Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 46 , Issue 10
Showing 1-50 articles out of 103 articles from the selected issue
  • Natsuko Shimizu, Kazuo Shimokoshi, Iwao Yasumori
    1973 Volume 46 Issue 10 Pages 2929-2932
    Published: 1973
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The state of adsorbed oxygen on metallic silver dispersed on silica gel has been studied by ESR. The spectra observed by the interaction of oxygen and the surface were found to be composed of spectra due to two different species. One of the species, which was formed separately by the contact with oxygen at −110 °C, was identified with O2 chemisorbed on metallic silver by a comparison of the observed g values and the other features with those previously reported. The other species has a doublet at g=2.036. This spectrum was reproduced by the interaction of N2O with the silver surface. Further, the γ-irradiation of the silver samples in the presence of O2 and N2O markedly enhanced the intensity of this spectrum, showing a low-field hump. On the basis of the g values and the splitting of the high-field doublet, assuming that the doublet is due to the hyperfine interaction of an unpaired electron with the silver nucleus, the species was assigned to Ag2+ in the present system. It is postulated that this species is possibly formed by the dissociative and/or charge-transfer chemisorption of O2 and N2O, suggesting the presence of non-paramagnetic oxygen species, such as O2−, as a counter ion of Ag2+.
  • Kazuhiko Ishizu, Muneki Ohuchi, Fujito Nemoto, Masao Suga
    1973 Volume 46 Issue 10 Pages 2932-2936
    Published: 1973
    Released: March 27, 2006
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    The cation radicals of some alkylbiphenyls such as 4,4′-bitolyl, 4,4′-di-t-butylbiphenyl, and 2,2′, 4,4′, 6,6′-bimesityl, were generated by SbCl5 oxidation in CH2Cl2. The ESR observation was carried out, and the Q, values of the methyl and t-butyl were estimated based on either the theoretical spin density or the experimentally-determined spin density from the 13C-hyperfine splitting. The Q, value of the methyl in the cation radical was found to be 1.5 times that for the anion radical. The t-butyl groups of the cation radical also showed a much larger Q value than that for the anion radical. The perturbation of the spin density due to the steric hindrance was investigated with reference to the prediction of the McLachlan’s MO calculations carried out for the hindered biphenyl. The experimentally-determined spin density derived from the Q value established for the para-derivative can be adequately interpreted on the assumption that the planar character of the biphenyl would be much reduced, contrary to the tendency found for the anion radicals. This effect suggests that a different delocalization of the unpaired electron may be expected between the cation and the anion radical: that is, the unpaired electron brings about a fair bonding on the central 1–1′ bond in the anion radical, but an antibonding for the cation radical, because the odd π-orbital of the cation has its node between the central 1–1′ bond.
  • Akiko Okumura, Nobukazu Okazaki
    1973 Volume 46 Issue 10 Pages 2937-2941
    Published: 1973
    Released: March 27, 2006
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    The rates of oxygen exchange between arsenate ions and water have been measured at 14.5 °C and 30 °C over the pH range of 6.5–12.5. The rate, R, may be expressed by the rate law:
    R=k_1[H_2AsO_4^-]+k_2[HAsO_4^2-]+k_3[AsO_4^3-]+k_4[H_2AsO_4^-]^2+k_5[H_2AsO_4^-][HAsO_4^2-]+k_6[HAsO_4^2-]^2.
    The exchange rates at 30 °C and I=0.55 have been analyzed in terms of this rate law to obtain the values of the rate constants, k1k6. The activation energy of the over-all exchange reaction is 13.2±0.2 kcal/mol at pH 7.51 and 22.14±0.02 kcal/mol at pH 9.79. The reaction shows a negative salt effect in the region of pH 7.5, and a positive salt effect at pH 9.3.
  • Katsutoshi Ohkubo, Futoshi Kitagawa
    1973 Volume 46 Issue 10 Pages 2942-2945
    Published: 1973
    Released: March 27, 2006
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    An MO-simulation of the geometrical change in the bimolecular methane oxidation, CH3+O2→CH3O2, was performed using the CNDO/2 approximation. The geometry of CH3O2 was predicted to take rOO=1.19 Å and ∠COO=111° with fixed distances of rCO=1.44 Å and rCH=1.09 Å. The coupling reaction proceeds smoothly, without any appreciable activation energy, with the geometric transformation of the momentarily-living CH3­-­-O2, with rCO=2.36∼1.44 Å, rOO=1.132∼1.19 Å, and ∠COO=90∼111°. The magnitude of the electron migration between CH3 and O2 throughout the reaction was estimated.
  • Hayao Kobayashi
    1973 Volume 46 Issue 10 Pages 2945-2949
    Published: 1973
    Released: March 27, 2006
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    Crystals of the 1 : 1 charge-transfer complex of N-MePZT–TCNQ, are monoclinic with those lattice constants: a=10.904, b=13.321, c=7.086 Å, and β=91.06°, and with the space group C2/m. X-ray structure analysis showed that the mixed-stacks of N-MePZT and TCNQ, exist along the c axis. N-MePZT is disordered, and its apparent molecular symmetry is C2h, taking four possible conformations. The molecular geometry of TCNQ, indicates that the amount of the charge transferred from N-MePZT is very small (<0.2e).
  • Hiroyuki Shinoda, Hidenobu Tatematsu, Tomoo Miyazaki
    1973 Volume 46 Issue 10 Pages 2950-2955
    Published: 1973
    Released: March 27, 2006
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    The effects of doubly-excited configurations, especially of the χk1mn type, on the results of P-P-P-CI calculations of unsaturated compounds have been discussed by comparing the results obtained by three different types of CI treatment. The calculations of the pi-electronic total energies of ground states, the electronic transition energies, the oscillator strengths, and the pi-electronic densities of sixteen molecules were performed. The core resonance integrals and electronic repulsion integrals were readjusted so that the transition energies, obtained by CI calculations considering all the singly- and doubly-excited configurations, might coincided with the experimental results. From the results of these calculations, it is found that χk1mn-type configurations play an important role in CI calculation.
