BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 22, Issue 4
Displaying 1-21 of 21 articles from this issue
  • Takao TSUDA, Daido ISHII
    1973 Volume 22 Issue 4 Pages 379-383
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    A new collective method by using the simultaneous condensation of a sample and an organic vapor which was fed into a carrier gas from a GC separation column was proposed in our former reports. By using this method the combination of GC-IR or GC-fraction colletor was also attempted.
    The present paper describes a fundamental study of the simultaneous condensation of a solvent vapor and a sample vapor in a small condenser. As an example of the gas mixture of a carrier gas, a sample vapor and a solvent vapor, a mixture of nitrogen, benzene and toluene was used. The gas mixture which contained the three components at a constant ratio was led into a condenser with a vertical cold tube of 120 mm in length and 4 mm in inner diameter. The vapors in the gas mixture were condensed on the wall of the cold tube, and the condensates formed a thin liquid layer.
    If the gas mixture stays sufficiently long in the condenser, the partial pressure of the condensed component in the gas phase will be equal to the vapor pressure in equilibrium, Po. When the mixture stays for a shorter time, the partial pressure in the condenser, Pobs, will be higher than Po. The degree of attainment of the vapor-liquid equilibrium in the condenser is conveniently expressed by the deviation factor, F, as defined by Pobs=F × Po.
    The flow rates of gas mixture at the inlet and at the outlet of the condenser were measured. The rate of the condensation was measured by weight. The compositions of the gas mixtures and the condensates were analyzed by GC, and vapor pressures, Pobs, were calculated. The time of stay of the mixture in the cold tube of the condenser was calculated by dividing the volume of the cold tube by the flow rate of the mixture at the outlet.
    The longer the time of stay, the smaller was the deviation factor. For a minor component of the mixture the vapor-liquid equilibrium was established in a surprisingly short time, about 1.5 sec. But when the time of stay was less than 1.0 sec, F became steeply larger.
    When the flow rate of vapors at the inlet was varied from 9 to 115 ml/min and the flow rate of nitrogen kept constant at 26 ml/min, the values of the deviation factors of benzene and toluene were constant. This fact suggests that the thickness of the condensate affected the values of F very little. It was easy to collect a minor component with 80% recovery.
    These results may be applied to the collective method by using the simultaneous condensation of a solvent vapor and a sample in GC effluent.
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  • Tomoo TAKAHARI, Yoshihiro YAMAMOTO, Mamoru NAKAMURA
    1973 Volume 22 Issue 4 Pages 383-389
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    The determination of 0.005 to 0.1% of cerium in stainless steel with a spectrophotometric method was described.
    Absorption spectrum of cerium(IV) (600 μg/50 ml) in sulfuric acid solution was shown in Fig. 1. The absorbance of cerium(IV) was maximum at 320 nm. At this wave length, iron, manganese, chromium, molybdenum, vanadium, and niobium interfered with the measurement of cerium(IV), but the absorbance of nickel, cobalt tungsten, titanium, and calcium could be neglected.
    The conditions for the oxidation cerium(III) to cerium (IV) were studied. The larger and smaller amounts of sulfuric acid decreased the absorbance of cerium (I V) (Fig. 4). The effects of silver nitrate and ammonium persulfate in the cerium (I V)-sulfuric acid solution were shown in Fig. 5 and Fig. 6. Fig. 5 showed that the absorbance of cerium (IV) increased slightly with the amounts of silver nitrate.
    In order to remove the interfering elements and to obtain a higher recovery of cerium(III), co-precipitation technique was employed in the present method. Cerium fluoride was co-precipitated with a large amounts of calcium fluoride from perchloric acid solution. The efficiency of the co-precipitation was shown in Table I. Calcium fluoride increased the recovery of cerium(III) from 6080% to 95100%. However, the correct values of cerium were not obtained in the presence of the interfering elements (Table II), and it was necessary to remove large amounts of iron, chromium, manganese, nickel, vanadium, and niobium. For this purpose the solution was treated with hydrogen peroxide and then electrolyzed with mercury cathode.
    The proposed procedure was as follows. Two grams of the sample is decomposed with 20 ml of aqua regia, 20 ml of perchloric acid is added to the solution, then the mixture is evaporated until the white fume evolves. The residue is dissolved in water, and a small amount of hydrogen peroxide is added to reduce iron etc. After filtration, the solution is electrolyzed with mercury cathode for about 1 hour. The electrolyzed solution is evaporated to about 50 ml, then 15 ml of perchloric acid, 20 ml of hydrofluoric acid(47%), 4 ml of calcium chloride solution (0.28%), and filter paper pulp are added to the solution, and it is diluted to 100 ml with water. The precipitate of cerium fluoride and calcium fluoride are digested on a water bath for about 20 minutes. The precipitate is collected and is ignited in a platinum crucible. The residue is dissolved in 3 ml of sulfuric acid (18 N) and 1 ml of hydrogen peroxide (15%). Cerium(III) is oxidized to cerium(IV) by adding 1 ml of silver nitrate solution (0.12%) and 0.2 g of ammonium persulfate. Cerium(IV) is determined by measuring the absorbance at 320 nm.
