BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 7, Issue 4
Displaying 1-16 of 16 articles from this issue
  • Some informations obtained by mass spectrometry
    Shigeru OHASHI, Yuji TAKAYAMA, Sachiko TAKI, Hiroshi TOYA
    1958 Volume 7 Issue 4 Pages 205-210
    Published: April 05, 1958
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    One of the authors has already published a method of determination of elementary nitrogen by use of strong phosphoric acid-potassium iodide. Although this method showed various merits, it was unutilizable for determination of nitrogen in pyridine ring. In order to elucidate its reason and to find a clue to finding the possibility of its application, mass spectrometry and chemical analysis of a gas collected in the azotometer have been carried out to confirm whether or not the gas is nitrogen. The result indicated that the nitrogen in a pyridine ring can be analysed by heating at about 255°C, but it is nccessary to remove the by-product oxygen. Thus, the gas in the azotometer is found to be a mixture of nitrogen and nitrous oxide and this tendency was the same in the Dumas method.
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  • Infrared spectroscopic analysis in organic chemistry. IV
    Masao YAMAGUCHI
    1958 Volume 7 Issue 4 Pages 210-214
    Published: April 05, 1958
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Characteristic absorption bands of three kinds of five-membered heteroaromatic compounds, namely furans, pyrroles, and thiophenes, have been investigated with the following results.
    νC=H of the furan and the thiophene nuclei appeared in shorter wave ranges (3. 163.21μ in furans and 3. 203.24μ in thiophenes) than νC=H of the benzene ring, and their intensities were fairly strong. νC=C of the furans and the pyrroles showed two absorption bands at almost the same position (6.346.42μ and 6.626.65μ in furans, 6.336.41μ and 6.516.71μ in pyrroles) as in the benzene ring, and considerably longer wave ranges of 6.546.58μ and 7.047.12μ in thiophenes. Their intensities were fairly strong the case of conjugated types, while in nonconjugated types, they showed irregularities, the two bands in the pyrroles being of medium intensity, and those of the furans being considerably weaker in a shorter wave range, while the thiophenes showed two obscure bands in many cases. By selecting a certain wave range for the furans an absonption band (11.311.45μ) could be singled out which was extremely useful in the identification of this nucleus.
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  • Yoshinaga OKA, Shigeki MATSUO
    1958 Volume 7 Issue 4 Pages 215-219
    Published: April 05, 1958
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Iron (III) reacts with tropolone to give green and brownish-red complexes. The green complex is formed in the presence of an excess of iron. When a large excess of tropolone is allowed to react, the brownish-red one is formed. Both complexes can be utilized for the determination of tropolone and iron respectively.
    The green complex shows absorption maxima at 435 and 582 mμ. It is stable over an acidity range from 0.05 to 1 N. The brownish-red one is stable over a pH range from 1.3 to 8.5, and has peaks at 425, 550, and 595 mμ, the first of them being very sharp.
    The composition of the green complex is 1:1, and that of the brownish-red one is considered to be 1:3. Formation constant of the green complex is evaluated to be 1.0×1011.
    Both complexes obey Beer's law, and with them iron and tropolone can be determined up to 3.9 γ/ml and 5.3×10-5 M/l respectively.
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  • Studies on analytical application of onium compounds. XIV
    Mutsuaki SHINAGAWA, Hiroshi MATSUO, Hiroshi OKASHITA
    1958 Volume 7 Issue 4 Pages 219-223
    Published: April 05, 1958
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Tetraphenylstibonium chloride, (C6H5)4SbCl, was synthesized and its polarographic behaviors have been investigated. The polarogram showed a two-step wave with the use of 0.1 N potassium chloride as a supporting electrolyte and a saturated calomel electrode. Its half-wave potentials were -0.72 V and -1.11 V, respectively. The half-wave potential of the first wave was not changed by a change in pH, but that of the second wave was. The electrode reaction of the first wave was found to be controlled by the rate of the diffusion, and there was a proportional relationship between the concentration and wave height when the concentration range was 5.76×10-55.76×10-3 M/l. The relationship between concentration and wave-height of the second wave was similar to that of an isothermal adsorption curve, and showed good agreement with Langmuirs adsorption equation. In the investigation of the reaction of (C6H5)4SbCl and various metal complex ions, those of bismuth, mercury, stibium, and cadmium were tested by amperometric titration. The first two were able to be titrated within an error of ±2% and ±3%, respectively.