  • Yôichi Iida
    1973 Volume 46 Issue 10 Pages 2955-2959
    Published: 1973
    Released: March 27, 2006
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    The infrared spectra (400–4000 cm−1) were measured with neutral p-bromanil and its anion radical. Appreciable frequency differences between their corresponding bands were observed. The fundamental frequencies were assigned, and the simple Urey-Bradley force fields were determined for both the neutral p-bromanil and its anion radical. The differences in the molecular and electronic structures between these two molecules were discussed on the basis of these results. The half-occupied molecular orbital of the p-bromanil anion radical was found to belong to the b3g irreducible representation.
  • Fusao Takusagawa, Ken Hirotsu, Akira Shimada
    1973 Volume 46 Issue 10 Pages 2960-2965
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of trimellitic acid(benzene-1,2,4-tricarboxylic acid) for the pseudo-cell was determined by the method of X-ray diffraction. The crystal is monoclinic, with the space group of I2/c and with a=15.91, b=61.35, c=8.99 Å, and β=95.4°. The appearence of diffraction patterns strongly indicated the existence of the pseudo-cell with b⁄5 and with the space group of I2/c. The structure of the pseudo-cell was determined by the symbolic addition method. The final R value is 13.6%. There is no intramolecular hydrogen bond between the adjacent carboxyl groups, and one of these carboxyl groups twists greatly out of the plane of a benzene ring so that the repulsion between the oxygen atoms is reduced. Each molecule is joined, through three kinds of hydrogen bonds, with three neighboring molecules. These hydrogen bonds are formed between the carboxyl groups related by the center of symmetry and the two-fold axis. The molecular dimensions and packing obtained by the refinement for the pseudo-cell do not seem to contain unacceptable results.
  • Haruo Nakayama, Masao Tahara
    1973 Volume 46 Issue 10 Pages 2965-2968
    Published: 1973
    Released: March 27, 2006
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    The solid-liquid phase diagram for the water +1,4-dioxane system has been determined by the ordinary cooling curve method and with the aid of a differential scanning calorimeter (DSC). The diagram shows the existence of a hydrate which is stable in rather narrow ranges of temperature (−15.8∼−13.5 °C) and of composition (37.0∼46.5 wt% dioxane). From the phase relations and an analysis of the calorimetric data, the composition and the heat of formation (from the liquid states of both components) of the hydrate have been estimated to be C4H8O2·mH2O with m=36∼39 and ΔH1=−51.3 (for m=36)∼−55.6 (for m=39) kcal/mol respectively. This hydrate seems to be the same as that recently reported by Rosso et al., though the compositions and the temperature ranges are very different.
  • Yoshiyuki Kawashima, Chiaki Hirose
    1973 Volume 46 Issue 10 Pages 2969-2975
    Published: 1973
    Released: March 27, 2006
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    The J=2←1 transitions of methyl iodide in the v3, v6, 2v3, v2, v3+v6, and v5 vibrationally-excited states are observed. In v3+V6, the central component, ν360, of the J=2←1, K=1←1 transition is observed at 14.6 MHz, higher than the ν36+ of the l-type doubling. This is interpreted by the fact that the E state with K=−l=±1 is affected more strongly by the Fermi resonance through k356 than is the A state with K=l=±1. The Fermi resonance through k356 causes the Coriolis coupling between v2 and v5 through ζ25(y) to be transferred to v3+v6. As a result, the l-type doubling constant, q6, is determined to be −5.8 MHz. The Stark effect in the presence of the l-type doubling and nuclear quadrupole splitting is formulated and used in the analysis.
  • Shunsuke Kobinata
    1973 Volume 46 Issue 10 Pages 2976-2981
    Published: 1973
    Released: March 27, 2006
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    The electronic structures of nickelocene have been investigated by means of the configurational interaction method. The locally-excited configurations of the central metal ion and the charge-transfer configurations corresponding to an electron transfer from the ligand system to the central metal ion have been taken into account. A correspondence with the crystal-field treatment has been obtained using the partitioning technique of solving the secular equation. The energies of the charge-transfer configurations, the resonance integrals, and the Racah parameters were determined so as to obtain the best fit with the observed d-d transition energies.
  • Akiko Okumura, Nobukazu Okazaki
    1973 Volume 46 Issue 10 Pages 2981-2984
    Published: 1973
    Released: March 27, 2006
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    Oxygen exchange between arsenate ions and crystal water in the course of hydration of anhydrous salt with water vapor and subsequent dehydration of the resulting hydrate has been studied with disodium hydrogen arsenate and with sodium dihydrogen arsenate. There is a remarkable difference in the exchange behavior between the anhydrous salt prepared by dehydration in vacuo at room temperature and that prepared at higher temperatures. In the former, the degree of exchange increases with increasing molar ratio of the reactants(arsenate to water), while in the latter, it is independent of the molar ratio. In the exchange reactions of the anhydrous salt prepared at higher temperatures, the number of exchangeable oxygen atoms of an arsenate ion is found to be 0.5 (that is, one atom for two arsenate ions) for disodium hydrogen arsenate, and 4 for sodium dihydrogen arsenate.
  • Katsue Shibata, Tadamitsu Kiyoura, Jun Kitagawa, Takashi Sumiyoshi, Ko ...
