Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 45 , Issue 11
Showing 1-50 articles out of 66 articles from the selected issue
  • Michihiko Ogata, Hiroshi Ichikawa
    1972 Volume 45 Issue 11 Pages 3231-3236
    Published: 1972
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A method of comparing the relative bond energies is applied to the interpretation of the simple cleavage and the McLafferty rearrangement reactions in organic mass spectrometry. A qualitative correlation between the relative bond energy and the charge density at the highest occupied orbital is found. The behavior of the highest occupied and some lower vacant orbitals is discussed.
  • Tadashi Yoshida, Tetsuya Ohsaka, Hajime Yamamoto
    1972 Volume 45 Issue 11 Pages 3236-3240
    Published: 1972
    Released: March 27, 2006
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    The adsorption of N-vinyl-2-pyrrolidone (NV2P) or the monomer of polyvinylpyrrolidone (PVP) at the mercury/solution interface was examined by means of differential capacity vs. potential relations (C-E curves). The usual C-E curve obtained in 1 N sulfuric acid was similar to that of the saturated aliphatic compounds. However, in 1 N sodium sulfate or sodium hydroxide potential dependence of Cmin (minimum differential capacity) was observed as a result of π-electron interaction of adsorbed molecules. The adsorption behavior in 1 N sulfuric acid followed the Langmuir isotherm. The peculiar behavior in 1 N sodium sulfate or sodium hydroxide was explained by means of the Frumkin isotherm with the potential dependence of interaction constant (g), which varied linearly with potential in a range more negative than ca. −0.6 V (SCE) in contrast to nearly constant values in a more positive range. At a relatively high bulk concentration, there was a slight deviation from the Frumkin isotherm and the standard free energy of adsorption (ΔG0) vs. θ3⁄2 plot revealed a sharp break in the same way as pointed out by Gonway and his co-worker. The Cmin value of NV2P coincided approximately with that of its polymer of PVP in aqueous sulfuric acid, sodium sulfate or sodium hydroxide, respectively. The results are utilized for the discussion on the configuration of adsorbed PVP at the interface.
  • Tadashi Yoshida, Tetsuya Ohsaka, Yasuo Iida
    1972 Volume 45 Issue 11 Pages 3241-3245
    Published: 1972
    Released: March 27, 2006
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    Competitive adsorption of polyvinylpyrrolidone (PVP, \barM=10000) with n-hexanol, n-pentanol, or n-butanol was examined by observation of the differential capacity at the mercury interface in 1 N sulfuric acid. Adsorption of PVP coexistent with alcohol hardly differed from the single adsorption1) controlled by its diffusion. The competitive adsorption curve of C (differential capacity) vs. t1⁄2 (adsorption time) was expected from the sum of the individual capacity depressions by the single adsorption at −0.5 or −0.6 V (SCE) and the expected curve of C vs. t1⁄2 was compared with the curve observed. The competitive behavior of alcohol coexistent with PVP was examined by the relation “θAlccom (coverage of coexistent alcohol) vs. t1⁄2” at −0.5 or −0.6 V (SCE), where θAlccom was estimated from the difference between the differential capacities with and without PVP, in view of the fact that behavior of PVP is nearly independent of the coexistent alcohol. The results are discussed in terms of four types of models assumed for the competitive behavior of coexistent alcohols with different adsorbability. It is considered that the alcohol is replaced with PVP as soon as the latter reaches the interface by diffusion, the adsorption equilibrium of an alcohol being achieved immediately. The relation θAlccom=(1−θpvpAlc holds in the case of n-butanol coxistent with PVP, where θPVP, θAlc, and θAlccom are coverages due to the single adsorption of PVP and butanol and to the competitive adsorption of butanol, respectively. The tendency of alcohol to be replaced with PVP is inversely proportional to its adsorption coefficient. n-Butanol was most sensitive to the coexistence of PVP.
  • Tadashi Yoshida, Tetsuya Ohsaka, Masayuki Suzuki
    1972 Volume 45 Issue 11 Pages 3245-3250
    Published: 1972
    Released: March 27, 2006
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    The adsorption of polyethyleneglycol (PEG) was investigated at the mercury/solution interface by the observation of the differential capacity and the inhibitive action on the deposition of cadmium or copper. From the differential capacity measurements, the adsorption of PEG was found to be controlled by the diffusion of the adsorbate to the dropping mercury electrode under the present experimental conditions. The relation between the time required to attain the saturated adsorption and the bulk concentration (a) was explained approximately by the Koryta equation, though its deviation from the Koryta equation was somewhat larger than that for polyvinylpyrrolidone. When the maximum surface concentration and the mean molecular weight of PEG were expressed by Γm and \barM respectively, the plot of logΓm-log\barM revealed two linear parts crossing each other at \barM=ca. 600. The slope for \barM≥600 was ca. −1, which implied the relation of “\barM·Γm=const.”, i.e., the segment numbers of PEG molecules adsorbed per unit area were constant, independently of \barM, in the region of \barM≥600. The configuration of PEG of \barM<600 at the interface was considered to be different from that of PEG of \barM≥600 because the slope for \barM<600 was different from that for \barM≥600. From the polarographic current measurements i.e., the inhibitive effect on the reduction of Cd2+ or Cu2+), the time (tmi) needed to achieve the maximum inhibition was obtained; it was then compared with that obtained from the capacity data. The relation of “loga=(−1⁄2)logtmi+const.” based on the Koryta equation was approximately applicable to the cases with a relatively large \barM value.
