Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 42 , Issue 2
Showing 1-50 articles out of 80 articles from the selected issue
  • Toshikatsu Sata, Reiichi Yamane, Yukio Mizutani
    1969 Volume 42 Issue 2 Pages 279-284
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The behavior of the diffusion boundary layer in the electrodialysis using ion-exchange membranes, mainly a cation-exchange membrane, was studied by means of six different measurements: 1) the determination of the current-voltage curve or the current-(voltage/current) curve; 2) the relation of the pH change of the solution to the current density; 3) the relation of the charge retention, i.e., the sum of the diffusion potential and the membrane potential generated from the concentration gradient across the membrane immediately after the current is shut off, to the current density; 4) the time required to reach a constant current value, namely, to obtain a stationary diffusion boundary layer, when a constant voltage is supplied to the system, versus the current density; 5) the change in the transport number of the counterion in the membrane with the current density, and 6) the relation of the permselectivity between sodium ions and potassium ions to the current density. The interrelation among these results was also examined. The quantity of hydrogen ions or hydroxide ions passing through the membrane increases abruptly at a current density lower than that at which the concentration at the membrane-solution interface in the desalting side attains its minimum. It was newly observed that the results of all the measurements, except for the pH change of the solution, show abnormal phenomena at a current density about twice the limiting current density.
  • L. J. Drummond
    1969 Volume 42 Issue 2 Pages 285-289
    Published: 1969
    Released: March 27, 2006
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    Reflected shock waves, generated in a 5×3 inch shock tube, have been used to ignite mixtures of methane-nitrous oxide and methane-nitric oxide. Monochromators, a pressure transducer and an oscilloscope were used to determine the induction period to ignition (τ) after the reflected wave passed the window. A flash lamp and spectrograph were also used to obtain spectra before and after explosion. For CH4-N2O mixtures it was found that the plot of log(τ[N2O]p5) against inverse temperature was linear and the activation energy was about 60 kcal/mol. This indicates that the rate controlling process was the reaction N2O(+M)→N2+O(+M). However, the reaction CH3+N2O→CH2+N2+OH may also be important. The results for CH4-NO mixtures could be expressed by log(τ[NO]p5)=−10.2+49000⁄4.58T which suggests to the reaction CH2+NO→CH+HNO may be rate controlling. Spectrographic plates showed that CN and OH were present during the induction period but only OH was detected after explosion. This indicates that the reactions CH+NO→CN+OH and CN+NO→N2+CO may be a significant mechanism for achieving the reduction of nitric oxide.
  • Sheo Prakash, S. K. Jain
    1969 Volume 42 Issue 2 Pages 289-291
    Published: 1969
    Released: March 27, 2006
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    Ultrasonic waves of high frequency (1 Mc/sec) have been employed to study the effects on the dilute aqueous solution of Eriochrome Black T. The deaeration of the solution by nitrogen does not greatly affect the rate of decolourization. The process is irreversible and the kinetic study shows it to be unimolecular. Oxidation and subsequent destruction of the dye molecule has been found to be the cause of the fading of the dye solution.
  • T. G. Sastry, S. N. Srivastava
    1969 Volume 42 Issue 2 Pages 291-298
    Published: 1969
    Released: March 27, 2006
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    An oil-in-water system (Nujol being the oil phase) stabilized by the phospholipid, lecithin, has been chosen in this study. The system being negatively charged initially, cationic detergents like lauryl pyridinium chloride (LPC), Cetyl pyridinium bromide (CPB), Phenyl trimethyl ammonium chloride (Ammonyx-200) and Cetyl dimethyl benzyl ammonium chloride (CDBAC) have been employed in order to study their influence on the flocculation and coalescence rates and the degree of aggregation haemocytometrically. Zeta potentials (ξ) have been determined at the corresponding concentrations of the detergents by microcataphoresis and with these values the potential energies and then ultimately the operating van der Waals constant of the system has been determined. From the log C-ξ values it is evident that except Ammonyx-200 which is not an effective cationic detergent, all the others have reversed the charge of the system and their efficiencies are in the order CDBAC>CPB>LPC. The different binding parameters, number of binding sites available for adsorption and free energy of the surface have also been calculated.
  • Kalyan K. Sengupta
    1969 Volume 42 Issue 2 Pages 298-302
    Published: 1969
    Released: March 27, 2006
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    The mechanism proposed by Waters (J. Chem. Soc., 1955, 217) for the oxidation of α-hydroxy acids by manganic pyrophosphate accounts for the kinetics of oxidation of citric acid by cerium(IV) ion. The oxidation appears to proceed through the initial formation of complex and subsequently through free radicals.
  • Kiyoshi Arakawa, Katsutaka Sasaki
    1969 Volume 42 Issue 2 Pages 303-308
    Published: 1969
    Released: March 27, 2006
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    A statistical thermodynamic theory was successfully applied to liquid water, based on the two state model which consists of an ice-like structure (class I) and unbonded monomers (class II). The resulting partition function was formulated and calculated using the two quantities, the energy difference between class I and class II, ε, and the free volume per molecule, vf, as the adjustable parameters which were varied within the physically-reasonable range. The magnitudes of ε and vf were estimated to be 3 kcal/mol and 4.0×10−25 cm3 respectively to give the best fit of calculated values to the experimental data. From the partition function obtained, the Helmholtz energy, the internal energy, the entropy, and the specific heat were calculated. The agreement between the calculated values and the experimental data was found to be satisfactory. From the obtained result it may be concluded that the simple two state model is adequate to explain the thermodynamical data for liquid water.