    1973 Volume 46 Issue 10 Pages 2985-2988
    Published: 1973
    Released: March 27, 2006
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    Eighteen binary metal oxides consisting of TiO2–MmOn, ZnO–MmOn and Al2O3–MmOn (MmOn: metal oxide) were prepared by the usual co-precipitation method, their acid amounts and strengths being determined by n-butylamine titration using various acid-base indicators. The acid strengths of fourteen of the tested binary oxides of molar ratio 1 : 1 were found to be remarkably higher than those of the component single oxides. High acid strengths were as follows: H0≤−8.2 for TiO2–SiO2, H0≤−5.6 for TiO2–Al2O3 and Al2O3–ZrO2 and H0≤−3 for TiO2–CdO, TiO2–SnO2 and ZnO–SiO2. The acid amounts of sixteen binary oxides were larger than those of the component oxides. The effect of the composition of binary oxides on acidity was examined for TiO2–Al2O3, ZnO–Al2O3 and Al2O3–ZrO2. The acidity maxima appearing for TiO2–Al2O3 and ZnO–Al2O3 were found to be of molar ratio\simeq9:1 and for Al2O3–ZrO2\simeq3:2. A fairly good correlation has been demonstrated between the observed highest acid strengths and the average electronegativities of metal ions of binary oxides.
  • Katsuhiro Tamura, Yoshiaki Ogo, Tatsuya Imoto
    1973 Volume 46 Issue 10 Pages 2988-2992
    Published: 1973
    Released: March 27, 2006
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    Rates of the reaction between 3,5-lutidine with ethyl iodide have been measured at 50 °C over the pressure range 1–1,940 kg/cm2 in benzene-nitrobenzene mixtures. The solvation number and average pressure within the solvation-shell of activated complex have been estimated from the rates and the compression of solvent. The solvation number was almost independent of solvent composition, but not the average pressure within the solvation-shell. Estimation of the structural term of the activation volume Δ1V\ eweq in the reaction has been discussed. The logarithms of the rate constants showed a linear relation with the ET-values under atmospheric pressure.
  • Sadakatsu Nishikawa, Tatsuya Yasunaga, Kojiro Takahashi
    1973 Volume 46 Issue 10 Pages 2992-2997
    Published: 1973
    Released: March 27, 2006
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    The ultrasonic absorptions in aqueous solutions of amylamine were measured in the frequency range of 3.5–220 MHz and in the concentration range of 0.01–3.06 M. Two kinds of relaxations were observed. One was attributed to the 5A–A5 reaction of non-ionized molecules of amylamine, and the rate constants were determined from the concentration dependence of the relaxation time at various temperatures. The thermodynamic parameters were determined from the temperature dependence of the rate and equilibrium constants. The other was attributed to hydrolysis, which is a diffusion-controlled reaction. In order to clarify the relation between the stability of the aggregate and the length of the hydrophobic group, the ultrasonic absorptions in aqueous solutions of propylamine were also measured. The excess absorption due to the association-dissociation reaction was not observed; only that due to hydrolysis was observed. It was deduced from this investigation that the aggregate formed by the hydrophobic bonding exists in the aqueous solutions of normal amines, the carbon numbers of which are more than 4.
  • Fusao Takusagawa, Akira Shimada
    1973 Volume 46 Issue 10 Pages 2998-3004
    Published: 1973
    Released: March 27, 2006
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    The crystal structure of hemimellitic acid dihydrate (benzene-1,2,3-tricarboxylic acid dihydrate) has been determined by the X-ray diffraction method. The crystals are triclinic, with a space group of P\bar1 and with cell dimensions of a=11.02, b=9.12, c=8.72 Å, α=106.2°, β=140.2°, and γ=84.2°. The structure was determined by an inspection of a sharpened Patterson map. The final R value was 9.25% for 1532 observed reflections. The hemimellitic acid molecule has the approximate Cs symmetry. Three carboxyl groups twist by 4.5°, 86.8°, and 10.3° out of the plane of a benzene ring. The hemimellitic acid and water molecules are joined by seven independent O–H···O hydrogen bonds to form a three-dimensional network. The water molecules are hydrogen-bonded to each other around a center of symmetry to form a unique four-membered ring. The hydrogen bonds observed are classified by means of the combination of donor and acceptor groups in five types. These types of hydrogen bonds are discussed in the comparison with several carboxylic acid hydrates.
  • Harumi Endo, Otohiko Nomoto
    1973 Volume 46 Issue 10 Pages 3004-3007
    Published: 1973
    Released: March 27, 2006
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    The adiabatic compressibility vs. concentration curves in aqueous solutions of t-butyl alcohol (t-Bu) over a certain temperature range have a common intersection at a fixed concentration (μcβ). The sound absorptions of solutions are nearly constant and are independent of the concentration up to a concentration (μiα) nearly the same as the μcβ. On the basis of the value of μcβ(≅μiα), the properties and the dissolved state of t-Bu in liquid water discussed in terms of the liquid clathrate hydrate model. At this concentration, the liquid clathrate hydrate of t-Bu. consists of 18-hedron, containing 32 water molecules for each t-Bu molecule. For higher concentrations than μcβ, the breakdown of the liquid clathrate hydrate by the addition of excess t-Bu occurs, accompanied by an increase in the number of clusters.
  • Mitsuo Sato, Yuzaburo Fujita, Takao Kwan
    1973 Volume 46 Issue 10 Pages 3007-3011
    Published: 1973
    Released: March 27, 2006
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    The interaction of bis(O,O′-diethyldithiophosphato)oxovanadium(IV), VOdtp2, with pyridine bases has been studied in toluene by ESR. It has been found that the four-membered chelate structure of VOdtp2 is disrupted by pyridine bases to form the complex species identified as VOdtp2·Py and VOdtp2·Py2 by their characteristic ESR spectra. The coordination structures of the newly-formed complexes are discussed in association with the substitution equilibria involved.
  • Hiroshi Hara, Ikuzo Tanaka
    1973 Volume 46 Issue 10 Pages 3012-3015
    Published: 1973
    Released: March 27, 2006
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    The photolysis of ethylene was carried out at room temperature at 1634 Å and 1849 Å. Products at both wavelengths were hydrogen, acetylene, ethane, n-butane and 1-butene. Product analysis and the radical scavenger technique indicate the primary processes to be as follows.
    (Remark: Graphics omitted.)