  • Toshinobu Imanaka, Yasuaki Okamoto, Shiichiro Teranishi
    1972 Volume 45 Issue 11 Pages 3251-3254
    Published: 1972
    Released: March 27, 2006
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    The selectivity and activity of propylene oxide isomerization have been investigated over zeolite catalysts at 100°C. It has been found that the acid strength of a catalyst is a dominant factor in the selectivity and activity. The stronger the acid strength, the larger the ratio of acetone to propionaldehyde. The reaction intermediates are deduced to be a propylene oxide protonated or that adsorbed on a Lewis-acid site. It has also been found that, in the cases of HY, Silnex (SiO2), and HY treated with pyridine, the selectivity and activity correlate with the strength of the interaction between the propylene oxide and the surface hydroxyl group. Moreover, it has been clarified that the H0 value of the surface hydroxyl group observed at 3660 cm−1 on HY is −8.2–−5.6, while that found at 3540 cm−1 is +4.0–+4.8.
  • Chihiro Tamura, Tadashi Hata, Sadao Sato, Noriko Sakurai
    1972 Volume 45 Issue 11 Pages 3254-3261
    Published: 1972
    Released: March 27, 2006
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    Many intermolecular complexes between N-acylamino acids and nucleotide bases have been found by means of X-ray powder diffractometry. Among these, the crystal structure of N-benzoylglycine cytosine complex monohydrate has been determined by the direct method. The crystal data are: a=18.71,b=7.11,c=18.37 Å, and β=144.0°. The space group is P21c; Dobsd=1.37; Dcalcd=1.35 g/cm3. The final R factor was 0.131. In the crystal, a cytosinyl cation and a N-benzoylglycyl anion are joined by two NH···O hydrogen bonds, of which the shorter one is 2.652 Å long. Such a complex formation may exist in vivo.
  • Haruo Takaya, Naoyuki Todo, Tadasuke Hosoya, Hideki Oshio, Mikio Yoneo ...
    1972 Volume 45 Issue 11 Pages 3262-3267
    Published: 1972
    Released: March 27, 2006
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    The liquid-phase isomerization of m-xylene was studied over a silica-alumina catalyst under pressure on the additions of 2% of 8 higher-boiling compounds and 20–50% of benzene to reactant m-xylene. The catalyst activity in the isomerization was not greatly affected by hexamethylbenzene, naphthalene, α-methylnaphthalene, diphenyl, or s-dibenzyl. On the other hand, the activity was greatly lowered by 1,6-dimethylnaphthalene, diphenylmethane, and anthracene. Moreover, a very rapid exchange reaction occurred between an aromatic ring of diphenylmethane and a reactant xylene molecule, while the content of the isomerization product decreased linearly with an increase in the amount of benzene. From these results, the chemisorption states of xylene were discussed as follows. Most xylene molecules may be deduced to be chemisorbed on acid sites by those benzene rings. On the other hand, the fact that diphenylmethane inhibits the isomerization implies the existence of such a chemisorption state of xylene as a methylbenzylcarbonium ion, which may be an intermediate in the disproportionation reaction of xylene. The acid sites available for the chemisorption of diphenylmethane and for the disproportionation were speculated to be common and to have both acidic characters, protonic and Lewis.
  • Seiichiro Hironaka, Takashi Kubota, Kenjiro Meguro
    1972 Volume 45 Issue 11 Pages 3267-3270
    Published: 1972
    Released: March 27, 2006
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    Poly(methyl acrylate), poly(n-butyl acrylate), and their copolymers were prepared by radical polymerization. The monolayers of these polymers and the mixed polymers were studied at the air/water interface. The limiting areas obtained experimentally for various copolymers corresponded well to the theoretical values as calculated from the areas per methyl acrylate and butyl acrylate residues. However, those obtained for their corresponding polymer mixtures were larger than the theoretical limting areas.
  • Harumi Endo
    1972 Volume 45 Issue 11 Pages 3270-3276
    Published: 1972
    Released: March 27, 2006
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    The adiabatic compressibility (β) and the partial molar volume at an infinite dilution (\barV0) were obtained for aqueous solutions of the sodium alkylsulfates (SAS) of homologues. The sound velocity (U) and the density (ρ) were determined by the use of an ultrasonic interferometer and the float-balance method respectively. The results indicate that the slope at an infinite dilution (dβ⁄dC)0 of β vs. the concentration (C) diagram is in a linear relation with the carbon number (φ) of SAS. A similar relation was obtained between \barV0 and φ. We have derived these two relations by a statistical thermodynamical treatment based on the interstitial model of water, consisting of two species, one constituting the framework of an extended ice-1 structure with many cavities, and the other species, non-hydrogen-bonded water, occupying part of these cavities. The occupancy of the cavity with alkyl radical leads to a decrease in the structural compressibility, while the hydration of the ionic parts of the solute leads to a decrease in the compressibility due to the electrostriction. According to the calculations, the theoretical dependency of (dβ⁄dC)0 on φ is about three times larger than the experimental value. The theoretical dependency of \barV0 on φ is nearly in agreement with the experimental value, while the constant-addivite term is different.
  • Makoto Ogasawara, Takao Iijima, Masao Kimura
    1972 Volume 45 Issue 11 Pages 3277-3282
    Published: 1972
    Released: March 27, 2006
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    Assuming a planar conformation with C2v symmetry, and using the estimated mean amplitudes of vibration, the bond alternation in tropone was confirmed. The average C–C and C=C distances were determined by the least-squares method to be 1.454±0.010 and 1.362±0.013 Å respectively; moreover, two probable sets of the structure parameters were obtained. On the basis of conformational arguments regarding the structures of related compounds, the following set of the bond lengths was preferred: C–H, 1.098±0.016 Å; C1–O, 1.225±0.012 Å; C1–C2, 1.445±0.012 Å; C2–C3, 1.364±0.012 Å; C3–C4, 1.462±0.012 Å; and C4–C5, 1.342±0.018 Å.
