarkable effect. The role of the metallic foil on the augmentation of the burning rate seems to be attributable to the improvement of the heat transfer from the burning zone to the burning surface. However, in the case of copper, the burning rate exceeded that of silver, so the increment of the burning rate can not be explained only in terms of the thermal conductivity of the metallic foil. In the case of copper foil, the effective increase in the burning rate may be due to its catalytic action plus a good thermal conductivity. The mechanical properties of the propellant grain, such as tensile strength and elongation at the yield point, were expected to be improved with the impregnation of metallic foil. However, this coluld not be confirmed in the present tests.
  • Mohd. Mahfooz Khan, Naseer Ahmad
    1967 Volume 40 Issue 5 Pages 1254-1255
    Published: 1967
    Released: March 27, 2006
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  • K. N. Mehrotra, S. C. Bhargava
    1967 Volume 40 Issue 5 Pages 1255-1257
    Published: 1967
    Released: March 27, 2006
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