  • Katsuya Inouye, Junichi Tatsuta, Tsutomu Sakabe
    1969 Volume 42 Issue 2 Pages 308-312
    Published: 1969
    Released: March 27, 2006
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    The flow property of catechol and phenol solutions of 14 bitumen fractions was examined by means of a horizontal viscometer to compare with the molecular weight values of the fractions determined in each solvent. The catechol solutions showed Newtonian flow which corresponds to the homogeneous solutions containing molecules of a limited value of molecular weight. The molecular weight from phenol solutions varies with the fractions, and all fractions showed non-Newtonian (structural) viscosity. The experimental results indicated that bitumens in phenol agglomerate to different extent particular to each fraction. It was presumed that the stress destroys the agglomerated state to a monodisperse state, which is gradually recovered to the original state on standing. It was noted however that the unit particle (or molecule) composing each fraction is not identical in the apparent size in phenol, but varies with fractions.
  • Kenichi Fukui, Katsutoshi Ohkubo, Tokio Yamabe
    1969 Volume 42 Issue 2 Pages 312-318
    Published: 1969
    Released: March 27, 2006
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    The catalytic activity of onium compounds was studied in the homogeneous liquid phase oxidation of cumene and α-pinene. The onium salts, particularly sulfonium, phosphonium, selenonium, arsonium and telluronium were found effective. This result is connected to the fact that the central atom in these onium has vacant d orbitals. Among the anions of the onium salts tested, phosphate and sulfate were most effective. The aryl substituents in the central sulfur in sulfonium lessened the activity, while alkyl substituents made it greater. These facts were attributed to charge migration from the substituents and the anionic part to the central atom.
  • Iwao Satake, Takashi Tahara, Ryohei Matuura
    1969 Volume 42 Issue 2 Pages 319-322
    Published: 1969
    Released: March 27, 2006
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    The counter-ion activity coefficient of sodium alkyl sulfate with chain length from C8 to C14 was determined in aqueous solutions and in the presence of added magnesium ion. The degree of association of sodium ion to the micelle (β) can be deduced from the concentration dependence of the counter-ion activity. The value of β so determined in the presence of magnesium ion was confirmed to decrease rapidly as the relative concentration of magnesium ion increases. The observed change of counter-ion activity with concentration was found to be interpreted in terms of a lameller micelle model.
  • Masaru Suzuki, Yoshimasa Nihei, Hitoshi Kamada
    1969 Volume 42 Issue 2 Pages 323-329
    Published: 1969
    Released: March 27, 2006
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    Expansion formulas are presented for one- and two-center moment integrals between Slater type s,p-orbitals with integer effective principal quantum numbers of 1 to 5, together with the procedure. These formulas are useful in the calculation of a dipole moment and a transition moment from a charge distribution calculated by LCAO-MO method. A FORTRAN subprogram containing most of these formulas, which are important in practice, occupies about 7.7K of the core memory of a computer, HITAC 5020.
  • Shigeru Tsunashima, Shin Satoh, Shin Sato
    1969 Volume 42 Issue 2 Pages 329-333
    Published: 1969
    Released: March 27, 2006
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    The relative efficiencies of sixteen hydrocarbons and of hydrogen in quenching triplet cadmium atoms have been measured at 270±1°C by the competitive quenching method, using the cadmiumphotosensitized cis-trans isomerization of cis-2-butene as a detector reaction. The quenching efficiencies of all the olefins studied and of acetylene were almost the same. The efficiencies of saturated hydrocarbons were, however, very low compared with those of unsaturated ones. Hydrogen was as efficient as unsaturated hydrocarbons.
  • Hirotaka Shimanouchi, Yoshio Sasada
    1969 Volume 42 Issue 2 Pages 334-343
    Published: 1969
    Released: March 27, 2006
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    Crystals of chamaecynenol 4-bromo-3-nitrobenzoate, C21H22O4NBr, are monoclinic, with two molecules in a unit cell of the dimensions, a=10.47, b=14.08, c=6.75Å, and β=101.8° and with the space group of P21. The intensities were recorded on multiple-film equi-inclination Weissenberg photographs and measured visually with a standard scale. The structure was determined by the heavy atom method. The positional and thermal parameters were refined by the least-squares method. The final R factor for the observed reflections is 0.090. The absolute configuration was also determined using anomalous dispersion effect of the bromine atom. It was thus established that chamaecynenol is 7β-ethynyl-4β-hydroxymethyl-10β-methyl-Δ1-cis-octaline in the steroid conformation.
  • Susumu Tsuchiya, Atsumu Ozaki
    1969 Volume 42 Issue 2 Pages 344-348
    Published: 1969
    Released: March 27, 2006
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    Adsorption measurements during the course of ammonia decomposition over molybdenum catalyst have been carried out in a closed circulating system. It was found that most of the nitrogen produced was taken up by molybdenum, and the initial rate of the reaction was independent of the ammonia pressure in a certain region. During the decomposition the nitrogen uptake was several times as much as the amount required to saturate the catalyst surface, which indicates the formation of nitride layers. The catalytic activity of molybdenum trioxide for ammonia decomposition was also observed, and the formation of nitride layers was again suggested. The nitrogen sorbed on molybdenum was removed as ammonia by admitting hydrogen and was displaced by oxygen added afterwards.