  • Tanekazu Kubota, Masumi Yamakawa, Yoshiko Mizuno
    1972 Volume 45 Issue 11 Pages 3282-3286
    Published: 1972
    Released: March 27, 2006
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    The singlet-triplet absorption (T1N) spectra of pyridine N-oxide, quinoline N-oxide, isoquinoline N-oxide, and acridine N-oxide have been observed by applying the oxygen-intensification technique. The correlation between the T1N absorption bands and the singlet-singlet (S*N) absorption bands of these N-oxides has been established and discussed theoretically. The lowest triplet state of the N-oxides has been assigned as the π-π* transition of a 3La (CT) nature. The T1N absorption bands obtained show a blue shift in polar solvents. The results have been compared with the case of S*N transitions and have been reasonably explained by taking into account the contribution from the intramolecular charge transfer.
  • Katsutaka Sasaki, Kiyoshi Arakawa
    1972 Volume 45 Issue 11 Pages 3287-3290
    Published: 1972
    Released: March 27, 2006
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    Ultrasonic experiments were carried out on aqueous solutions of diamines (ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, and 1,6-hexanediamine) by means of pulse technique in order to study solute-solvent interactions. Sound velocity and absorption coefficient were determined in the frequency range 15–45 MHz. The magnitude of absorption coefficient for each solution increased rapidly with concentration up to about 0.4 mol%. It is concluded that the initial rapid increase is attributed to the proton transfer in base equilibria. The absorption coefficient at the same molar concentration of each solution increases appreciably with the size of hydrocarbon chain from –(CH2)2– to –(CH2)3–. This is ascribed to the formation of icebergs around hydrocarbon groups.
  • Takayuki Fueno, Kizashi Yamaguchi
    1972 Volume 45 Issue 11 Pages 3290-3293
    Published: 1972
    Released: March 27, 2006
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    The ultraviolet absorption spectra of the cis and trans isomers of various 1,2-disubstituted ethylenes were measured in isopentane solution. Each isomer showed a single intense band assignable to the lowest π–π* transition. For the majority of the compounds studied, both energy and oscillator strength of transition are found to be greater for trans isomers than for the corresponding cis isomers, in accord with the general trend predicted by the Pariser-Parr-Pople calculations. Existence of some anomalous cases which contradict the generalization indicates a limited validity of the usual assumption of virtual orbitals.
  • Takayuki Fueno, Kizashi Yamaguchi, Yuji Naka
    1972 Volume 45 Issue 11 Pages 3294-3300
    Published: 1972
    Released: March 27, 2006
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    The ultraviolet absorption spectra of cis and trans isomers of various β-substituted styrenes have been measured both in the gaseous state and in n-hexane solution. The excitation energies observed for cis isomers are either smaller or greater than those of the trans, depending on the type of β-substituents. The isomeric difference in the energy of the lowest allowed transition was found to be linearly correlated with Taft’s steric substituent constants. The electronic states of the various isomeric pairs were calculated by the LCAO–SCF–CI method of the Pariser-Parr-Pople type. The results were found to be entirely in line with the observed spectral features.
  • Safee Chaudhri, Yoshiya Kera, Kozo Hirota
    1972 Volume 45 Issue 11 Pages 3301-3306
    Published: 1972
    Released: March 27, 2006
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    The 18O-oxidation of carbon monoxide was studied on nickel oxide catalysts, and the oxygen exchangeability with the oxide during the reaction was determined. The activities of three oxide samples, obtained under different preparation conditions, were compared. The samples were prepared at 350, 600, and 850°C; they are denoted as NiO-I, NiO-II, and NiO-III respectively. In the case of NiO-I, two kinds of oxygen species, weakly and strongly bound to the surface, were observed. Above 120°C, not only weakly but also strongly bound surface oxygen become reactive; however, the binding energy distribution was quite broad. Similar observations were made in the case of NiO-II, with a similar change above 170°C and with a sharp energy distribution. In contrast, for NiO-III, only a small percentage of the monolayer of the surface oxygen became active and exchangeable below 200°C, but above 250°C about three layers became activated. Models are proposed for the surface state of these oxides on the basis of the behavior of the surface oxygen.
  • Isao Ando, Atsuo Nishioka, Masao Kambe
    1972 Volume 45 Issue 11 Pages 3306-3308
    Published: 1972
    Released: March 27, 2006
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    The values of the directly-bonded carbon-hydrogen coupling constants (JC–H) of the methyl and methylene groups in n-pentane were calculated by using the CNDO/2 method, taking into account its rotational isomers, and it was found that the calculated values of JC–H agree closely with the observed values.
  • Tomoichi Kamo, Masao Kimura
    1972 Volume 45 Issue 11 Pages 3309-3314
    Published: 1972
    Released: March 27, 2006
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    The infrared spectra of zinc halide complexes with acetonitrile, ZnX2·2CH3CN (X=Cl, Br, I), in the solid state were recorded in the region from 4000 to 96 cm−1. The Zn–N stretching bands for the chloride and bromide were observed, at 210 and 212 cm−1 respectively, as composite bands of the A1 and B1 species. For the iodide, the Zn–N stretching band of the B1 species was observed at 219 cm−1, while the A1 mode was coupled with the Zn–I stretching mode and was absorbed at 252 and 179 cm−1. The N–Zn–N bending bands were observed at 163, 162, and 153 cm−1 and the Zn–N≡C bending bands, at 125, 128, and 132 cm−1, for the chloride, bromide, and iodide respectively. The normal coordinate analysis was carried out by the use of the Urey-Bradley force field, and the Zn–N stretching force constant was obtained as 0.56 mdyn/Å. The force constant is much smaller than the corresponding ones in complexes containing nitrogen donors in the sp3 and the sp2 valency states.
  • Nobuko Sakai, Ichimin Shirotani, Shigeru Minomura
    1972 Volume 45 Issue 11 Pages 3314-3320
    Published: 1972
    Released: March 27, 2006
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    The temperature dependence of the electrical resistivity of single crystals of TCNQ anion radical salts with alkali metal, quinolinium, and triethylammonium cations has been investigated at temperatures between 300 and 540°K. It has been observed in these salts that the activation energy increases in the region of higher temperatures. In the cases of Na- and K(TCNQ) crystals, the reversal of the sign of the thermo-e.m.f. from the p-type to the n-type has been observed around the temperatures at which the activation energy increases. An interpretation of the experimental results is presented.