    The time required for the analysis is about 4 hours/ sample.
    The elements commonly contained in stainless steel, except large amounts of niobium, did not interfer.
    Good accuracy and reproducibility were obtained as shown in Table III and Table IV.
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  • Studies on relationships between thin-layer chromatography and column chromatography. V.
    Masao SUZUKI, Shoji TAKITANI
    1973 Volume 22 Issue 4 Pages 389-393
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    The relations between the discontinuous gradient front and the composition of polar and non-polar solvents in two-component solvent systems in thin-layer (TLC) and dry column chromatography (DCC) have been investigated.
    For the experiments with TLC and DCC, silica gel and mixtures of the following non-polar and polar solvents were used. Non-polar solvents : benzene, cyclohexane and carbon tetrachloride. Polar solvents : alcohols (methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, 2-butanol, 2methyl-1-propanol and 3-methyl-1-butanol), carboxylic acids (acetic acid, propionic acid and butylic acid), ketones (acetone, methylethyl ketone, methylpropyl ketone, methylisopropyl ketone and methylisobutyl ketone), esters (methyl acetate, ethyl acetate, propyl acetate and butyl acetate) and bases (diethylamine, triethylamine, tributylamine and pyridine). In the TLC, a BN-chamber was used as the developing chamber, and the running distance was 12 cm from the lower side of the layer and in the DCC, a column of inner diameter 1 cm and length 12 cm was used. The, β-front formed by chromatographic demixing was detected by the fluorescence under ultra-violet ray (3600 Å) and color of the components (e. g. pigments, and 2, 4-dinitrophenyl derivatives of amines and amino acids) concentrated on the β-front.
    In both TLC and DCC, the linear relationship based on the adsorption isotherm of Freundlich was observed between the migration rate of the demixing line (K β value) and the concentration (mole percent) of the polar component. The range of the concentration in which this relationship hold was about 5 30 mole percent except for the following solvent systems (Fig. 15) : tributylamine systems, propyl acetate systems and butyl acetate systems (120 mole percent) ; acetic acid-cyclohexane or carbon tetrachloride system and methanol systems (2060 mole percent). The following tendencies with regard to K β values were found within the above mentioned concentration range if the concentrations were the same. The K β values of normal- and iso-alcohol systems were nearly the same (Table I). The K β values in most of the systems which contained the same polar components decreased in the order of benzene systems, carbon tetrachloride systems and cyclohexane systems (Table II). It was also found that the K β values in each series of non-polar solvent systems which contained those solvents having the same functional group, increased with the increase in the molecular weight of the polar solvent (Fig. 1, 2, 4, 5).
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  • Studies of relationships between thin-layer chromatography and column chromatography. VI
    Masao SUZUKI, Shoji TAKITANI
    1973 Volume 22 Issue 4 Pages 394-398
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Those factors affecting the magnitude of the values of K β and K γ which indicate the migration rate of the demixing line of thin-layer (TLC) and dry column chromatography (DCC) have been investigated.
    The experiments with TLC and DCC were carried out by using the same adsorbents and developers : the results were compared when the adsorbent was silica gel, alumina, and cellulose powder. Developers used were diisopropyl ether-acetic acid [diisopropyl ether system: (A) 100 : 2.13, (B) various mole ratio], benzene-ethanol (benzene system, 100 : 16.42), water saturated 2-butanol, and chloroform- 1 -butanol-diethylamine [chloroform system: (A) 43 : 6 : 1, (B) 35 : 14 : 1]. In the experiments with TLC, samples (pigments, and 2, 4-dinitrophenyl derivatives of amines and amino acids) were spotted on a site of 2 cm from the lower end of the layer, the developing chamber used was, in most cases, the BN-chamber, and the running distance was 10 cm from the spotting site. The DCC was examined by using a column of inner diameter 1 cm and length 12 cm. The front was detected by the fluorescence under ultra-violet ray (3600 Å) and color of components concentrated on the front. As the factors affecting the values of Kβ and K γr on the silica gel layer, the temperature for development, the thickness of the layer (0.1250.75 mm), the distance of development (015 cm), the activity of the adsorbent (as relative humidity), and the vapor of the developer were studied.