  • Kenichi Fukui, Hideyuki Hao, Hiroshi Fujimoto
    1969 Volume 42 Issue 2 Pages 348-355
    Published: 1969
    Released: March 27, 2006
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    The relative ease of the occurrence of SN2 and E2 reactions and the mechanism of related bimolecular processes, such as the base-catalyzed hydrolysis of carboxylic esters and the acid-catalyzed halogenation of aliphatic ketones, are discussed in connection with the MO-theoretical reactivity indices. The results indicate that the valence-inactive populations in the lowest unoccupied (LU) MO are useful reactivity indices for these nucleophilic reactions.
  • Yoshihisa Matsuda, Shoji Makishima, Shigeo Shionoya
    1969 Volume 42 Issue 2 Pages 356-362
    Published: 1969
    Released: March 27, 2006
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    The purpose of this paper is to clarify the mechanism of intramolecular energy transfer from the triplet state of the ligand to the excited levels of the central ion in rare earth chelates. As to seven kinds of samarium β-diketonates, the frequency of infrared absorption due to the stretching vibration of the chelate bond, \ ildeνMO, and the manner of energy transfer are investigated. The probability of energy transfer is estimated from the ratio of the intensity of the samarium emission to that of the ligand phosphorescence, ISmIPh. The overlap integral, S, between the ligand phosphorescence spectrum and the samarium absorption spectrum is obtained. It was found that a linear relation roughly holds between log{(ISmIPh)⁄S} and \ ildeνMO. On the basis of this fact, one is led, by making some arguments, to the conclusion that intramolecular energy transfer is dominated by the resonance mechanism due to the exchange interaction of the π electron system of the ligand triplet state with the f electron system of the central rare earth ion.
  • Tetsuo Miyazaki, Kuniyasu Tanno, Shoji Shida
    1969 Volume 42 Issue 2 Pages 362-365
    Published: 1969
    Released: March 27, 2006
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    The fragmentation of excited ions in the liquid-phase radiolysis of hydrocarbons is explained by a new mechanism, which involves the fragmentation of a highly excited ion (M+**). The M+** ion is considered here to be the electronic excited states and to decompose by the following mechanism. The electronic excitation energy can spread over all C–C bonds in a molecule before its fragmentation and, when the mean excitation energy per C–C bond exceeds its bond energy, the excited ion decomposes instantaneously in one vibration. Further, the mass spectra of isobutane and isooctane are calculated by a simplified quasi-equilibrium theory by introducing the highly excited ion and are compared with experimental mass spectra and with the calculated values without introducing the highly excited ion.
  • Ichimin Shirotani, Takashi Kajiwara, Hiroo Inokuchi, Syun-iti Akimoto
    1969 Volume 42 Issue 2 Pages 366-369
    Published: 1969
    Released: March 27, 2006
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    With an increase in the pressure, the electrical resistance of several TCNQ anion radical salts dropped rapidly in the low-pressure region and levelled off at high pressures. The temperature dependence of the resistance of compressed salt was studied over the region from 77°K to 200°K. The values of the activation energy decreased with an increase in the pressure. However, the metallic behaviour was not observed under very high pressures. The conduction mechanism of TCNQ, salts was discussed from the point of view of a band scheme.
  • Kiyoshi Kawai, Naoto Yamamoto, Hiroshi Tsubomura
    1969 Volume 42 Issue 2 Pages 369-372
    Published: 1969
    Released: March 27, 2006
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    Flash illumination of an oxygen-free acetonitrile solution containing p-dimethoxybenzene (DMB) and s-trinitrobenzene or chloranil gave a transient absorption spectrum of DMB cation. The decay of the transient absorption spectra follows the second-order reaction kinetics proving that the decay is brought about by the recombination of the anion and the cation after the flash illumination. The formation of the ion-pair may be explained as follows:
    (Remark: Graphics omitted.)
  • Hiroatsu Matsuura, Tatsuo Miyazawa
    1969 Volume 42 Issue 2 Pages 372-378
    Published: 1969
    Released: March 27, 2006
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    Optical and acoustic branches of chain vibrations of polyethylene glycol were treated. The nature of these branches was elucidated on the basis of potential-energy distributions and phase relations. From dispersion curves (frequency versus phase difference), the frequency distribution of chain vibrations was calculated, in order to analyze thermal-neutron scattering spectra. Vibrational assignments of scattering peaks in the region 600–200 cm−1 were made with reference to the frequency distribution peaks and potential-energy distributions calculated for the single chain.
  • Tsutomu Fukuyama, Kozo Kuchitsu, Yonezo Morino
    1969 Volume 42 Issue 2 Pages 379-382
    Published: 1969
    Released: March 27, 2006
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    The average structure of vinylacetylene has been determined by making combined use of the electron-diffraction intensities obtained in the present study and the rotational constants supplied by microwave spectroscopy. The two sorts of data have been found consistent to the uncertainties given below. With the molecular symmetry assumed to be Cs, the following parameters have been obtained in regard to the zero-point average structure: r(C–C)=1.4310±0.0034, r(C=C)=1.3416±0.0042, r(C≡C)=1.2086±0.0028, r(C–H)vinyl=1.087±0.010, r(C–H)ethynyl=1.062±0.018Å, ∠(C=C–C)=123.1±0.5°, ∠(C–C≡C)=177.9±1.2°, ∠(H–C=C)=120.6±1.5°, ∠(C≡C–H)=182.3±3.8°. There seems to be a significant difference between the C–C length of vinylacetylene and that of propynal. The result has been discussed in terms of the bond-order bondlength correlation.