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  • Nobuyuki TANAKA, Yasuhiko SAKUMA
    1958 Volume 7 Issue 4 Pages 223-228
    Published: April 05, 1958
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    A semi-convection mercury electrode has been used for an indicator electrode in constant-current potentiometric titrations. Copper (II), lead (II), and cadmium (II), as low as 2×10-5M in concentration, were titrated with disodium ethylenediamine tetraacetate solutions in an acetate buffer of pH 4.2 or 5.2.
    The experimental results indicate that the titration method with the semi-convection mercury electrode has an advantage over that with the conventional dropping mercury electrode when micromolar solutions are titrated, because the former electrode has a greater sensitivity and a smaller charging current than the latter. On the other hand, the titrations with the semi-convection mercury electrode give less accurate and less reproducible results than those with the dropping mercury electrode. Nevertheless, the method was found to be useful in analyses of micromolar solution's.
    It was also confirmed that the titration curves obtained at the semi-convection electrode satisfy the relation given by Tanaka et al. previously,
    C=ia-ir/k V+v/V+cv/V,
    where C represents the concentration of metal ion initially present in the solution (in mole/l), c the concentration of titrants expressed in mole/l, V the initial volume of the solution expressed in ml, v the volume (in ml) required before indicator electrode reaches the given potentials, ia the applied current expressed in microampere, ir the residual current in microampere at the given potentials for the observed end points, and k the sensitivity of the electrode expressed in microampere/mole/l.
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  • Shunji UMEMOTO, Michio ICHIKAWA, Syosuke WATANABE
    1958 Volume 7 Issue 4 Pages 228-231
    Published: April 05, 1958
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    On a filterpaper, potassium ferrocyanide reacts with uranium and develops a brown color. An attempt has been made to determine the uranium content of ores of domestic mines by measuring the light absorbancies of the homogeneous spots made in about the same size on the filterpapers. The method proposed here can be applied to samples containing not much copper or nickel. The procedure is as follows: the sample is treated with aqua regia for 3 hours, the residue is filtered off, and the uranium is precipitated by ammonium hydroxide with other elements including iron. The precipitate is then dissolved in a few ml of conc. nitric acid, and the solution is evaporated to dryness on a water-bath. To this residue, 0.15 ml of conc. nitric acid and 5 ml of aluminum nitrate solution {100 g Al (NO3)3·10 H2O in 100 ml H2O} are added, and the residue is dissolved on the water-bath. The solution is transferred to a 10 ml stoppered measuring cylinder, and the volume of the solution is adjusted to 5 ml with rinsing water. The previous vessel is once more rinsed with 1ml of aluminum nitrate solution, the rinsing solution is poured into the measuring cylinder, and the volume of the solution is adjusted to 6 ml. Two ml of ethyl acetate are added, the uranium is extracted in the ethyl acetate layer, and 1 ml of ethyl acetate containing uranium is washed with 1 ml of aluminum nitrate. Five hundredth ml of this ethyl acetate solution is dropped on the filterpaper. The dried filterpaper is dipped in 2% potassium ferrocyanide solution for 20 sec, and then washed in running water for 10 sec. 2 filterpaper is dried in a dark place. The light absorbancy of the spot thus prepared on the filterpaper is measured by a densitometer. A working curve must be prepared for every determination. Maximum error is within 10 %.
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  • Organic elemental analysis using a microbomb. IV
    Asaji KONDO
    1958 Volume 7 Issue 4 Pages 232-234
    Published: April 05, 1958
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    An organic compound containing chlorine and bromine was decomposed, as described in the preceding report, in a microbomb by the sodium peroxide method. The product was treated as usual and concentrated to 10 ml of a neutral solution ( the concentration of NaNO3 was 2.53.0 M). This was absorbed in Dowex 1-X 10 column (3 cm2×10 cm) previously exchanged with NO3-; and 70ml of 0.5 M NaNO3 was passed through at the rate of 3.0 ml/min to obtain the first effluent containing Cl- only. Then 70 ml of 2 M NaNO3 was passed through to obtain the second effluent containing Br- only; and each of the separated ions was determined by a gravimetric method as the silver salt. The error of analysis was ±0.5% About 10 mg of the sample is required.