    With regards the adsorbents, the Kβ value in the diisopropyl ether system (A) increased in the order of alumina, silica gel and cellulose powder. The slope of the straight line of alumina which can be related with the adsorption isotherm of Freundlich was larger than that of silica gel in the diisopropyl ether system (B) (Fig. 1). The Kβ value in the diisopropyl ether system (A) was not affected by the thickness of layer (Table I). Nearly no effect of the temperature (728°C) on the Kβ and Kγ values was observed in the diisopropyl ether system (A) and in the chloroform system (A) (Table II). However by increasing temperature (1030°C), the Rf value of erythrosine and phloxine B became higher, and the value of ponseau SX and indigo carmine became lower in the water saturated 2-butanol (Table III). The Kβ and K γ values were not affected by the running distance when it is in the range about 13 cm from 5 cm, but they were affected when the running distance is less than 5 cm in the benzene system and in the chloroform system (A) (Fig. 2). When the vapor of the developer was saturated, the Kβ and K γ values became lower in the diisopropyl ether system (A) and in the chloroform system (B), and when the amount of the adsorbed vapor was kept constant, the Kβ and K γ values were nearly constant (Fig. 3, 4). The K β and K γvalues were affected by the activity of the adsorbent in the diisopropyl ether system (A) and in the chloroform system (A) (Table IV), but when the vapor of the developer was saturated, this effect could be decreased (Table V).
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  • Shukichi OCHIAI, Yuji HIROTA, Yoshihiro KUDO, Shin-ichi SASAKI
    1973 Volume 22 Issue 4 Pages 399-404
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    The automated chemical structure analysis of organic compounds has attracted much recent interest. In this paper, the identification of monoalkenes by a computer aided-13C NMR spectrometry is reported as a link of our work op automated analysis. The computation for the identification of monoalkenes is carried out along the flowdiagram shown in Fig. 1 by feeding the molecular formula, the 1H NMR spectrum, and the complete proton decoupling 13C NMR spectrum of a certain sample of monoalkene as input. First, all probable structural and geometric isomers are constructed based on the molecular formula and the components (Tables II and III) designated by the 1H NMR analysis. Then the chemical shift of each carbon in every structure is computed by using both the 13C-chemical shift prediction parameters of Lindeman and Adams for alkanes and our correction parameters for α-, γ- and trigonal carbons of alkenes (Table IV, V and VI). Finally, the structure whose predicted spectrum is consistent with that of the sample within the limit of ± 5 ppm is typed out as the most likely candidate.
    The structure identification of an unknown sample whose 13C NMR spectrum is 180.10, 180.00, 171.10, 164.30, 69.70 and 62.80 is explained as an example. The components, CH=, C, CH, CH2, CH3, DCH3, and DRH are designated for this sample by the 1H NMR analysis (Tables VII and VIII). Here, DCH3 and DRH express C=CCH3 and the number of hydrogens attached to α-carbon of olefinic linkage, respectively. Then four probable structures, STRUCTURE(1)(4), are constructed based on the molecular formula, C6H12, and these components. The predicted spectra for these four structures by an aid of both Lindeman'sparameters and the parameters of Tables IV, V and VI, are as follows:
    STRUCTURE (1)
    5 CH3 178.94-3 CH2 172.95-1CH 61.95=2 CH 61.95-4 CH2 172.95-6 CH3 178.94
    STRUCTURE (2)
    5 CH3 178.94-3CH2 167.45-1 C H 61.25=H C 2 61.25-4 CH2 167.45-6 CH3 178.94
    STRUCTURE (3)
    6 CH3179.94-4 CH2 170.15-3 CH2 164.05-1 C H 61.95=2 C H 69.75-5 CH3 181.14
    STRUCTURE (4)
    6 CH3 179.94-4 CH2 170.15-3 CH2 158.35-1 C H 61.25=H C 2 69.05-5 CH3 175.94
    By comparing the predicted spectra of STRUCTURE, (1)(4) with the observed spectrum, it can be suggested that the STRUCTURE (3), cis-hexene-2, is the most plausible structure for this sample.
    The above-mentioned computation system has been applied to more than twenty monoalkenes, and all the results obtained are satisfactory(Table IX).
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  • Kanamycin A, Kanamycin B and Neomycin B
    Takeshi MURATA, Seiji TAKAHASHI, Tsunezo TAKEDA
    1973 Volume 22 Issue 4 Pages 405-410
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Trimethylsilyl derivatives (TMS) of Kanamycin A, Kanamycin B and Neomycin B were analysed by a GC-MS combined system. As the trimethyl silylation reagent, bis (trifluorosilyl) acetoamide (BSTFA) was used instead of tri-sil Z and N-trimethyl-silyldiethyl-amine.