  • Nobuko Sakai, Ichimin Shirotani, Shigeru Minomura
    1972 Volume 45 Issue 11 Pages 3321-3328
    Published: 1972
    Released: March 27, 2006
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    The phase transition at 1 bar has been observed in alkali metal cation-TCNQ anion radical simple salts by means of measurements of the electrical resistivity of their single crystals. The temperature dependence of the resistivity under high hydrostatic pressures has been studied in order to investigate the effect of the pressure on this phase transition. The nature of this phase transition has been discussed. The pressure-induced new phase has also been found in these TCNQ salts at room temperature; thus, more than three phases (α, β, γ···) are considered to exist in the solid phase of these TCNQ, salts.
  • Takayoshi Uematsu
    1972 Volume 45 Issue 11 Pages 3329-3333
    Published: 1972
    Released: March 27, 2006
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    The isomerization of n-butenes and the polymerization of propylene were studied in a gas-phase reaction on a sulfonic acid-type resin catalyst. These reactions were considered to proceed via the carbonium ion formation on the functional groups, and a strong correlation was found between the activities in these two reactions. The acidity and the acid strength of the resin catalyst were measured by means of amine titration in a nonpolar solvent using Hammett indicators. The value of the acidity obtained at pKa=6.8 seemed to correspond to the number of the ion-exchangeable hydrogen on the functional groups. The effects of poisoning by ion exchange with Na+, Mg2+ or by adsorption of NH3 were also studied. The decrease in the activity for the isomerization was not proportional to the amount of cations exchanged. The catalytic activities of the protonic hydrogen seemed not to be equal as was suggested by the result of resin catalysts in polar solvents. The possible heterogeneity of the active sites on the resin catalyst was discussed. The six relative rate constants were calculated on the basis of the mutual interconversion among the three isomers of n-butene. The apparent energy of activation for the double-bond migration of 1-butene was found to be 17 kcal/mol on the H-form resin, but it was changed by ion exchange with Na+. The selectivities were characteristic of solid acid catalysts of the protonic type.
  • Keiichi Ohno, Hiromu Murata
    1972 Volume 45 Issue 11 Pages 3333-3342
    Published: 1972
    Released: March 27, 2006
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    The infrared spectra of ClCH2SiH3, ClCH2SiD3, BrCH2SiH3, BrCH2SiD3, ClCH2GeH3, and ClCH2GeD3for both the gaseous and solid states in the 250–4000 cm−1 region have been obtained. All the fundamental vibrations except for the skeletal bending and YH3(–D3) (Y=Si, Ge) torsional vibrations have been observed and assigned. The normal vibration calculation has been carried out using a modified Urey-Bradley force field. The transferability of the force constants has also been investigated.
  • Haruhiko Tanaka, Tsutomu Kado, Hisao Negita
    1972 Volume 45 Issue 11 Pages 3342-3345
    Published: 1972
    Released: March 27, 2006
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    A considerable dilution of tritiated water in the water of crystallization was observed in the crystal-growth process of KCr(SO4)2·12H2O from a slightly supersaturated aqueous solution. This was explained in terms of an ionic process in aqueous solution and a surface-diffusion mechanism of crystal growth. It was also found that the tritium content in the hexahydrate was appreciably smaller than that in the liberated water during the course of reaction;
    KCr(SO4)2·12H2\xrightarrow[invacuo]40°CKCr(SO4)2·6H2O+6H2O.
    It seems that the step wise dehydration supports the dehydration mechanism proposed by Garner.
  • Yoshio Matsunaga, Nobuhiko Miyajima
    1972 Volume 45 Issue 11 Pages 3345-3349
    Published: 1972
    Released: March 27, 2006
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    The diffuse reflection spectra of sixteen 1-arylazo-2-naphthols deposited on polypropylene, polyacrylonitrile, polyethylene terephthalate, and Nylon-6,6 were recorded in the range from 350 to 700 nm. The spectra indicate the coexistence of the azo and hydrazone tautomers in these systems. By a comparison with the absorption spectra of the compounds dissolved in n-hexane, acetonitrile, methyl benzoate, and formamide, it was concluded that the nature of the fibers is the major factor determining the tautomeric equilibria. The effect of moisture on the spectra was found to be rather small except in the cases of the p-OH and p-MeO derivatives deposited on polyacrylonitrile.
  • Katsutoshi Ohkubo, Tohru Hashimoto
    1972 Volume 45 Issue 11 Pages 3350-3355
    Published: 1972
    Released: March 27, 2006
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    The mechanism of the liquid-phase oxidation of cumene (RH) catalyzed by triphenylsulfonium chloride was investigated by the computer simulation on the basis of the kinetic analysis. We will discuss particularly the initial short stage of the reaction through the time-conversions of the concentrations of components produced or consumed: R·, RO2·, ROOH, a complex between the catalyst and O2 (Cat.–O2), etc. We determined the values of the rate constants appearing in the reaction steps with a good analytic fit to the experimental results, together with the activation energies of all the reaction steps. The following relationships were found between the initial rate of the component formation, ri (component), and the initial concentration of reactants ((Cat.)i, (RH)i, and (O2)i):
    ri(Cat.–O2)\simeq1.243×10−2(Cat.)i0.970(RH)i0.0(O2)i0.964 mol⁄l·min
    ri(R·)\simeq4.705×10−12(Cat.)i0.648(RH)i1.886(O2)i−0.422 mol⁄l·min
    ri(RO2·)\simeq5.837×10−12(Cat.)i0.316(RH)i0.509(O2)i0.737 mol⁄l·min
    ri(ROOH)\simeq4.860×10−4(Cat.)i0.436(RH)i1.842(O2)i−0.850 mol⁄l·min
  • Keikichi Nakamura
    1972 Volume 45 Issue 11 Pages 3356-3362
    Published: 1972
    Released: March 27, 2006
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    The deuteron magnetic resonance in the tantalum-deuterium system has been measured as a function of the composition (0.45 to 0.198 D/Ta) and of the temperature (90 to −179°C), and the results has been discussed in relation to the neutron diffraction and the heat capacity data. The most probable arrangement of the deuteriums in the polymorphic varieties has been proposed. For the low temperature form β1 form), it has an ordered structure which belongs to the space group A222, with the four tantalums at the 4K positions and the two deuteriums at the 2a positions. Since the deuterium positions are described by a single Z′ principal axis direction, which coincides with the c axis, the quadrupole coupling constant is not averaged by the rapid diffusion of the deuteriums. For the intermediate temperature form (β2 form), a structure constructed with four types of domains has been proposed. In this structure, the space group is the same as that of the β1 form, and the deuterium positions in the domains are 2a, 2b, 2c, and 2d respectively. For the high temperature form (α form), the observed quadrupole coupling constant, which is averaged to zero, can be accounted for if the deuteriums are randomly distributed over all the available tetrahedral sites. However, the calculated configurational entropy based on this assumption is larger than the measured value.