  • Bimal C. Bera, M. M. Chakrabartty
    1969 Volume 42 Issue 2 Pages 383-386
    Published: 1969
    Released: March 27, 2006
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    New selective methods are described for the gravimetric determination of palladium, silver, copper and mercury with 2-mercaptomethylbenzimidazole. In the presence of EDTA or tartrate, palladium, silver and mercruy are determined at pH of 4–5. Copper is determined as the copper(I) complex in the same pH range using cyanide as a reducing and complexing agent. Thermogravimetric studies reveal adequate thermal stability of the complexes. X-Ray studies confirm the identity of the end products in the thermolysis of the copper(I) and copper(II) complexes.
  • Yoshinaga Oka, Toyoaki Kato, Nobuyoshi Sato
    1969 Volume 42 Issue 2 Pages 387-393
    Published: 1969
    Released: March 27, 2006
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    The yields of a number of radioactive nuclei produced by (γ,xnyp) reactions on titanium and vanadium targets have been determined at four different bremsstrahlung maximum energies, 30, 45, 55 and 60 MeV, with the aid of radiochemical methods and gamma-ray spectrometric measurements. The linear electron accelerator of Tohoku University was the bremsstrahlung source. Yields have been expressed as production rates of given radioactive end-products relative to that of the 12C(γ,n)11C process. Over the range of energies investigated, the yield of each nuclide increases with increasing maximum energy. The yield of a reaction with the emission of more than one nucleon appeared to be strongly energy dependent. Reaction paths leading to the formation of each nuclide were investigated. The photoproduction of 47Ca from titanium has been observed.
  • Mutsuo Kodama, Yayoe Tominaga
    1969 Volume 42 Issue 2 Pages 394-399
    Published: 1969
    Released: March 27, 2006
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    D.c. polarographic behavior of copper(II) ion in N-(2-hydroxyethyl)ethylenediamine-N,NN′-triacetate (EDTA-OH) and 2,2′-ehtylenedioxybis[ethyliminodi(acetate)] (GEDTA) solutions was studied systematically. In an EDTA-OH solution, copper (II) ion gave invariably a single well-defined wave corresponding to the following two-electron reduction.
    GuX+nH++Hg+2e\ ightleftarrowsCu(Hg)+HnXn−3
    On the other hand, in a GEDTA solution, two waves were obtained. The height of the first wave, which is reversible in nature, increases with increasing pH of the solution at the expense of the height of the irreversible second wave. From the relation between the half-wave potential and the concentrations of hydrogen ion, GEDTA and acetate ion, determined experimentally, the compositions and the stability constants of copper(II)-GEDTA chelates in solution were determined and the electrode reaction mechanism established:
    (Remark: Graphics omitted.)
  • Masao Sekizaki, Masakazu Tanase, Kazuo Yamasaki
    1969 Volume 42 Issue 2 Pages 399-404
    Published: 1969
    Released: March 27, 2006
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    The 1 : 1 complexes of pyridine-2-carboxamide (piaH) with the bivalent metals, nickel, copper, cobalt, zinc and cadmium, were prepared and their structures determined through measurements of diffuse reflectance spectra, magnetic moments and infrared spectra. In these complexes, MX2-(piaH) (X=halogen), pyridine-2-carboxamide is likely to be coordinated to the metal through N(pyridine) and O(amide) atoms with two halogen atoms in the cis-position.
  • Masaru Kimura
    1969 Volume 42 Issue 2 Pages 404-406
    Published: 1969
    Released: March 27, 2006
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    The kinetics of the substitution reactions of cobalt(II) ions and manganese(II)-ethylene-diaminetetraacetate complexes have been studied in acetate buffer solutions at 25°C and at ionic strength of 0.2. The reaction was treated as to proceed through both hydrated metal ions and monoacetato complexes. The rate constants for six elementary reaction paths, three of which involve hydrated cobalt(II) ions and the others, monoacetatocobalt(II) complexes, were determined. The values obtained indicate that all the reactions proceeding through monoacetatocobalt(II) complexes are about three times faster than the corresponding reactions proceeding through hydrated cobalt(II) ions.
  • Masaru Kimura
    1969 Volume 42 Issue 2 Pages 407-411
    Published: 1969
    Released: March 27, 2006
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    A kinetic study of the substitution reactions of nickel(II) ions and cobalt(II)-nitrilotriacetate complexes in phthalate and in acetate buffer has been carried out using a procedure previously reported. The reaction was made to proceed through both hydrated nickel(II) ions and monophthalatonickel(II) complexes or monoacetatonickel(II) complexes. The rate constants for eight elementary reaction paths, four of which involve the hydrated nickel(II) ions, while the others involve the monophthalatonickel(II) complexes (the monoacetatonickel(II) complexes in the case of the measurements in acetate media), were determined at an ionic strength of 0.2 at 25°C. The values obtained indicate that all the reactions proceeding through the monophthalatonickel(II) complexes are slower than the corresponding reactions proceeding through hydrated nickel(II) ions; however, all the reactions proceeding through monoacetatonickel(II) complexes are faster than the corresponding reactions proceeding through hydrated nickel(II) ions. Thus, the kinetic reactivity is in the order of: NiOAc+>Ni2+>NiPh, where Ph2− indicates a bivalent phthalate anion.