    The molecular elimination process in the primary processes varied with wavelengths, and was determined to be 47% and 53% at 1634 Å and 1849 Å, respectively. With reference to the percentage reported at other wavelengths, it is pointed out that molecular elimination is suppressed with the increase in excitation energy.
  • Nobuaki Narashima, Noboru Mataga
    1973 Volume 46 Issue 10 Pages 3016-3020
    Published: 1973
    Released: March 27, 2006
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    Electrostatic self-complex formation of p-(N,N-dimethylamino)-benzonitrile and its hetero-complex formation with benzonitrile in cyclohexane matrix were studied in detail. The possibilities of ground state complex and excimer formation in various liquid solvents were examined thoroughly.
  • Koji Kishimoto, Hiroshi Suga, Syûzô Seki
    1973 Volume 46 Issue 10 Pages 3020-3031
    Published: 1973
    Released: March 27, 2006
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    The heat capacities of isopropylbenzene were measured with an adiabatic calorimeter for the crystal from 14 to 177.13 K (Tm), for the glassy state from 14 to around 126 K (glass transition temperature: Tg) and for the liquid from Tg to 313 K, with a sample of 99.93% purity. The heat and entropy of fusion were found to be 7326 J mol−1 and 41.36 J K−1 mol−1, respectively. Based on these data, a set of thermodynamic functions are tabulated at rounded temperatures. In addition to the primary glass transition phenomenon, a secondary enthalpy relaxation as well as a step-like heat capacity anomaly was observed at around 70 K. These facts were discussed in correlation with the β-relaxation already observed by dielectric measurement. Gonfigurational entropies of the supercooled liquid and of the glassy state were calculated to investigate a relation with relaxational properties. The agreement is found between the temperatures where catastrophe occurs in viscosity (T0), and where the configurational entropy vanishes (T2). Finally, a kind of heat capacity break observed in the liquid state is discussed against the view that this behavior is compatible with a third-order thermodynamic transition.
  • Hiroatsu Matsuura, Tatsuo Miyazawa
    1973 Volume 46 Issue 10 Pages 3031-3035
    Published: 1973
    Released: March 27, 2006
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    The Brillouin scattering of KBr crystals was measured by using a helium–neon laser and a pressure-scanned Fabry-Perot interferometer. The Brillouin shifts were measured for various crystal orientations with the scattering vector in the [110] plane. In addition to the strong Brillouin peaks due to the longitudinal acoustic mode, relatively weak Brillouin peaks due to the transverse mode with admixture of the longitudinal mode were clearly resolved for a certain range of crystal orientations. From these Brillouin shifts, the frequencies and velocities of thermally excited sound waves of the wavelength 286.9 nm were obtained, and the three independent elastic constants of the KBr crystal for sound waves of microwave frequencies 6–12 GHz were determined as C11=3.37×1011, C12=0.61×1011 and C44=0.51×1011 dyn/cm2. The elastic constants determined in the present study were close to the ultrasonic values, indicating little dispersion of the sound velocities for the regions between 10 MHz and 10 GHz.
  • Hitoshi Ogata, Hatsuki Onizuka, Yoshimasa Nihei, Hitoshi Kamada
    1973 Volume 46 Issue 10 Pages 3036-3040
    Published: 1973
    Released: March 27, 2006
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    The HeI photoelectron spectra of aliphatic amines, alcohols and mercaptans were measured. These spectra, especially those of methylsubstituted compounds, were interpreted in terms of the orbital energies and corresponding eigenvectors calculated by the CNDO/2 and the INDO type self-consistent field molecular orbital techniques. Modification of CNDO/2 was also performed and the results are briefly discussed.
  • Tetsuo Morimoto, Shigeharu Kittaka
    1973 Volume 46 Issue 10 Pages 3040-3043
    Published: 1973
    Released: March 27, 2006
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    The electrification of iron oxides pretreated at various temperatures from 600 to 1200 °C has been investigated in water by measuring the ζ-potential as a function of the pH. From the surface-chemical point of view, iron oxides pretreated at temperatures lower than 800 °C behave differently from those pretreated at higher temperatures ; the isoelectric point of the former samples reaches an equilibrium value in a few hours, while that of the latter samples increases slowly to an equilibrium value with an increase in the surface hydration. On the other hand, the equilibrium isoelectric point of iron oxide decreases sharply upon heat treatment at 800–1000 °C, corresponding to the change in the chemical composition of iron oxide from Fe2O3 to Fe3O4.
  • Hiroko Hoshino, Susumu Tajima, Toshikazu Tsuchiya
    1973 Volume 46 Issue 10 Pages 3043-3048
    Published: 1973
    Released: March 27, 2006
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    The decomposition of the (M–18)\underset.+ ion of aliphatic alcohols and that of the M\underset.+ ion of 1-alkenes are studied. The temperature effect of the ion source of a mass spectrometer on the ratios of the intensities of these ions, those of the ions produced from them by C2H4 elimination, and those of the metastable ions for the corresponding fragmentation was measured and was compared with the results to be expected from a simple QET consideration. A discrepancy between the result expected and the experimental result was found for 1-alkenes. In order to clarify the cause of the discrepancy, the photoelectron spectrum was measured for 1-hexanol and for 1-hexene and was assumed to represent the internal energy distribution function, P(E), for each of these substances. Taking the shape of the P(E) into account, the result for 1-alkenes was explained.
  • Mitsuo Kitano, Kozo Kuchitsu
    1973 Volume 46 Issue 10 Pages 3048-3051
    Published: 1973
    Released: March 27, 2006
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    The bond distances (rg) and angles (rα) in acetamide CH3CONH2 have been determined by gas electron diffraction as follows: C–C=1.519±0.006 Å, C–N=1.380±0.004 Å, C=O=1.220±0.003 Å, C–H (average)=1.124±0.010 Å, N–H (average)=1.022±0.011 Å, ∠N–C=O=122.0±0.6°, ∠C–C–H (average)=109.8±2°, and ∠C–C–N=115.1±1.6° (or 112.2±1.6°). In comparison with the molecular structure in the crystal, the C–N bond is about 0.05 Å longer, whereas the C=O bond is about 0.04 Å shorter. The C–N and C=O bonds appear to be slightly shorter than the corresponding bonds in N-methylacetamide.