    Glass column 1m×3mmφ was packed with 1% OV-1 on silanized chromosorb W 80100 mesh. Because of the high operating temperature and to eliminate background peaks on mass spectra, the OV-1 column was conditioned approximately 5 days. Chromatogram of samples run at 250°C to 290°C (2°C/ min) of programed temperature. As the molecular ion of fully silylated samples were beyond the optimum capability of the LKB 9000 at 3.5kV of accelerating voltage, we used the 1.75 kV accelerating voltage. The mass spectra of the derivatives of Kanamycin A, Kanamycin B and Neomycin B were exhibited as minute molecular ion peaks at m/e 1276, m/e 1275 and m/e 1550. This means that all active hydrogens on both hydroxy and amine groups in Kanamycin A, and Kanamycin B and Neomycin B were completely silylated.
    Fig. 1 shows the chromatogram of TMS samples. Fig. 2, 3 and 7 show the mass spectra of them and Fig. 5, 6 and 9 show the fragmentation schemes. The mass spectra of Kanamycin A exhibited strong intensities at m/e 810, m/e 723, m/e 450, m/e 360 and m/e 342 and Kanamycin B at m/e 810, m/e 809, m/e 722, m/e 450, m/e 449, m/e 360 and m/e 342. The difference of mass fragments of Kanamycin A and B appeared at the m/e 810, m/e 809, m/e 723, m/e 722, m/e 450 and m/e 449. This means that the difference of the -OTMS and the -NHTMS in Kanosamine ring is just one mass unit. The mass spectrum of Neomycin B exhibited strong intensities at m/e 1084, m/e 1010, m/e 741, m/e 725, m/e 449, m/e 377 and m/e 344. The absence of m/e 810 fragment ion (A-O-B.) is very interesting.
    This method is a reliable technique for identifing the impurities and metabolites of antibiotics.
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  • Tomihito KAMBARA, Masamitsu KATAOKA, Koichi SAITOH
    1973 Volume 22 Issue 4 Pages 411-414
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    In AC polarography many surface-active substances show nonfaradaic waves, which are caused by the adsorption-desorption process of the surfactant at the electrode surface. Breyer school has given the name of tensammetric peak to this type of wave and pointed out that the tensammetric peak height obeys the Langmuir adsorption isotherm, shown by eqn.(1), where
    a=amount of adsorbed substance per unit area of electrode surface,
    Z=the maximum number of adsorption sites per unit area,
    ω=adsorption coefficient,
    C=concentration of surfactant in the bulk of solution.
    If the tensammetric peak height ip is proportional to the amount of adsorbed substance a, as Breyer states, then the reciprocal of peak height plotted against the reciprocal of concentration should give a straight line, as eqn. (2) shows.
    On the other hand, upon investigating the concentration dependence of the tensammetric peak potential, Senda and Tachi report that ip plotted against log C shows a roughly linear relationship.
    Employing the nine species of surface-active substance, as tabulated in Table I, the concentration dependence of the tensammetric peak height is measured. The concentration range is so chosen that the peak height dose not exceed 500 MΩ-1; otherwise the effect of circuit resistance is not negligible. In general, a surfactant shows two peaks, namely, the peak at a potential more positive than the electrocapillary maximum potential ip+ and the peak at a more negative potential ip-. In the present investigation, the peak height of ip+ is measured with exception of benzyl alcohol with which both ip+ and ip- are measured.
    The method of linear regression is applied to the 1/ip vs. 1/C and the ip vs. log C plots, and the corresponding two correlation coefficients r1 and r2 are evaluated. The difference between r1 and r2 is tested according to the method given in the review of Doerffel by means of eqn. (3). As shown in Figs. 2, 3, 4 and 5, and also in Table I, the linear relationship between 1/ip and 1/C holds, in general, much better than that between ip and log C does.
    In the plot of 1/ip vs. 1/C, however, with several surface-active substances, the straight line crosses the ordinate at a negative value of 1/ip, as illustrated in Figs. 2 and 4. If 1/C tends to zero, 1/ip should show a positive value on the basis of Langmuir adsorption isotherm. This contradiction remains theoretically unsolved.
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  • Itsuhiko MORI, Noriko MOTOHASHI
    1973 Volume 22 Issue 4 Pages 415-420
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Hg2+, Pb2+, Cd2+, Cu2+ and Bi3+, i.e., hazardous heavy metal ions, were rapidly separated from each other by electrophoresis and determined quantitatively by colorimetry.
    The suitable condition for the electrophoretic separation was found by analyzing pH-migration mobility curves (Figs. 1, 2, 3) obtained by the multicell-electrophoresis.
    Cellulose acetate(2 cm×11 cm strips) and “Cellogel” (2.5 cm×15 cm strips) were used as supporting material.