  • S. Ramamoorthy, M. Santappa
    1969 Volume 42 Issue 2 Pages 411-416
    Published: 1969
    Released: March 27, 2006
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    Stability constants of complexes of uranyl ion with various carboxylic acids were determined by the pH titration method at 31°C and μ=0.1 (NaClO4) in the pH range 2.5–3.5. The 1 : 1 and 1 : 2 complexes were formed with crotonic, pyruvic, malonic, and diglycolic acids and only the 1 : 1 complex with formic, propionic, succinic, adipic, maleic, fumaric acids. The effect of ring size and presence of oxygen atom as keto or ether oxygen or that of double bonds in the ligand acids on the stabilities of the corresponding complexes are discussed.
  • Yoneichiro Muto, Michinobu Kato, Hans B. Jonassen, Louis Chopin Cusach ...
    1969 Volume 42 Issue 2 Pages 417-431
    Published: 1969
    Released: March 27, 2006
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    In order to test the substituent effect or the effect of variations in chemical structures on the demagnetization and d–d band shift in dimeric copper(II) halide complexes with pyridine N-oxides and some related ligands, a variety of electron-donating or electron-withdrawing substituents attached in 2-, 3- and 4-positions in the pyridine ring of the ligand were extensively studied. In these dimeric complexes, no correlation was observed between the Hammett’s σ constants and the observed d–d band positions or magnetic moments. However, irrespective of the nature of the substituents, a linear relation was observed to exist between the d–d band positions and the magnetic moments, indicative of a magnetochemical support for the interpretation of the spectrochemical series through the idea of symmetry-restricted covalency. For the monomeric complexes with the same ligands, a linear relation exists between Hammett’s constants and the d–d band positions for each series of the electron-donating and electron-withdrawing substituents. Experimental results indicate that the most important factor determining the non-applicability of Hammett’s Rule in these dimeric complexes is the steric condition of the metal ions which shields them from the influence of other molecules or ions. The larger demagnetization effect of the bromide ion compared to the chloride ion has been interpreted as due to its larger nephelauxetic effect. On the basis of the established structure of the parent compound, two pathways for superexchange interaction have been proposed. The importance of a σ type orbital overlap compared to the π type is discussed.
  • Tatsuya Sekine, Yasuaki Koike, Yuko Hasegawa
    1969 Volume 42 Issue 2 Pages 432-436
    Published: 1969
    Released: March 27, 2006
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    Distribution behavior of lanthanum(III) and actinium(III) at tracer concentrations was studied in metal chelate extraction systems where the organic phase was chloroform containing dibutylphosphate, thenoyltrifluoroacetone (TTA), β-isopropyltropolone or 5,7-dichloroxine. The separation factors for this pair of ions by extraction with these four chelating ligands were determined. The distribution behavior was also studied in the adduct chelate extraction systems where the organic phase was carbon tetrachloride containing mixed ligands, TTA-tributylphosphate (TBP) or TTA-methyl isobutyl ketone (MIBK). The adduct formation constants for actinium-(III)-tris-TTA chelate with these neutral ligands were determined. Results were compared with previous results on the distribution behavior of other trivalent actinide and lanthanide ions in these systems. It was concluded that the separation of lanthanum-actinium was somewhat different from the separation of europium-americium in the same chelate extraction systems. The stabilities of the first adducts with TBP or MIBK of actinium TTA chelate were smaller than those of americium TTA chelate, but the stabilities of the second adducts showed just the reverse order. This tendency in adduct formation is the same as that observed among the lanthanum and europium adduct TTA chelates in previous work. Finally, the use of TTA-TBP mixture was recommended for the extraction of lanthanum(III) or actinium(III) at tracer concentrations based on the fact that the use of these mixed ligands resulted in much better recovery of material and better reproducibility of results than a single chelating ligand.
  • Takanobu Shiokawa, Hiroshi Kudo, Takashi Omori
    1969 Volume 42 Issue 2 Pages 436-439
    Published: 1969
    Released: March 27, 2006
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    The chemical behavior of 144Pr formed by the β–decay of 144Ce in crystals of 144Ce(III)-EDTA complexes has been investigated by means of ion-exchange techniques. The initial yield of 144Pr3+ ion, which reflects the distribution of the 144Pr atoms in the crystal, is independent of the dissolving condition, but is affected by the amount of hydration in the crystal. Abnormal behavior of 144Pr atom has not been found in the ammonium salt. These results suggest that in the solid phase 144Pr3+ or its precursor may be produced as a result of multiple charging of the daughter following electron shake-off and internal conversion of γ-rays.
  • Kiyoshi Matsuda, Reita Tamamushi
    1969 Volume 42 Issue 2 Pages 439-442
    Published: 1969
    Released: March 27, 2006
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    The integral readout technique was applied to the accurate determination of average polarographic currents. The long-term integration of polarographic currents provides a useful method of compensating residual currents and thus of increasing the sensitivity and accuracy of the d. c. polarographic analysis. The analytical utility of the proposed method was tested with cadmium, lead, and zinc ions in chloride solutions; these ions were found to be determined with reasonable accuracy even at concentrations as low as 10−6 M. Depolarizers at concentrations of the order of 10−4 M can be determined accurately in air-saturated solutions. The present method has the considerable merit that its sensitivity is not affected by the degree of reversibility of the electrode reaction. The integral technique was also applied successfully to the compensation of residual currents by the twin-cell system, in which a pair of dropping mercury electrodes is not necessarily synchronized.