  • Kunihisa Sogabe, Akinori Hasegawa, Yoshio Yamada, Masaji Miura
    1972 Volume 45 Issue 11 Pages 3362-3366
    Published: 1972
    Released: March 27, 2006
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    The hindered motion and the structure of the CO2 radical adsorbed on various zeolites were investigated by means of ESR spectroscopy. The adsorbed CO2 radical was obtained by the γ-irradiation of zeolites with carbon dioxide labeled with 13C. The results show that the interaction of the CO2 radical with the zeolite surface changes with the electrostatic field on the surface. The motion and the structure of the adsorbed CO2 radical are affected by the properties of the zeolite surfaces; the former is also influenced by the extent of exchange of the cation on zeolite, regardless of the time of irradiation, before or after the introduction of carbon dioxide. The formation of the CO2 radical on zeolites was interpreted on the basis of such a mechanism that electrons are initially trapped by the surface of zeolite upon the irradiation and then transferred to carbon dioxide molecules. The results also show that the process of the electron transfer depends on the kind of cation.
  • Isao Matsuzaki, Radmilo Simic, Herman A. Liebhafsky
    1972 Volume 45 Issue 11 Pages 3367-3371
    Published: 1972
    Released: March 27, 2006
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    For the purpose of isolating elementary reactions responsible for the decomposition of hydrogen peroxide by iodine and its compounds, the reaction at 50°C of acid solutions containing I2, I, HIO, etc. with [I] and [I2] controlled by use of TlI(s) and I2(s) was studied. The rates of the evolution of oxygen, consumption of hydrogen peroxide and production of H+ were subjected to measurement and led to a formulation of a complex mechanism consisting of the following reactions: HIO2+H2O2→HIO+H2O+O2; H2OI++H2O2→HIO2+H++H2O; HIO+H2O2→H++I+H2O+O2; HIO2+H++I→2HIO; H2OI+\ ightleftharpoonsHIO+H+; I+H++H2O2→HIO+H2O; and I2+H2O\ ightleftharpoonsHIO+H++I. Absolute or relative rate constants for the first four reactions were evaluated by using equilibrium and rate constants of the others.
  • Hiroshi Hosaka, Norimichi Kawashima, Kenjiro Meguro
    1972 Volume 45 Issue 11 Pages 3371-3375
    Published: 1972
    Released: March 27, 2006
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    The electron-donor property of silica-alumina, silica-titania, and alumina-titania system surfaces was investigated by means of TCNQ adsorption. When TCNQ was adsorbed on the surfaces of the metal oxide systems from its acetonitrile solution, the surfaces of the metal oxides acquired the coloration characteristic of each oxide. The coloration was caused by the formation of TCNQ anion radicals on the metal oxide surfaces. The presence of the TCNQ anion radicals was confirmed by studying the ESR absorption and the electronic spectrum. The silica-alumina, silica-titania, and alumina-titania systems showed lower radical-ion-forming activity (electrondonating power) than the parent oxides-silica, alumina, and titania. The change in the activity with the composition was characteristic of each metal oxide system.
  • Yoshio Matsunaga, Yukio Suzuki
    1972 Volume 45 Issue 11 Pages 3375-3379
    Published: 1972
    Released: March 27, 2006
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    The electrical resistivities and Seebeck coefficients of the 2 : 3 iodine complexes of phenoxazine, phenoselenazine, and benzophenothiazines were measured as a function of the temperature. They have resistivity values at 20°C ranging from 10 ohm·cm for the phenoxazine complex to 34 ohm·cm for the benzo[a]phenothiazine complex. Employing the equation of Johnson and Lark-Horowitz for the Seebeck coefficient of an intrinsic semiconductor, the ratio of the electron-to-hole mobility in the phenoselenazine complex was found to be 1.07 and the electron mobility was estimated as 0.26 cm2/V sec. By an examination of the vibrational spectra, the expected cation-radical character was confirmed for the complexes of phenoselenazine and benzophenothiazines. The presence of a broad electronic absorption band in the rock-salt region characteristic of low-resistivity organic semiconductors was noted in every case.