    As electrolyte, sodium citrate, lactic acid and α-hydroxyisobutyric acid (α-HIBA), each at 0.1M, were examined, and pH was adjusted to 18 with 0.1 M HCl and 0.1 M NaOH.
    At 4 cm from the strip-end(anodic side) 0.5 μl of sample solution(2 mg/ml) was spotted.
    The migration rates(shown in Figs. 1, 2, 3) in each solution at different values of pH on the cellulose acetate strip were obtained by applying the electric field of 300 V/11 cm for 5 min. Good separation was obtained in 0.1 M α-HIBA solution of pH 2.3 as shown in Fig 3.
    For the concentrations of α-HIBA ranging from 0.2 M to 1.0 M, the higher the concentration the less was the migration mobility, and the narrower and clearer were the electrophoretic spots except for the solutions of 0.8 and 1.0 M, since in such solutions the suporting material, cellulose acetate, shrunk by being electrically heated too much. In the solutions more dilute than 0.2 M the separated spots became not clear due to the diffusion. Therefore, 0.4 M α-HIBA solution (pH 2.2) was used.
    For quantitative determination, “Cellogel” was used as supporting material, instead of cellulose acetate, because of its pure quality and little affinity to the samples.
    One microliter of a mixture of the five metal ions was spotted at 1.5 cm from the strip-end (anodic side). Migration was carried out for 10 min under the electric field of 800 V/15 cm.
    As developing color reagents, 0.01 g/100 ml dithizonecarbontetrachloride and ammonium vapour were used, and after being dried the metal-ionogram was cut into five strip pieces. Ten milliliter of 10 g/100 ml NaOH solution was added to the Cd strip, and 10 ml of 10 g/100 ml ammonium citrate solution of pH 10 to the strips of Pb, Bi or Hg, respectively. Two milliliter of 10 g/100 ml ammonium citrate solution of pH 10 and 10 ml of water was added to the Cu strip. Each strip was shaken with the solution for 10 min. The pH of each solution was adjusted before the extraction by adding hydrochloric acid (1 : 1); for Pb and Cu to pH 9, for Hg to pH 4.8 (solutions of Cd and Bi were left unadjusted).
    The metals were extracted from the solution with dithizone-carbontetrachloride, except copper, which was extracted with sodium diethyldithiocarbamate-carbontetrachloride. The absorbances of the organic phases were measured at 518 nm for Cd and Pb, at 436 nm for Cu, and at 490 nm for Bi and Hg.
    The experimental error was within 5%. The minimum limits of determination were 0.5 μg for Bi, 1.0 μg for Cd and Hg, while 1.5 μg for Pb and Cu.
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  • Minoru TANAKA, Toshiyuki SHONO
    1973 Volume 22 Issue 4 Pages 420-424
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    An analytical method for determining the composition of polystyrene-modified poly(2, 6-dimethyl-1, 4-phenylene ether) was investigated by means of curie point pyrolysis gas chromatography.
    Using pure polystyrene and poly(2, 6-dimethyl-1, 4-phenylene ether) prepared by the well established method, the dependence of the pyrogram on the pyrolysis temperature and heating period was investigated. Among temperatures studied the optimum one was 590°C considering the simplicity of the pyrogram and the amount of the polymer pyrolysed. The pattern of the pyrogram was a function of the heating period, and then the period was fixed for 4 seconds.
    The ratio of the peak area of styrene/2, 6-dimethyl-phenol, (y), on the pyrogram under these conditions, i. e., at 590°C for 4 sec, was plotted against the weight ratio of polystyrene/poly(2, 6-dimethyl-1, 4-phenylene ether), (x), within the range of 30/7070/30. By means of the method of least squares in the regression analysis it was found that the regression line of y on x was y=4.794x+0.150 and that the error variance, Vyx, was 0.084. Linear relationships were also obtained between the ratios of styrene/o-cresol, styrene/2, 4-dimethylphenol, and styrene/2, 4, 6-trimethylphenol peak areas and the weight ratio of polystyrene/poly (2, 6-dimethyl-1, 4-phenylene ether).
    In practice it is necessary to investigate the effects of the additives and molecular weight of polymers blended on the pyrolysis pattern. It has been reported in the case of polystyrene with molecular weight higher than 20000 that the yield of styrene on the pyrogram is nearly constant under the same conditions. In this paper two kinds of pure poly (2, 6-dimethyl-1, 4-phenylene ether), i.e., ηinh=0.63 and 1.38 in which range commercial ones have their inherent viscosities, were chosen and blended with the same polystyrene (50/50 weight ratio). Differences in the ratios of the peak area were 5 per cent at most in these two cases. On the other hand, the additives showed differences above 10 per cent. It was found possible to determine the composition of polystyrene-modified poly(2, 6-dimethyl-1, 4-phenylene ether), the effect of the additives being eliminated and a gas chromatograph being operated continuously to minimize the variation from the elaspe of time.