  • Yoshisato Tezuka, Tetsuya Ogura, Shinichi Kawaguchi
    1969 Volume 42 Issue 2 Pages 443-446
    Published: 1969
    Released: March 27, 2006
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    The ethanolysis of diketene is accelerated by the addition of sodium tetrachloropalladate(II). Yellow crystals separated in the end of this reaction were identified as di-μ-chlorobis(π-1-ethoxycarbonyl-2-hydroxyallyl)dipalladium(II) on the ground of analytical data, molecular weight and infrared spectrum. The same complex was also prepared directly by the reaction of palladium(II) chloride with ethyl acetoacetate in water.
  • Kazuko Ogino
    1969 Volume 42 Issue 2 Pages 447-452
    Published: 1969
    Released: March 27, 2006
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    Association constants of [Co en3]3+ (en=ethylenediamine) and d- and l-[Co d-pn3]3+ (pn=propylenediamine; d- and l- refer to the sign of optical rotation at sodium D-line) with some anions have been determined spectrophotometrically. Values are as follows: [Co en3]3+·SO42−49, [Co-en3]3+·glycollate ∼5, d-[Co d-pn3]3+·SO42− 70, d-[Co d-pn3]3+·d-tart2− (tart2−=bivalent tartrate anion) 30, d-[Co d-pn3]3+·l-tart2− 28, l-[Co d-pn3]3+·SO42− 43, l-[Co d-pn3]3+·d-tart2− ∼7, l-[Co-d-pn3]3+·l-tart2− ∼16. These association constants are discussed in terms of the microscopic interaction between the ions. The effect of outer-sphere association on the circular dichroism and optical rotatory dispersion is also discussed.
  • Yasuo Nakao, Naoki Nonagase, Akitsugu Nakahara
    1969 Volume 42 Issue 2 Pages 452-456
    Published: 1969
    Released: March 27, 2006
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    Relative stability of sixteen aldehyde- and the corresponding ketone-Schiff base chelates has been investigated in terms of their decomposing temperature and half-wave potential against the reduction of copper(II) at the dropping mercury electrode. The previous conclusion, established for copper(II) tridentate Schiff base complexes, that Schiff base chelates of aldehydes are generally less stable than those of corresponding ketones has been proved to be valid also for copper(II) tetradentate Schiff base complexes if there is no serious steric hindrance in the Schiff base ligand. As a result of this investigation, six new copper(II) chelates were synthesized and characterized.
  • Kôichi Tonosaki, Takayoshi Sakai
    1969 Volume 42 Issue 2 Pages 456-459
    Published: 1969
    Released: March 27, 2006
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    Bromopyrogallol red reacts with thorium(IV) to form a stable complex with an absorption maximum at 645 mμ against a reagent blank. The maximum absorbance is obtained in the pH range of 5.6 to 5.9 when the solution is heated in a boiling water bath for 20 min. The color system obeys Beer’s law in the range 6 to 106 μg of thorium in 25 ml. The molar absorptivity of the complex is calculated to be 5.0×104 at 645 mμ. The sensitivity of the reaction is 0.004 μg thorium per cm2. The complex has the composition 1 to 2 in metal to ligand. The effect of diverse ions on the determination is also examined.
  • Hidetsuru Matsushita, Yasutomo Suzuki
    1969 Volume 42 Issue 2 Pages 460-464
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    A two-dimensional dual-band thin-layer chromatographic procedure for the separation of a mixture containing many polynuclear hydrocarbons is described. A chromatoplate composed of two adsorbent layers, aluminum oxide G and acetylated cellulose, is used in this chromatography. A sample containing various polynuclear hydrocarbons is first developed on an aluminum oxide G layer with n-hexane - ether (19:1, v/v) and then on an acetylated cellulose layer with methanolether-water (4:4:1, v/v). A mixture of 15 polynuclear hydrocarbons was completely separated into its components by this treatment. This method was then applied to the separation of a vacuum-sublimation extract of particulates obtained from Tokyo air. The extract was separated into 69 spots, and it was proved that several hydrocarbons, including benzo(a)pyrene, has been isolated in a pure state.
  • Mitsuo Masai, Etsuro Echigoya, Kiyoshi Morikawa
    1969 Volume 42 Issue 2 Pages 464-469
    Published: 1969
    Released: March 27, 2006
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    A small amount of allyl chloride, 1,1-dichloroethane, or chloroform was added to the reactant in the oxidation of propylene in an inert fluidized-bed reactor. A negative temperature coefficient is observed in the conversion of propylene and in the formation of various products, but not propylene oxide, in the experiments with allyl chloride or 1,1-dichloroethane added. The results of the chloroform-adding experiments show a positive temperature coefficient in the conversion of propylene and in the formation of gaseous products. The results of the work described here are discussed on the basis of the probable reaction scheme. The results of the chloroform-adding experiments support the proposed catalytic effect of the chlorocarbene on the decomposition of acetaldehyde. It is concluded that the negative temperature coefficient is attributable to the apparent inactivity of acetaldehyde (the branching agent) in the high-temperature region in this reaction atmosphere.