  • Hitoshi Taniguchi, Hideyo Hasumi, Hiroyuki Hatano
    1972 Volume 45 Issue 11 Pages 3380-3383
    Published: 1972
    Released: March 27, 2006
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    Free-radical intermediates in the reaction of the hydroxyl radical with amino acids and structurally related compounds such as alcohols, amine, and carboxylic acids have been studied by ESR spectroscopy using a continuous-flow method. The hydroxyl radical is generated by a ferrous ion-hydrogen peroxide system (Fenton’s reagent). ESR spectra with fairly good signal-to-noise ratios are obtained for the first time in a Fenton’s reagent system from glycine, valine, leucine, glutamic acid, lysine, methionine, tyrosine, ethylamine, acetic acid, pro-pionic acid, n-butyric acid, and succinic acid. Structures, g-values, and hyperfine coupling constants of these radicals are tabulated. The analysis of ESR spectra shows that the same radical species are produced mainly in a Fenton’s reagent system as in a titanous chloride-hydrogen peroxide system. This is consistent with the existence of the hydroxyl radical in both systems. The observed ratio of C2–H to C1–H proton hyperfine coupling constants gives information concerning steric conformations, freedom in the internal rotations, and s-character of the intermediate radicals.
  • Fuyuhiko Inagaki, Issei Harada, Takehiko Shimanouchi, Mitsuo Tasumi
    1972 Volume 45 Issue 11 Pages 3384-3388
    Published: 1972
    Released: March 27, 2006
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    The resonance Raman spectra were observed from dilute aqueous solutions of the poly (vinyl alcohol)-iodine complex, using the He–Ne 632.8 run and Ar+ ion 488.0 nm lines for excitation. Two kinds of poly (vinyl alcohol) were used; one (A) had the degree of polymerization of 500, and the other, (B) 2000. For both samples, the resonance Raman spectra taken with the 632.8 nm line are similar to that of the starch-iodine complex, the intensity of the Raman band at 155 cm−1 being strongly enhanced. This band is assigned to the antisymmetric stretching vibration of the I3 ion aligned in the helical poly(viny alcohol) molecule. On the other hand, the intensity of the Raman band at 106 cm−1 is enhanced for Sample A when the 488.0 nm line is used for excitation. This band is assigned to the symmetric stretching vibration of the I3 ion. Its overtones were observed until the sixth. It is clear that the enhancement of the intensities of the 155 and 106 cm−1 bands is closely connected with the absorption bands at 670 and 490 nm respectively.
  • Yasushi Kai, Noritake Yasuoka, Nobutami Kasai, Masao Kakudo
    1972 Volume 45 Issue 11 Pages 3388-3396
    Published: 1972
    Released: March 27, 2006
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    The molecular structure of a stereospecific (isotactic) polymerization catalyst of the acetaldehyde-Lewis base adduct [Me2Al·O·CPh:NPh,ONMe3] has been determined from three-dimensional X-ray data collected on a single crystal diffractometer. The crystal belongs to the triclinic system (space group P\bar1), with two formula units in a cell with dimensions of; a=8.517±0.004, b=10.096±0.005, c=12.256±0.005 Å, α=104.67±0.04, β=106.97±0.04, and γ=98.10±0.04°. The structure was solved by the symbolic addition method and refined by the block-diagonal, least-squares procedure. The molecule is monomeric, and both amide and ONMe3 groups are connected to the aluminum atom through oxygen atoms. The amide moiety has an imino-ether type structure and two adjacent benzene rings take trans configuration about the N–C bond. The co-ordinated ONMe3 group has a structure similar to that of the free molecule.
  • Yasushi Kai, Noritake Yasuoka, Nobutami Kasai, Masao Kakudo
    1972 Volume 45 Issue 11 Pages 3397-3402
    Published: 1972
    Released: March 27, 2006
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    The molecular structure of a stereospecific (isotactic) polymerization catalyst of the acetaldehyde-monomer complex, [Me2Al·O·CPh: NPh,MeCHO]2, has been determined on the basis of three-dimensional X-ray data collected photographically. The crystal belongs to the orthorhombic system (space group Pcca) with four dimer formula units in a cell with the dimensions of: a=15.83(3), b=12.61(1), and c=17.66(1) Å. The structure was established by the heavy-atom method and refined by block-diagonal, least-squares procedure. The molecule is dimeric and has a C2-2 symmetry. A monomer molecule, acetaldehyde, is inserted in the Al–N bond of the original polymerization catalyst. The oxygen atom bridges both aluminum atoms, Al–O=1.858(6) and 1.985(6) Å. The α-carbon atom of acetaldehyde bonds to the nitrogen atom of the amide moiety, C–N=1.469(12) Å. The aluminum atom is penta-co-ordinated and has a trigonal bipyramidal conformation.
  • Yasushi Kai, Noritake Yasuoka, Nobutami Kasai, Masao Kakudo
    1972 Volume 45 Issue 11 Pages 3403-3408
    Published: 1972
    Released: March 27, 2006
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    The molecular structure of a stereospecific (isotactic) polymerization catalyst of the acetaldehyde-monomer-Lewis acid complex, [Me2Al·O·CPh:NPh,MeCHO,AlMe3], has been determined from three-dimensional X-ray-diffraction data collected photographically. The crystal belongs to the monoclinic system (space group P21n), with four formula units in a cell with dimensions of: a=13.60(3), b=13.74(2), c=12.40(2) Å, β=95.9(2)°. The structure was solved by the heavy-atom method and was refined by the block-diagonal, least-squares procedure. The trimethylaluminum forms a bond with the electron-rich oxygen atom of acetaldehyde through the electron-deficient aluminum atom. The polymerization mechanism can reasonably be concluded to be the “co-ordinated cationic polymerization”.
  • Jun-ichiro Take, Tetsuo Tsuruya, Tetsuo Sato, Yukio Yoneda
    1972 Volume 45 Issue 11 Pages 3409-3414
    Published: 1972
    Released: March 27, 2006
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    A new UV-spectrophotometric n-butylamine titration method was proposed for measuring acid-strength distribution of acid sites on solid acid catalysts. The method can provide information on acid-strength distribution of acid sites beyond H0=−8.2, which can not be obtained by the conventional visual n-butylamine titration method. Acid-strength distributions were measured for a series of silica-alimina catalysts differing in sodium content, using 4-benzeneazodiphenylamine (pKa=1.5), trans-benzalacetophenone (pKa=−5.6), 4-nitrotoluene (pKa=−10.5), and 2,4-dinitrotoluene (pKa=−12.8) as indicators. The results revealed that about one-half of the acid sites on an unpoisoned silica-alumina catalyst lay in the H0 region from −10.5 to −12.8, and the strongest ones in the H0 region beyond −12.8. The strong acid sites were eliminated with the modification of acid-strength distribution as the catalyst was poisoned with sodium ions. UV spectra of the above indicators in adsorbed state were discussed.