  • Hiroshi Tsubomura, Teruo Yagishita, Hiroo Toi
    1973 Volume 46 Issue 10 Pages 3051-3055
    Published: 1973
    Released: March 27, 2006
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    The electronic absorption spectrum caused by the charge transfer interaction between oxygen and triethylamine was studied quantitatively. It is concluded that there is no particular stabilization between them due to the charge transfer interactions. The intermediate radicals produced by the excitation of triethylamine–O2 in the region of the charge transfer band were studied by the ESR method at various temperatures from 77 to 300 K. The chemical analysis of the irradiation products of the same system was also carried out. The radicals observed are methyl, ethyl, and possibly, (C2H5)2N\dotCHCH3, \dotOOH and (C2H5)2NO·. The products identified are acetaldehyde and diethylamine. Based on these results, the various reactions taking place in the overall photochemical process were speculated.
  • Michio Kitamura, Hiroaki Baba
    1973 Volume 46 Issue 10 Pages 3056-3061
    Published: 1973
    Released: March 27, 2006
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    Absorption and fluorescence spectra of 1- and 2-naphthoic acid (1- and 2-NA) have been studied in a hydrocarbon rigid-glass matrix at 77 K and in the crystal. Each of these acids is associated to form a hydrogen-bonded dimer. On increasing the concentration of 1- or 2-NA, the dimer is further associated to give a higher-order complex that may be assumed to be a tetramer. The fluorescence spectra of the monomer and dimer are in mirror-image relation to their respective absorption spectra in both 1- and 2-NA. When the tetramer of 1-NA is photo-excited, a broad structureless fluorescence emission appears, with the maximum at ca. 7000 cm−1 to the red from the 0–0 band of the dimer fluorescence. The structureless fluorescence spectrum, which has no mirror-image relation to the absorption spectrum of the tetramer, is supposed to originate from an “excimer-like tetramer” of 1-NA. Photo-excitation of the 2-NA tetramer results in a structured fluorescence emission which is considered to come from the simple excited state of the tetramer. The fluorescence lifetimes, quantum yields, and fluorescence-polarization spectra were measured for various molecular species of 1- and 2-NA. The natural fluorescence lifetime of the excimer-like tetramer of 1-NA is evaluated to be 320 nsec, which is 51 times as long as that of the dimer, and the fluorescence from the excimer-like tetramer is polarized mainly along the short molecular axis of the naphthalene nucleus. It is concluded from these observations that the excimer-like tetramer has a symmetrical configuration, with the planes of the constituent dimer molecules parallel to each other, and its fluorescence process is essentially symmetry forbidden.
  • R. Abu-Eittah, M. M. Hamed
    1973 Volume 46 Issue 10 Pages 3062-3066
    Published: 1973
    Released: March 27, 2006
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    The electron-donating strengths of some ketimines have been investigated via the formation of charge transfer complexes with iodine as electron-acceptor. Two types of ketimines were chosen as electron-donors, namely, the =N– unsubstituted as well as the =N– substituted ketimines. With the first type of donors the “n” charge transfer complex was obtained whereas with the second type the “π” charge transfer complexes were obtained. The equilibrium constants were computed for the different types of complexes. An attempt is made to estimate the ionization potentials of the donors from the position of the charge transfer band characteristic of the specific complex.
  • B. N. Misra, S. K. Gupta
    1973 Volume 46 Issue 10 Pages 3067-3069
    Published: 1973
    Released: March 27, 2006
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    Electron Spin Resonance Spectra of 1-1 Diphenyl-2-Picryl Hydrazyl (DPPH) recrystallized from some aliphatic and aromatic solvents have been studied at room temperature in the X-band region. Measurements of lineshape, linewidth and g value were carried out, all the samples being subjected to microchemical analyses with determination of density and melting point. A theoretical study of ESR linewidths has been carried out by means of the Kubo-Tomita theory of ESR linewidth. A quantitative estimation of dipolar width, exchange frequency, exchange integral and asymptotic Curie temperature for each sample was made. A reduction of exchange narrowing has been suggested to be the main cause of broadening.
  • Arati Das, Alpana Ghatak, Abul Hasan, S. B. Roy
    1973 Volume 46 Issue 10 Pages 3070-3071
    Published: 1973
    Released: March 27, 2006
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    Dielectric measurements have been made in 1,2-dimetboxy- and 1,2-diethoxyethane in the liquid state in 1.62, 3.17, and 3.49 cm microwave region. Both the molecules are found to relax mostly by methoxy/ethoxy group rotations.
  • Md. Shamsul Haque, Miloslav Kopanica
    1973 Volume 46 Issue 10 Pages 3072-3076
    Published: 1973
    Released: March 27, 2006
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    The mechanism of substitution reaction between nickel ion and Cu–TTHA chelate was studied by polarographic technique. During the study of the substitution reaction the existence of mixed binuclear chelate CuXNi2− was verified and the value of the stability constant was calculated on the basis of polarographic data. Formation of the mixed binuclear chelate was further verified by the amperometric tit ration of the equimolar mixture of both metal ions with TTHA. Finally the existence of mixed binuclear chelate CuXNi2− was verified by potentiometric titration method. When nickel is present in large excess the replacement of Cu2+ ions from Cu2X2− occurred directly without formation of intermediate mixed binuclear chelate. The stability constant of Cu2X2− was calculated from equilibrium study.