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  • Hitoshi SATOH, Yoshiro ASAKURA, Kazuomi KAGAMI, Masayuki KAMATA
    1973 Volume 22 Issue 4 Pages 424-431
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    This paper describes the results of a study on the necessary amounts of plutonium in order to make an accurate determination of isotopic composition of plutonium by mass spectrometry.
    We made an L-type glove box and a sample-loading apparatus (for trial). The glove box is used to exchange the filament assembly and to set up or remove a vacuum lock of the mass spectrometer. The sample-loading apparatus is used to load a sample solution onto the filament in the glove box. A Nuclide Analysis Associates 12-90-SU mass spectrometer was connected with the glove box.
    The glove box has two pair gloves and one port. These gloves and the port are used to exchange the filament assembly, to set up or remove the vacuum lock system, and to carry in or out the materials.
    The sample-loading apparatus is used to deposit the sample solution on one of the side filaments of the assembly, and about 10 μl solution can be treated. A capillary type loading-pipet is drawn from glass tubing which is 5 mm in diameter. The pipet is fixed by a holder in such a way that it can be freely moved up and down, right and left, and around the center. A filament assembly mounting can also be freely moved toward and backward. The most suitable contact angle between the surface of the firament and the outlet of the pipet is 45°. For drying and converting the sample to oxide, the mounting is connected to an electrical lead from D. C. power supply, which can be adjusted from 0 to 5 amp. currents, at an output voltage 3 volts.
    A portion of plutonium nitrate solution is loaded onto a filament with the sample-loading apparatus. A current applied to the filament was set at about 1 amp. About 10 μl of the solution was automatically deposited on the filament from a small pipet under this condition, and was evaporated to dryness. After the evaporation, the filament current was increased to 2.0 to 2.2 amp. in order to decompose plutonium nitrate to oxide, and then the filament assembly was set up into the ion source by using the vacuum lock system. All the above procedures were carried out in the glove box.
    The plutonium sample was analyzed by surface ionization method under the following conditions.
    analytical ion Pu+
    measuring peak numbers 21 pairs filament currents 3A (sample filament)
    4A (ionization filament)
    quantity of plutonium 0.2μg resolving power 500 M/e
    accelerating voltage 10 kV
    The suitable amount of plutonium was 0.2μg under the above conditions. Where, PuO+ and Pu2O+ peak are lower than that of Pu+; the Pu+ peak was 1000 times as high as peaks of other Pu ion, and it was very stable. A mixed solution which consists of a 10 : 1 mixture of uranium and plutonium could be analyzed without any trouble.
    The precision of the results under the above conditions was as follows;
    atomic % of plutonium isotope precision (relative)
    8090% ±0.1±0.2%
    515% ±0.2±0.4%
    15% ±0.4±0.6%
    0.11% ±0.6±1.0%
    smaller than 0.1% ±1± 5%
    The limit of detection for the isotopic abundance is 0.01% and samples in which the abandance is greater than this can be measured by the present method.
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  • Study of micro-analysis by EDTA masking-coprecipitation method. VI
    Harunc OKOCHI, Emiko SUDO
    1973 Volume 22 Issue 4 Pages 431-437
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    “EDTA masking-coprecipitation method” is a separation method in which a sample element and interfering ones are masked with EDTA and analysing trace elements are coprecipitated as hydroxides with a collector. This method is applicable to many metallic samples and excellent in simplicity, quickness and ease of subsequent treatments. This will be useful as an analytical method for trace elements in metals by using it together with atomic absorption, s. w. polarography and so on.
    The similar separation methods will be able to be developed by changing the masking agent and the precipitant or by using more than two chelating agents together.
    The theoretical consideration of EDTA masking-coprecipitation method has been performed. An equation for the pH-shift for hydroxides precipitation in the presence of EDTA is derived from the equation of equilibrium of the chelate formation and that of solubility product. The measures for the selection of analysing trace elements, matrix ones and collectors are given by this calculations.
    This time, bismuth(III) and iron(III) have been selected as analysing trace elements, lead as the matrix element and magnesium as the collector. Various analytical conditions were examined and EDTA masking-coprecipitation of bismuth and iron was established as follows.