  • Teruo Hiraki
    1969 Volume 42 Issue 2 Pages 470-474
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    The reaction of 2-propanol under a silent electric discharge was studied using two kinds of discharge tubes. One was Siemen’s tube, which was used for investigating a silent discharge decomposition of 2-propanol. The other was a special tube that had one side of the walls made of copper or its salts; it was used for studying the effects of the wall on the decomposition. The main liquid products were acetaldehyde, acetone, dl-2-butanol, 2-methyl-2-propanol, 2-methyl-2-butanol, and hydrocarbons. The gaseous products were methane, C2–C4-hydrocarbons, carbon monoxide, carbon dioxide, and hydrogen. These components were obtained in every run, regardless of the type of tube used. However, the distribution of the products varied with the sort of tube. The formation of 2-methyl-2-butanol can be explained by the addition of a 1-hydroxyisopropyl radical with the ethylene produced; the only product formed by adding this radical to ethylene was the one-to-one adduct. By replacing one side of the glassy walls with a wall of a glass-filter-packed copper or its salts, the yield of 2-methyl-2-propanol was increased relatively, and those of 2-methyl-2-butanol and dl-2-pentanol were decreased.
  • Yoshitsugu Sakuda
    1969 Volume 42 Issue 2 Pages 475-478
    Published: 1969
    Released: March 27, 2006
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    The 6,8(9)-p-Menthadien-trans-2,4-diol (I) and 6,8(9)-p-menthadien-cis-2,4-diol (II) were obtained by the oxidation of l-cis-carvyl acetate with selenium dioxide. The hydrogenation of each 6,8(9)-p-menthadien-2,4-diol gave a different pair of p-menthane-2,4-diols, one pair being p-menthane-2,4-diols (III and IV) from trans-2,4-diol (I) and the other pair being p-menthane-2,4-diols (V and VI) from cis-2,4-diol (II). The absolute configurations of the p-menthane-2,4-diols (III, IV, V and VI) were assigned as follows on the basis of the chemical evidence, the IR and NMR data, and the Cotton-effect sign of the oxidation products of these isomers: III, (1S : 2R : 4S); IV, (IR : 2R : 4S); V, (1R : 2R : 4R) and VI, (1S : 2R : 4R)-p-menthane-2,4-diol. The identification of these diastereoisomeric diols III–VI made possible the assignment of a configuration to diols I and II.
  • Tadao Hayakawa, Yoshiyuki Kondo, Hiroyuki Yamamoto, Yukiko Murakami
    1969 Volume 42 Issue 2 Pages 479-482
    Published: 1969
    Released: March 27, 2006
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    Pure crystalline Nω,ω′-dicarbobenzyloxy-L-arginine N-carboxyanhydride hydrochloride was obtained from Nα,ω,ω′-tricarbobenzyloxy-L-arginine and thionyl chloride. It was polymerized to poly-Nω,ω′-dicarbobenzyloxy-L-arginine. This polymer was converted to poly-Nω-carbobenzyloxy-L-arginine by treating it with alcoholic potassium hydroxide; also, both carbobenzyloxy groups of the protected polymer were completely removed into poly-L-arginine by treating them with hydrogen bromide in glacial acetic acid. Several copolymers containing L-arginine residue were also prepared by the copolymerization of the above NCA and the NCAs of other amino acids, such as γ-benzyl-L-glutamate, L-alanine, and Nε-carbobenzyloxy-L-lysine.
  • Nobuo Mori, Yuzuru Asano, Toshiko Irie, Yojiro Tsuzuki
    1969 Volume 42 Issue 2 Pages 482-487
    Published: 1969
    Released: March 27, 2006
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    The infrared hydroxyl and carbonyl stretching absorption spectra of salicylic, mandelic, and α-hydroxyisobutyric acids have been measured in dilute carbon tetrachloride solutions. The spectral data indicate that the first two acids exist exclusively in an internally-bonded conformation, one where the phenolic and the alcoholic hydroxyl groups form a hydrogen bond with the carbonyl oxygen atom of the cis-carboxyl structure, while the last acid takes, apart from such a conformation, another internally-bonded conformation, one where the hydroxyl group of the trans-carboxyl structure interacts with the alcoholic oxygen atom.
  • Nobuo Mori, Yuzuru Asano, Yojiro Tsuzuki
    1969 Volume 42 Issue 2 Pages 488-491
    Published: 1969
    Released: March 27, 2006
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    The infrared OH and C=O stretching spectra of methyl 4- or 5-substituted salicylates have been measured in dilute carbon tetrachloride solutions, and the respective peak-frequencies have been correlated with ordinary Hammett’s σ-constants. The best linear relationship has been established between the γOH and the (σOH−0.38σCOOMe) values and between the γC=O and the (σCOOMe−0.49σOH) values, where σOH and σCOOMe are the σ-constants of a substituent with respect to the OH and the COOMe group respectively. Besides, in other internally-bonded phenol systems, including o-bromophenols, o,o′-dihalophenols, and salicylic acids, the plotting of the OH frequencies against the (σOHAσX) values gave the best linear relationship, where A is a constant depending on the kind of proton acceptor, X. The value of A can be a measure of the electronic effects of the substituent, influencing the bonded OH frequency through X.
  • Takashi Maeda, Masumi Kiyokawa, Kanji Tokuyama
    1969 Volume 42 Issue 2 Pages 492-498
    Published: 1969
    Released: March 27, 2006
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    The ethylidenation of L-sorbose (I) with acetaldehyde dimethylacetal in the presence of an acid was studied. When the reaction was interrupted at the initial stage, an equilibrium mixture of the two possible cyclic acetals, 1,2-O-(III) and 1,3-O-ethylidene-α-L-sorbopyranose (V), was obtained. When the reaction was allowed to proceed for longer periods of time, 1,3:4,6-di-O-ethylidene-β-L-sorbofuranose (IX) was mainly isolated; the transformation of this to two diastereoisomeric 2,3:4,6-di-O-ethylidene-α-L-sorbofuranoses (XV and XVIII) required the use of highly acidic conditions. A pathway of I→(III\ ightleftarrowsV)→IX→(XV+XVIII) was tentatively proposed for the ethylidenation of I.