  • V. D. Anand, W. R. Carper
    1973 Volume 46 Issue 10 Pages 3077-3078
    Published: 1973
    Released: March 27, 2006
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    The interaction between magnesium and haematoporphyrin has been studied spectrophotometricaly as a function of concentration, pH and temperature and the existence of a strong 1 : 1 complex has been established. The Benesi-Hildebrand equation was used to determine Kc’s at various wavelengths and temperatures, at pH’s of 7.4, 8.2, and 9.0. The enthalpy of complex formation is seen to change from +9.78 kcal/mol to −9.50 kcal/mol as the pH changes from 8.2 to 9.0. This change may be a reflection of the change in the various ligands which coordinate to the magnesium ion in addition to the porphyrin ring.
  • P. C. Rawat, C. M. Gupta
    1973 Volume 46 Issue 10 Pages 3079-3081
    Published: 1973
    Released: March 27, 2006
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    Complexes of zinc and uranyl ions with L-hydroxyproline (LHP) have been investigated by polarographic method of analysis at 25±1 and 35±1 °C. At pH 4.5, formation of uranyl-LHP complex was observed with metal to ligand ratio of 1: 1 in aqueous and aqueous-methanolic solutions. The stability constant for the complex species is logKc=1.50, 1.30, 1.61, 1.87 in aqueous (25 °C), aqueous (35 °C), aqueous-methanolic (10% v/v) and aqueous-methanolic (50% v/v) media respectively. Between pH 3.0–12.0, zinc–LHP complex has been observed to be reduced irreversibly at DME. Detailed investigations have been reported on the system at 25±1 °C and 35±1 °C at pH 10.0 in varying concentrations of the ligand. Kinetic parameters—the formal rate constant Kf,h° and transfer coefficient α have been calculated.
  • K. R. Solanke, S. M. Khopkar
    1973 Volume 46 Issue 10 Pages 3082-3085
    Published: 1973
    Released: March 27, 2006
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    The thioderivative of 2-thenoyltrifluoroacetone [1,1,1-trifluoro-4-(2-thienyl)-4-mercaptobut-3-en-2-one (STTA)] is used for the simultaneous extraction and direct photometric determination of zinc. About 68 μg of zinc was quantitatively extracted at pH 7–7.5 with 10 ml of 0.001 M STTA in carbon tetrachloride as yellow green colored complex. It was measured spectrophotometrically at 450 nm. The system conformed to Beer’s law over the concentration range of 0.4 to 30 μg of zinc per ml. The color of the complex was stable for more than 96 hr. Zinc was extracted quantitatively and was determined in the presence of large excess of (1 : 300) ions which are associated with it. The method was made selective by using sequestering agents like ascorbic, oxalic, citric acids or alkali cyanide to form unextractable negatively charged complexes. The selective extraction with mesityl oxide was used to eliminate the interferences due to iron and chromium. The procedure was found to be applicable for the analysis of zinc in gun metal and brass. The proposed method is comparable with the standard methods for the extraction of zinc.
  • Nobutoshi Kiba, Tsugio Takeuchi
    1973 Volume 46 Issue 10 Pages 3086-3090
    Published: 1973
    Released: March 27, 2006
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    To define the properties of molybdenum-containing species which appear in the acidification of neutral molybdate solution with mineral acid, the reverse process, i.e. the titration of molybdic acid of acidified molybdate solution with sodium hydroxide, was examined and the titration curves were obtained thermometrically as well as potentiometrically. In the thermometric titration curves there are inflections not found on the pH-titration curves of the same systems. Titration curves of both methods change with molybdenum concentration, the reaction process being found to be responsible for the change. Polymolybdate anions were identified with the aid of the ultraviolet spectrophotometry of Punger et al. A neutral salt such as sodium perchlorate or lithium perchlorate was found to affect the shape of the thermometric titration curve, since in the presence of such salt octamolybdate ion was readily converted into heptamolybdate ion.
  • Mitsuhiro Kasai, Yoshiyuki Kudo, Shuichi Hamada
    1973 Volume 46 Issue 10 Pages 3091-3094
    Published: 1973
    Released: March 27, 2006
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    The DTA patterns of synthesized coprecipitated gels, SiO2–Al2O3–Ga2O3–H2O system, resembled that of allophane, and the exothermic peak temperature in the DTA was lowered continuously from 980 to 810 °C with an increase in the gallium content, while that on mixed gels scarcely lowered. The apparent activation energy for this exothermic reaction on the coprecipitated gels decreased with an increase in the gallium content, while that on the mixed gels hardly changed. The crystallization process during the heat treatment of the gels depended on the content and on the coexistence state of the gallium. A unit cell volume of a mullite crystallized at 1200 °C in the coprecipitated gels was enlarged by forming a solid solution with the gallium ion, in contrast to the small change in that formed in the mixed gels. Further, the exothermic peak in the DTA was considered to originate not only from the formation of the mullite, but also from that of the silico-alumina spinel in the gallium-bearing gels; the exothermic reaction products seem to depend on the composition or the coexistence state of gallium in the gels.
  • Katsutoshi Ohkubo, Hirokazu Kanaeda, Kohji Tsuchihashi
    1973 Volume 46 Issue 10 Pages 3095-3098
    Published: 1973
    Released: March 27, 2006
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    The mechanism of the reductive cleavage of organic halides (RX) by pentacyanocobaltate(II) Co(CN)53− was investigated by means of the extended Hückel MO theory. First, the molecular structure of Co(CN)53− was considered to be the square-pyramidal C4V configuration, without H2O as its sixth ligand. Secondly, the order of the observed rate constants for the Co(CN)53−+RX→Co(CN)5X3−+R. reaction was found to be in satisfactory accordance with that of the calculated binding energies of the R-X bond. Thirdly, the reductive cleavage of RX by Co(CN)53− proceeds by the aid of the predominant electron-migration from the highest-occupied, lone-pair halogen-orbital to the singly-occupied dz2 Co-orbital and from the highest-occupied dxz (or dyz) Co-orbital to the lowest-unoccupied, antibonding pσ* orbital of the R–X bond. Finally, the mode of the interaction between Co(CN)53− and RX was precisely discussed in terms of the homolytic cleavage of the R–X bond.