    The sample solutions are prepared by dissolving 00.5g of lead sample in 5ml of nitric acid and water and transferred to a 200ml centrifuge tube. 1ml of magnesium solution(10mglml) and 010mlof 10% EDTA which is slightly in excess of that equivalent to the sample taken are added. The volume is made up to about 100ml with water and 4F sodium hydroxide is added until the precipitating point and 23ml in excess. The solution is centrifuged at about 2700 rpm for 5 minutes and the precipitate is washed once with 100 ml of 0.1 F sodium hydroxide.
    In addition, in the case of bismuth(III) coprecipitation, the sample taken is 0.10.5 g, magnesium solution is 3ml and 10% EDTA is 210 ml.
    Determination method of bismuth is s. w. polarographic one with 1N hydrochloric acid supporting electrolyte and that of iron is ο-phenanthroline extraction spectrophotometric method.
    In the absence of the matrix element, the percentage of coprecipitation of bismuth decreases. This effect is explained by the facts that bismuth has the tendency of precipitating as a basic salt and that the possibility of forming colloidal precipitate.
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  • Chushiro YONEZAWA, Nori TAMURA, Hiroshi ONISHI
    1973 Volume 22 Issue 4 Pages 437-443
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    Extraction-chromatographic separation of 182Ta from 95Zr, 95Nb, 51Cr, and 60Co was performed using methyl isobutyl ketone (MIBK) sorbed on polytrifluoromonochloroethylene (Daiflon) particles as a stationary phase and 1N hydrofluoric and 2N hydrochloric acid as a mobile phase. The separation method was used for the determination of tantalum in zirconium, Zircaloy, and nickel-base alloy by neutron activation using 182Ta ( T1/2=115.1 days) produced by the reaction 181Ta(n, γ) 182Ta.
    The procedure is as follows : Samples (550 mg) together with standard solutions (Ta0.55μg, 0.0050.1 μg) were irradiated in JRR-2 at a thermal neutron flux of about 7×1013 n/cm2· sec for 20 min or at a flux of 2×1013 for 290 hr. The samples irradiated were cooled for about 30 days. Zirconium and Zircaloy were dissolved in 1N hydrofluoric acid- 2N hydrochloric acid. The nickel-base alloy was dissolved in a mixture of nitric and hydrochloric acids containing a few drops of hydrofluoric acid. The solution of zirconium, Zircaloy, or nickel-base alloy was adjusted to 1 N hydrofluoric acid- 2 N hydrochloric acid solution saturated with MIBK. Daiflon which sorbed MIBK was packed in a polyethylene column (Fig. 1), and the column was conditioned. The sample solution was poured into the column. The column was washed with 1 N hydrofluoric acid-2 N hydrochloric acid saturated with MIBK. Tantalum was retained on the column, but zirconium, niobium, chromium, and cobalt were not. Tantalum was eluted with 30 ml of hydrogen peroxide solution (30% H2O2 1+20). The effluent was evaporated to about 3 ml and transferred to a polyethylene vial, and its volume was adjusted to 5 ml with 1 N hydrofluoric acid-2N hydrochloric acid. Counting was made with a 3×3 inch NaI (Tl) detector and a 400-channel pulse-height analyzer. The 1.05 to 1.55 MeV gamma rays of 182Ta were used for the determination. The standard solutions were treated in the same way as the samples.
    The recoveries of 182Ta were more than 97%, and no correction for chemical yield was necessary. Retention of other nuclides on the column is shown in Table II. Only cerium was appreciably retained. Nuclides produced from zirconium, Zircaloy, and nickel-base alloy did not interfere with the determination of tantalum. In the presence of 0.4 m mole of oxalic acid, 1 m mole of sulfate, or nitrate, 182Ta was quantitatively recovered. Tantalum in standard zirconium, Zircaloy, and nickel-base alloys was determined by using the above-mentioned procedure, and satisfactory results were obtained.
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  • Shigeru IGARASHI
    1973 Volume 22 Issue 4 Pages 444-446
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    It is found out that an addition of not only potassium permanganate, phosphoric acid, but also propionaldehyde accelerates more oxidation of methanol to formaldehyde.
    By using this fact the following procedure of the spectrophotometric determination of methanol is proposed.
    Oxidize 1ml of the test solution containing 115 μg of methanol by adding 0.2 ml of 0.3 v/v% propionaldehyde solution, 0.4 ml of potassium permanganate solution which is prepared by dissolving 1.5 g of the salt in 30 ml of water and 7.5 ml of 85% phosphoric acid, and by diluting the mixture to 50 ml. Swirl the mixture, and keep it at the room temperature for 5 minutes. Reduce excess permanganate by adding 0.2 ml of 0.2 g/ml sodium sulfite solution. Swirl the mixture, and add 0.3 ml of 0.02 g/ml aqueous chromotropic acid solution. Slowly add 4 ml of 75 v/v% sulfuric acid. Heat the mixture at 8085 °C for 10 minutes with occasional swirling. After cooling to the room temperature, measure the absorbance at 575 nm against the reagent blank obtained by the same procedure.