  • Shigeo Nishimura, Hisashi Yoshino
    1969 Volume 42 Issue 2 Pages 499-501
    Published: 1969
    Released: March 27, 2006
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    Hydrogenation of methoxy- and ethoxyanilines with a ruthenium catalyst was investigated at 80°C under the hydrogen pressure of 80–100 kg/cm2. The amount of hydrogenolysis which occurred during hydrogenation varied with solvent from 35.1% in methanol to 8.5% in t-butyl alcohol in the hydrogenation of p-methoxyaniline. With use of t-butyl alcohol as solvent, good yields of methoxy- and ethoxycyclohexylamines were obtained from corresponding alkoxyanilines. It was shown that the rate of formation of cyclohexylamine increases with increasing polarity of solvent. m-Alkoxyanilines were found to hydrogenolyze more readily than the corresponding ortho or para isomers. For the greater tendency of meta isomers toward hydrogenolysis, an explanation based on the ionic cleavage of the carbon-oxygen bond was suggested.
  • Hideo Endo, Masao Tada, Ken Katagiri
    1969 Volume 42 Issue 2 Pages 502-505
    Published: 1969
    Released: March 27, 2006
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    A number of new piperidinophenazines have been prepared by the reactions of various halogenophenazines and their oxides, including several new compounds, with piperidine. The halogenactivating effect of the oxide groups in 1- or 2-halogenophenazine oxides, which had previously been known, was also observed in the present piperidination. It has been found that 1-chlorophenazine was considerably less reactive than 2-chlorophenazine in the piperidination, that but the 5-oxide group in 1-chlorophenazine-5-oxide enhanced the reactivity of chlorine.
  • Hideo Endo, Masao Tada, Ken Katagiri
    1969 Volume 42 Issue 2 Pages 506-507
    Published: 1969
    Released: March 27, 2006
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    A number of new morpholinophenazines have been prepared by the reactions of various halogenophenazine derivatives with morpholine. It has been found that the replacement of the halogen atom of halogenophenazine-N-oxides with morpholine is accompanied by the removal of the oxide group and that no morpholinophenazine-N-oxides are formed in these reactions.
  • Takeshi Nakai, Hideo Kawaoka, Makoto Okawara
    1969 Volume 42 Issue 2 Pages 508-512
    Published: 1969
    Released: March 27, 2006
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    In order to demonstrate that neighboring-group participation of the N,N-disubstituted dithiocarbamate function is involved in the substitution reaction of poly (vinyl chloride) (PVC) with the dithiocarbamate anion, the rates of reactions of PVC and the copolymer (vinyl chloride-S-vinyl N,N-diethyldithiocarbamate) with SCS-NEt2 were compared under the same conditions. These polymer reactions were undertaken in dimethylformamide or tetrahydrofuran at 45°C. The rate enhancements with the copolymer were observed in both solvents. From these observations, it was concluded that the chloromethylene groups in PVC neighboring the dithiocarbamate function were activated .toward the nucleophile via neighboring-group participation. This is the first time that neighboring-group participation involving the polymer main chain might be observed in the polymer reaction. The difference in reaction mechanism between the polymer reaction and the model reaction was discussed.
  • Etsuo Niki, Yoshio Kamiya, Nobuto Ohta
    1969 Volume 42 Issue 2 Pages 512-520
    Published: 1969
    Released: March 27, 2006
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    The cooxidations of cumene (C) and tetralin (T) and of styrene (S) and tetralin were studied in the presence of azobisisobutyronitrile; the reactivity ratios, r, were obtained as rC=0.21 and rT=5.0 for the cumene-tetralin system at 80°C and as rS=2.7 and rT=0.49 for the styrene-tetralin system at 70°C. A new method for the determination of r values from the rates of cooxidation has been developed. The merits and demerits of several methods for the determination of r values are discussed. In cases where a large curvature, preferably a rate minimum, is obtained by plotting the rates against the reactant compositions, the determination from the rates of cooxidation may be most suitable. In other cases, the use of the copolymerization equation may be preferable by product analyses. The hydroperoxide method may be valid for some systems.
  • Sho Takahashi
    1969 Volume 42 Issue 2 Pages 521-527
    Published: 1969
    Released: March 27, 2006
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    The synthesis of polypeptides with a repeating sequence of glycines and L-alanines, i. e., poly-(L-Ala-Gly-Gly), poly-(L-Ala-L-Ala-Gly), and poly-(L-Ala-L-Ala-L-Ala-Gly), are reported. Polymerization was achieved by a self-condensation of p-nitrophenyl esters of the corresponding tri- or tetrapeptides.
  • Jiro Tsuji, Yoichi Mori
    1969 Volume 42 Issue 2 Pages 527-529
    Published: 1969
    Released: March 27, 2006
    JOURNALS FREE ACCESS
    It was found that cyclopentadienyliron dicarbonyl dimer is an active catalyst for oxo reaction and the characteristic features of the catalysis have been studied.
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