  • Haruo Hosoya, Keiko Kawasaki, Kimiko Mizutani
    1972 Volume 45 Issue 11 Pages 3415-3421
    Published: 1972
    Released: March 27, 2006
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    Empirical relations are proposed for the boiling point (bp) and the topological index (ZG) of a saturated hydrocarbon as
    bp=alogZG+b
    or bp=(alogZG+c)⁄\sqrtN+b,
    where N is the number of the carbon atoms. A number of compounds with or without ring(s) are plotted for these relations. Correlation is generally better for cyclic compounds than for chain compounds. Sterically hindered paraffins deviate appreciably. Several empirical rules on the isomeric lowering of the boiling point of saturated hydrocarbons are presented and most of them are shown to be consistent with the above relations. Several empirical formulae for the boiling point of normal paraffins are compared and discussed.
  • Masao Kiyama, Toshikazu Akita, Shigeki Shimizu, Yoshiro Okuda, Toshio ...
    1972 Volume 45 Issue 11 Pages 3422-3426
    Published: 1972
    Released: March 27, 2006
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    Dilute solutions of ferrous sulfate, sulfuric acid, hydrochloric acid, nitric acid and acetic acid in which iron powders are dispersed have been oxidized at below 80°C by blowing air into them. The resulting precipitates have been examined by means of X-ray diffraction, chemical analysis and optical and electron microscopy. When the iron powder is well dispersed, γ-FeOOH is formed with or without α-FeOOH, α-Fe2O3, or Fe3O4. The mode of formation depends on such factors as particle size, amount of iron powder, kind of anion present and temperature. Particle size greatly influences the formation of γ-FeOOH in the sulfate system, but not in the other systems.
  • Yasuo Wakatsuki, Shun-ichi Nozakura, Shunsuke Murahashi
    1972 Volume 45 Issue 11 Pages 3426-3429
    Published: 1972
    Released: March 27, 2006
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    Stable complexes with the general formula [Cl2ML]2 (M=Pt, Pd; L=vinyl ethers, propenyl ethers, 1,2-dimethoxyethylene) have been prepared. The IR spectra of [Cl2Pt(trans-CH3CH=CHOCH3)]2 showed a change which was attributed to the transcis isomerization of the coordinated olefin. A similar cistrans isomerization was also suggested for the other propenyl ether and 1,2-dimethoxyethylene complexes. The palladium complex of vinyl t-butyl ether was found to react with aqueous NaOH in a way similar to the Wacker process.
  • Masanobu Sakanoue, Mitsuo Nakatani
    1972 Volume 45 Issue 11 Pages 3429-3433
    Published: 1972
    Released: March 27, 2006
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    Determination of the complex formation constant of actinides (Am, Cm) and lanthanides (Pm, Eu, Lu) with lactic acid was carried out by means of the electrophoretic method. “Cellogel”, a gelatinized cellulose acetate was used as the supporting medium for electrophoresis at 10°C. Electrolyte solutions of various pH at an ionic strength of 1.5 were prepared from 0.5M lactic acid solution for electrophoresis at various pH values. The migration zones of α- and β-emitter were determined by α track on cellulose nitrate and autoradiographic image on X-ray film, respectively. The mobility of each nuclide at different pH was analyzed to obtain the formation constants of lactate complex of each element with reference to dissociation equilibrium. The β1 values thus obtained were consistent with those obtained by other methods. The method was found to be especially useful for determining the complex formation constants of trans-uranium elements with only tracer amounts of these elements.
  • G. Gopala Rao, P. V. Krishna Rao, G. Bala Bhaskara Rao
    1972 Volume 45 Issue 11 Pages 3434-3437
    Published: 1972
    Released: March 27, 2006
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    Conditions have now been developed for a direct potentiometric titration of iron(III) with hydrazine sulphate at room temperature. Osmium tetroxide markedly catalyses the reaction in medium of 2.0–3.0 pH. Under the conditions prescribed four moles of iron(III) are reduced per every mole of hydrazine oxidised. Application of the new method to the assay of iron(III) in an alloy is also considered.
  • G. Gopala Rao, C. Radhakrishnamurty
    1972 Volume 45 Issue 11 Pages 3437-3439
    Published: 1972
    Released: March 27, 2006
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    Accurate and convenient procedures have now been devised for the titrimetric determination of iron(II), molybdenum(V), and thallium(I) with potassium chlorate using visual indicators. These procedures are more advantageous than the procedures involving bromate. Further, chlorate is to be preferred as it is more inexpensive than bromate or iodate. Potassium chlorate is now obtainable at the purity required of a primary standard at a nominal cost. The chlorate titration procedure for iron(II) works satisfactorily even in the presence of organic materials such as oxalic acid, tartaric acid, and citric acid, so that it can be used for the determination of ferrous iron in pharmaceutical preparations or of ferric iron after reduction. It has been observed by us that oxygen of the air interferes in the titration of iron(II) in 6–7M hydrochloric acid medium using naphthol blue black or methyl orange as a redox indicator but not in the titration of iron(II) in sulphuric acid medium using ferroin as an indicator. An inert atmosphere is not necessary for the titration of molybdenum(V) and thallium(I) in hydrochloric acid medium.