    The improved method has higher sensitivity in comparison with the common method, and the calibration curve follows Beer's law over the range of 115 μg/ ml of methanol.
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  • Shigeru IGARASHI
    1973 Volume 22 Issue 4 Pages 446-448
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    A sample of vapor of methyl ester is passed at a rate of 0.5 l/min through a midget impinger (with fritted glass beads attached to the tip of bubbler) containing 20ml of 0.5N sodium hydroxide solution. The solution is allowed to stand for 20 minutes or longer at room temperature until the ester is hydrolyzed to methanol.
    The recommended analytical procedure is as follows. Acidify a 20 ml portion of the 0.5 M sodium hydroxide solution containing 20300μg of methyl ester by adding 2ml of 2.7M sulfuric acid. Swirl, add 1ml of 0.01g/ml potassium permanganate solution and 2ml of 0.3% (by volume) propionaldehyde solution. Swirl, keep the mixture at room temperature for 10 minutes. Reduce the excess oxidizing reagent by adding 1 ml of 0.02g/ml sodium sulfite solution. Swirl, add 2ml of p-rosaniline hydrochloride solution (dissolve 0.16g of the reagent completely in 24ml of conc. hydrochloric acid, and dilute to 100 ml) and 1ml of 2.7 M sulfuric acid. Swirl, and let stand for 30 minutes at room temperature. Measure the absorbance at 585 nm against the reagent blank obtained by the same procedure.
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  • Keiichiro ISHII, Takeji IWAMOTO, Kazuhiko YAMANISHI
    1973 Volume 22 Issue 4 Pages 448-450
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    The pyridine-pyrazolone method for the determination of cyanide ion has been used widely as Testing Method for Industrial Waste Water (JIS K 0102) and Testing Method for Supplying Water, etc., because of the selectivity and high sensitivity. But, as the pyridine-pyrazolone reagent has an unpleasant odor owing to pyridine and the reagent solution is unstable and its preparation is time-consuming, pyridine-pyrazolone method is unsuitable for routine work.
    For establishing a simpler analytical procedure without using pyridine, a spectrophotometric method using isonicotinic acid and pyrazolone has been developed and the optimum conditions have been established. This reagent has no unpleasant odor and is stable in N, N-dimethylformamide-water solution. A colored product with cyanide ion has an absorption maximum at 638 nm. The calibration curve followed the Beer's law in the range of 02.5 ppm CN- in samples.
    To 1 ml of sample containing 0.052.5 ppm CN- 2 ml of 0.05 M phosphate buffer solution (pH 6.8) and 0.1 ml of 1% chloramine T solution were added. The mixture was allowed to stand at 1525°C for 5 min. Three ml of isonicotinic acid-pyrazolone reagent was added, and the mixture was kept at 40°C±2°C for 30 min. The amount of CN- was determined from the absorbance at 638 nm.
    The presence of 1000 ppm of NH4+, CNO-, hydroquinone did not interfere, but the presence of 10 ppm of Cu2+, Zn2+, or Ni2+interfered. Thiocyanate ion gave a color similar to that of the cyanide compound.
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  • Yasunori NARA, Katura TUZIMURA
    1973 Volume 22 Issue 4 Pages 451-452
    Published: April 05, 1973
    Released on J-STAGE: February 16, 2010
    JOURNAL FREE ACCESS
    N- (9-Acridinyl) maleimide (NAM) was synthesized as a new fluorescent sulfhydryl reagent. This reagent when combined with thiols exhibits strong fluorescence with the emission maximum at 426 nm, being excited at 362 nm, whereas the reagent itself emits practically no fluorescence. The addition reaction with cysteine was investigated at various pH (3.06.0). Fluorometric determination of the thiol and disulfide compounds in the range of 0.4 × 10-616 × 10-6 M could be performed very simply by using NAM.
    All the other amino acids did not react with NAM; this reagent seems to react selectively with thiol group.
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  • [in Japanese]
    1973 Volume 22 Issue 4 Pages 453-465
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
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  • [in Japanese]
    1973 Volume 22 Issue 4 Pages 465-471
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Download PDF (1080K)
  • [in Japanese]
    1973 Volume 22 Issue 4 Pages 471-475
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
    Download PDF (673K)
  • [in Japanese]
    1973 Volume 22 Issue 4 Pages 476-484
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
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  • [in Japanese]
    1973 Volume 22 Issue 4 Pages 485-495
    Published: April 05, 1973
    Released on J-STAGE: June 30, 2009
    JOURNAL FREE ACCESS
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