  • Shigeru Nagashima, Takashi Katsura
    1973 Volume 46 Issue 10 Pages 3099-3103
    Published: 1973
    Released: March 27, 2006
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    The solubility of sulfur in Na2O–SiO2 melts with the Na2O/SiO2 molar ratios of 1/3, 1/2, and 1/1 was investigated by varying the oxygen partial pressure at 1100, 1250, and 1300 °C. The results at 1100 °C are complicated, for the equilibrium state within the gas phase is not established. From the experiments at 1250 and 1300 °C, the following conclusions are reached: (1) When the temperature and the Na2O/SiO2 ratio in the melt are constant, the solubility of sulfur increases with an increase of the total amount of sulfur in the gas phase. (2) When the temperature, the Na2O/SiO2 ratio, and the total amount of sulfur in the gas phase are constant, the solubility of sulfur shows its minimum at a specific oxygen partial pressure; at higher oxygen partial pressures, the sulfur dissolves in the melts mostly as sulfate, while at lower oxygen partial pressures, the sulfur dissolves mostly as sulfide. (3) When the temperature and the total amount of sulfur in the gas phase are constant, the solubility rises greatly with an increase in the Na2O/SiO2 ratio in the melt. (4) When the Na2O/SiO2 ratio in the melt and the total amount of sulfur in the gas phase are constant, the minimum point of the solubility shifts in the direction of higher oxygen partial pressures as the temperature increases. This corresponds to the shifts of the equilibrated gas composition as the temperature increases.
  • Toshitsugu Matsuda, Muraji Shibata
    1973 Volume 46 Issue 10 Pages 3104-3109
    Published: 1973
    Released: March 27, 2006
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    Mixed complexes with L-proline and L- or D-aspartic acid, [Co(L-pro)3−n(L-(or D-)asp)n]n (n=1,2), have been prepared and separated into a number of stereoisomers by means of ion-exchange chromatography. The structures of the isomers have been characterized by various spectral data. As to the [Co(L-pro)(D-asp)2]2− and [Co(L-pro)2(D-asp)] complexes, all of three possible mer-isomers have been isolated in their Δ-forms. The formation ratios among the isomeric species in the reaction system have been estimated spectrophotometrically. Marked differences in stereoselectivity have been found between the L-aspartato complexes and the corresponding D-aspartato complexes. These selectivities have been qualitatively explained in terms of the interaction between the dangling β-carboxylate group in a chelated aspartate ion and the adjacent ligand.
  • Hiroshi Kobayashi, Mitaka Kobayashi, Youkoh Kaizu
    1973 Volume 46 Issue 10 Pages 3109-3116
    Published: 1973
    Released: March 27, 2006
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    Arenetricarbonylchromium forms a charge-transfer molecular complex with electron acceptors such as 1,3,5-trinitrobenzene and tetracyanoethylene but not with electron donors such as N,N,N′,N′-tetramethyl-p-phenylenediamine. The ionization potentials of arenetricarbonylchromium complexes were determined from the charge-transfer transition energies in the molecular complexes. The molecular complexes are formed by a charge-transfer interaction of electron acceptor toward the π-coordinating benzene ring of arenetricarbonylchromium in the case of 1,3,5-trinitrobenzene, and by a charge-transfer toward the central chromium in the case of tetracyanoethylene.
  • Tasuku Murakami, Masahiro Hatano
    1973 Volume 46 Issue 10 Pages 3116-3118
    Published: 1973
    Released: March 27, 2006
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    The circular dichroism (CD) spectra of copper(II) complexes containing the asymmetric tetradentate ligands, such as ethylenediamine-N,N′-di-L-α-propionate, ethylenediamine-N,N′-di-L-α-isovalerate, and ethylenediamine-N,N′-di-L-α-hydrocinnamate, were measured in an aqueous solution. Each of the CD curves can be resolved into four components in the d–d region by Gaussian analysis; these components are related to the four possible d–d transitions of the copper(II) ion. The visible CD spectrum profile of the complexes varies with the variation in ligands; this implies that the conformation of the complexes is affected appreciably by the bulkiness of the side chain in the ligand.
  • Ryokichi Tsuchiya, Tatsuo Murakami, Eishin Kyuno
    1973 Volume 46 Issue 10 Pages 3119-3124
    Published: 1973
    Released: March 27, 2006
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    The thermal ligand-exchange reaction was investigated by derivatographic and isothermal methods for the following complex thiocyanates: cis-[CoCl2en2]SCN, cis-[CoClBren2]SCN·H2O, cis-[CoBr2en2]SCN·H2O and the corresponding trans-complexes, and several corresponding triethylenetetramine complexes cis-α-[CoXYtrien]SCN·H2O, where X and Y represent Cl and Br ion, respectively. cis-Complexes, except for cis-[CoCl2en2]SCN were found to exhibit obviously the ligand-exchange reaction in which Cl or Br is substituted by SCN just after the liberation of lattice water takes place. On the other hand, cis-[CoCl2en2]SCN showed only partial ligand-exchange reaction accompanied by immediate thermal decomposition even at higher temperature than in the other monohydrates. In contrast, all the anhydrated trans-complexes trans-[CoCl2en2]SCN, trans-[CoClBren2]SGN and trans-[CoBr2en2]SCN did not give such a reaction upon heating. The activation energies of cis-[CoClBren2]SCN·H2O were found to be Ea=26±2 kcal/mol for dehydration and Ea=54±2 kcal/mol for ligand-exchange. The thermal ligand-exchange reaction proceeded in cis-type complexes without change in the geometrical configuration of the original complexes. No racemization or inversion could be observed in the optically active complex.