  • Charles A. Kingsbury, D. C. Best
    1972 Volume 45 Issue 11 Pages 3440-3445
    Published: 1972
    Released: March 27, 2006
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    The stereochemistry of the various conversions in the 1,2-diphenyl-1-propyl system was measured as a function of aromatic substituent. For β-anisyl groups the reaction occurred with retention of configuration. For compounds with indifferent electron donating aryl groups, the conversions were stereoselective forming mostly threo product. For β-p-nitrophenyl groups the stereochemical course of the reaction was “racemization.” The latter reactions were associated with the presence of open ions. In certain reactions, acetate products were formed in low yield with retention of configuration, irrespective of substituent. The kinetics of ethanolysis were consistent with (partial) bridged ion formation for the threo isomers and with extensive open ion formation for the erythro species.
  • Shigeru Nagashima, Minoru Yoshida, Takejiro Ozawa
    1972 Volume 45 Issue 11 Pages 3446-3451
    Published: 1972
    Released: March 27, 2006
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    A method for the determination of minute amounts of sulfide- and sulfate-sulfur in igneous rocks was investigated. A rock sample is easily dissolved by heating with tin(II)-strong phosphoric acid or strong phosphoric acid. When the rock sample is dissolved with tin(II)-strong phosphoric acid, total-sulfur is evolved as hydrogen sulfide. With strong phosphoric acid, sulfide-sulfur is evolved as hydrogen sulfide, but sulfate-sulfur is not. The hydrogen sufide evolved is fixed as zinc sulfide, and then determined by the photometric method, using mercuric thiocyanate and ferric iron. The conditions for separating sulfide- and sulfate-sulfur in rocks were examined by using samples which had been prepared by mixing rock or silica (each of them, <0.001% S) with sulfides or sulfates. The application of the method to some igneous rock samples gave results with a coefficient of variation of about 5% for sulfur contents of 0.01–0.02%. The sulfur in samples with more than 0.001% can be determined by using about 0.1 g of samples. The sulfide- and sulfate-sulfur in two standard rock samples were also determined: W-1 (Total-S, 0.012%; Sulfide-S, 0.005%; Sulfate-S, 0.007%) and G-1 (Total-S, 0.004%, Sulfide-S, <0.001%; Sulfate-S, 0.004%).
  • Yuzo Yoshikawa, Ekyo Fujii, Kazuo Yamasaki
    1972 Volume 45 Issue 11 Pages 3451-3455
    Published: 1972
    Released: March 27, 2006
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    The cobalt(III), cobalt(II), and nickel(II) complexes of N,N,N′,N′-tetrakis(2-aminoethyl)ethylenedianime and -1,2-propanediamine were prepared, and the cobalt(III) complex of the former ligand was resolved by fractional crystallization and column chromatography on SE-Sephadex. The absolute configurations of the cobalt(III) complexes were assigned on the basis of the stereospecificity of the latter ligand; they were later confirmed by the X-ray analysis. The electronic absorption, circular dichroism, and optical rotatory dispersion spectra of the complexes prepared were also measured.
  • Kikumasa Sato, Seiichi Inoue, Haruhito Sato
    1972 Volume 45 Issue 11 Pages 3455-3457
    Published: 1972
    Released: March 27, 2006
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    2,3-Dimethoxy-5-methylbenzoquinone, the key intermediate of the synthesis of coenzyme Q, was synthesized via two new routes. The methylation of 5-nitrovanillin gave 5-nitroveratraldehyde, which was then catalytically reduced to afford 5-aminohomoveratrol. The oxidation of 5-aminohomoveratrol gave 2,3-dimethoxy-5-methylbenzoquinone. 2,3,4-Trimethoxyphenol was obtained by the decarboxylation of 3,4,5-trimethoxysalicylic acid. This was converted via Mannich reaction to 2,3,4-trimethoxy-6-methylphenol, which was then easily oxidized to 2,3-dimethoxy-5-methylbenzoquinone.
  • Toshifumi Hirata
    1972 Volume 45 Issue 11 Pages 3458-3464
    Published: 1972
    Released: March 27, 2006
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    The optical rotatory dispersion and the circular dichroism curves were measured for some bicyclo[3.1.1]heptane derivatives. The applicability of the octant rule to a bicyclo[3.1.1]heptane system was discussed in connection with its preferred conformation; the conformation was determined on the basis of nuclear magnetic resonance spectrum measurements.
  • Tsuneo Suga
    1972 Volume 45 Issue 11 Pages 3464-3472
    Published: 1972
    Released: March 27, 2006
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    Es wurde der Mechanismus des Litheffektes diskutiert. Um dieses Problem zu behandeln, wäre es nützlich, daß man sich den Litheffekt in Verbindung mit Lithemulsion und Lithentwickler überlegt. Nach Yule beschleunigen die bei der Entwicklung entstandenen Oxydationsprodukte des Hydrochinons die Lithentwicklung. In der vorliegenden Arbeit wurde die Rolle der Oxydationsprodukte weiter vom Standpunkt der Oxydation aus elektrochemisch untersucht. Die Oxydationsprodukte beschleunigen die Entwicklung der stärker belichteten Körner durch die Herabsetzung des Ladungsbarriereeffektes und hemmen die Entwicklung der schwächer belichteten Körner durch die Oxydationsfähigkeit. Wenn diese beiden Faktoren miteinander ins Gleichgewicht gebracht werden, könnte man einen guten Litheffekt erhalten. Nach dieser Ansicht konnte man die Ursache für den guten Litheffekt einer Lithemulsion gut erklären.
  • Fumio Nozaki, Keiichi Ohki
    1972 Volume 45 Issue 11 Pages 3473-3474
    Published: 1972
    Released: March 27, 2006
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  • Katsutoshi Ohkubo, Hidetoshi Shimada, Masahide Okada
    1972 Volume 45 Issue 11 Pages 3475-3476
    Published: 1972
    Released: March 27, 2006
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  • Yuhei Uzu, Michihiro Hattori
    1972 Volume 45 Issue 11 Pages 3476-3478
    Published: 1972
    Released: March 27, 2006
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