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  • Studies on organic reagents for inorganic analysis. III
    Hirotoshi SANO
    1958 Volume 7 Issue 4 Pages 235-238
    Published: April 05, 1958
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    2, 2, 7-Trihydroxy-9-phenylfluorone reacts sensitively with titanium, and the coloration of the product is proportional to the amount of titanium. The sensitivity estimated from the slope of an estimation curve was 20 times as high·as that by the hydrogen peroxide method, twice as high as that by the titanium(III)-alizarin S method, and about the same as that by the conc. sulfuric acidthymol method. Thus, this is one of the most sensitive reactions. The titanium-phenylfluorone complex is difficultly soluble in many solvents. However, in contrast to other metal phenylfluoronates, it has the advantage of dissolving completely and forming no precipitate in a solution of above 0.1 N acid, while it has the disadvantage that the coloration is influenced by the presence of certain ions co-existing in an acid solution. These ions, such as Fe (III), Ge (IV), Sb (III) Sn (IV), and Zr (IV), have exhibited considerable interference.
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  • Fumikazu KAWAMURA, Hiroshi NAMIKI
    1958 Volume 7 Issue 4 Pages 238-242
    Published: April 05, 1958
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    In the quantitative determination of phosphate by the colorimetric method of molybdenum blue with the use of stannous chloride as a reducing agent, the conditions for this reaction have been investigated in detail and the following results were obtained.
    (1) The temperature of reaction affected the intensity of coloration. The error was about 1%/1°C at around 25°C, and the determination became impossible at above 70°C due to the formation of a white precipitate.
    (2) The concentration of acid and the concentration of ammonium molybdate showed considerable influence on the intensity of coloration. Many experiments were carried out on these problems, and the relationships among these three factors are shown by a graph. The results indicated that the optimum concentration of sulfuric acid for quantitative determination was 0.65 N and that of ammonium molybdate was 0.15%.
    (3) A change in the amount of stannous chloride added had practically no effect on the intensity of coloration.
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  • Hiroshi HAMAGUCHI, Nagao IKEDA, Toshi KAWASHIMA
    1958 Volume 7 Issue 4 Pages 243-246
    Published: April 05, 1958
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    A rapid method has been devised for isolating carrier-free yttrium of radiochemically high purity from the parent radioactive strontium by electrodeposition. The radiochemical purity of the yttrium-90 separated is more than 99.9%. The effect of pH, temperature, and voltage on the yield and purity has been examined. The yttrium is deposited on the platinum foil cathode by electrolyzing the 90Sr-90Y solution of pH 56 with 26 volt at room temperature for a desired period of time using a rotating platinum wire anode. It can easily be leached out of the platinum cathode with dilute acids as needed. Ammonium chloride, nitrate, or sulfate can be used as a supporting electrolyte. Addition of chelating agents will effect an improvement in the purity of the isolated yttrium, though with decreased yield
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  • [in Japanese], [in Japanese], [in Japanese], [in Japanese]
    1958 Volume 7 Issue 4 Pages 247-248
    Published: April 05, 1958
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
  • [in Japanese], [in Japanese]
    1958 Volume 7 Issue 4 Pages 248-250
    Published: April 05, 1958
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
  • [in Japanese], [in Japanese]
    1958 Volume 7 Issue 4 Pages 250-252
    Published: April 05, 1958
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
  • [in Japanese]
    1958 Volume 7 Issue 4 Pages 253-259
    Published: April 05, 1958
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
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  • [in Japanese]
    1958 Volume 7 Issue 4 Pages 260-269
    Published: April 05, 1958
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
  • [in Japanese]
    1958 Volume 7 Issue 4 Pages 270-273
    Published: April 05, 1958
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
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