  • Shoji Harada, Hideyuki Tanabe, Tatsuya Yasunaga
    1973 Volume 46 Issue 10 Pages 3125-3127
    Published: 1973
    Released: March 27, 2006
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    The nickel lactate complex formation reaction in an aqueous solution was studied by the pressure-jump method and the overall rate constants, the stability constants, and the activation parameters were determined. The results were interpreted by the use of the step-by-step complex formation mechanism, and it was revealed that the rate-determining step is the chelate-ring formation process. The ligand effect on the rate of the complex formation was also considered.
  • Shigeru Maeda, Hiroshi Kobayashi, Keihei Ueno
    1973 Volume 46 Issue 10 Pages 3128-3133
    Published: 1973
    Released: March 27, 2006
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    A new equation is derived which gives the solute distribution along a column after a zone melting chromatography (ZMG) process, where the initial charge of a sample mixture of k<1 is placed on the upper end of the column, one zone length high. The solute distribution differs significantly from that obtained by Pfann’s equation on an infinite ingot, in the neighborhood of the upper end as expected from the difference in the initial conditions. The solute distribution is calculated numerically for the case in which the initial charge is placed by several zone lengths on the column top. The present multiple zone charge method shows little difference in solute distribution from the conventional single zone charge method, having the advantage of increasing the sample amount to be fractionated. Numerical calculation is performed to find the zone length with which the greatest amount of the solute of k<1 is concentrated into the bottom fraction of a certain length of a given column after each zone pass. A series of resulting zone lengths, showing a stepwise shortening, pass after pass, provides the optimum mode of decrease in the zone length.
  • Ken-ichi Okamoto, Jinsai Hidaka, Yoichi Shimura
    1973 Volume 46 Issue 10 Pages 3134-3138
    Published: 1973
    Released: March 27, 2006
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    cis(O)- and trans(O)-Trianimine(sarcosinate-N-nionopropionato)cobalt(III) salts, which have an asymmetrically coordinated nitrogen atom, were prepared and the cis(O) isomer was optically resolved through its diastereomeric salt with (+)546-(ethylenediaminetetraacetato)cobaltate(III) anion. The less soluble diastereomeric salt produced (+)546-cis(O) isomer of the triammine cation, and its absolute configuration (R) was established from circular dichroism spectrum, referring to the stereochemistry of the several analogous triammine complexes stereo-specifically formed, which contain L-alaninate- and L-prolinate-N-monocarboxylate ligands, where the carboxylate stands for acetate or propionate. Two diastereomeric isomers, R(N)–L(C) and S(N)–L(C), were synthesized for the cis(O)-(L-alaninate-N-monopropionato)triamminecobalt(III) perchlorate salt.
  • Shunzo Yamamoto
    1973 Volume 46 Issue 10 Pages 3139-3141
    Published: 1973
    Released: March 27, 2006
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    The tautomeric equilibrium constants, Kt=[ammonium ion]/[azonium ion], of the first conjugate acids of 2- and/or 2′-methyl-4-dimethylaminoazobenzene derivatives were estimated by the spectrophotometric method. The effects of the 2- and 2′-methyl groups on the basicity of the amino and the azo nitrogens were examined in order to explain the effects on the tautomeric equilibrium. The effects of the 2- and 2′-methyl groups on the basicity of the amino nitrogen is an inductive one only, while the effects on the basicity of the azo nitrogens are both electronic and steric. The latter effect of the 2′-methyl group is very large, but that of the 2-methyl group is not significant. The order of Kt in a series of compounds is almost the same as that of the basicity of the azo nitrogens. That is to say, the magnitude of Kt is mainly governed by the basicity of the azo nitrogens.
  • Kei Murase, Haruaki Watanabe
    1973 Volume 46 Issue 10 Pages 3142-3143
    Published: 1973
    Released: March 27, 2006
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    In order to obtain low-temperature mesomorphic materials, thirty-two p-alkyl-p′-alkoxy-azo- and -azoxybenzenes have been synthesized. The former have been made by the condensation of p-n-alkylnitrosobenzenes and p-n-alkoxyanilines, and the latter, by the oxidation of the former. Twenty-nine of the compounds show nematic behavior. In the majority of cases, the nematic temperature range of the azoxy compounds, which have been considered to consist of two isomers synthesized simultaneously, is appreciably wide.
  • Eizo Matsumura, Masahiro Ariga
    1973 Volume 46 Issue 10 Pages 3144-3146
    Published: 1973
    Released: March 27, 2006
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    Some nucleophilic substitutions on the β-position of the pyridine nucleus were carried out. The reactions of 3-bromo-4-nitropyridine N-oxide(1) with diethyl sodiomalonate, ethyl sodiocyanoacetate, and ethyl sodioacetoacetate in diethyl carbonate or pyridine afforded 3-bis-(ethoxycarbonyl)methyl-4-nitropyridine N-oxide (2), 3-cyano(ethoxycarbonyl)methyl-4-nitropyridine N-oxide (3), and 3-acetyl(ethoxycarbonyl)methyl-4-nitropyridine N-oxide (4) respectively, and ethyl sodioacetoacetate, when treated at a higher temperature, gave 3-ethoxycarbonyl-2-methyl-furo(3,2-c)pyridine N-oxide (5). A probable mechanism of the reaction was presented.
  • Takeo Shiojima, Yoji Hashida, Kohji Matsui
    1973 Volume 46 Issue 10 Pages 3147-3150
    Published: 1973
    Released: March 27, 2006
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    The catalytic effect of bases on the O→N migration of the s-triazinyl group in O-(s-triazinyl)-2-aminophenols has been studied kinetically. In the rearrangement of N-(acyl)-O-(s-triazinyl)-2-aminophenols (II) in alkaline aqueous methanol, the reactive species was found to be an ion formed by the ionization of the acylamino group. In the case of O-(s-triazinyl)-2-aminophenols (I), the rearrangement was subjected to a general base catalysis, although the extent was small.
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