NIPPON KAGAKU KAISHI
Online ISSN : 2185-0925
Print ISSN : 0369-4577
Volume 1982, Issue 8
Displaying 1-29 of 29 articles from this issue
  • Koushin TAKAHASHI, Teruhisa KOMURA, Hiroto IMANAGA
    1982 Volume 1982 Issue 8 Pages 1275-1280
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The proton chemical shifts of solvent molecules were measured for dissolving or not dissolving NaC1 in water-1-prcipanol mixtures at 32°C. Only one peak was observed as 'H-NMR spectrum for both water protons and 1-propanol hydroxyl protons in the mixed solvents which contained less than 85% of alcohol in mass fraction. In mixed solvents without NaC1, a slight shift of this average peak to the low field was observed when the concentration of 1-propanol was from 0% to about 10%. But this peak gradually shifted to the high field above about 10%. It was inferred from these results that the addition of a small amount of 1-propanol to water enhanced the solvens structure by the formation of hydrogn bonds. When NaC1 was dissolved in a mixed solvent, the proton sign als for solvent molecules shifted straightforwardly to the high field with the increase of NaC1concentration. From these results and structual changes in mixed solvents, it was inferred that water molecules preferentially solvated to ions at lower concentration of 1-propanol but molecules of both water and alcohol solvated at its higher concentration.
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  • Fukuzo ITOH, Minoru SATOU
    1982 Volume 1982 Issue 8 Pages 1281-1286
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The coercivity of nonstoichiometric iron oxide parti cles has been increased remarkably by coating with chain like sodium metaphosphate (NaPO3), t and by subsequent heating under a reduced pressure. In this paper, the chemical properties of coated (NaPO3), , onto an acicular iron oxides and a bond-state between phosphate and iron ion were studied to explain the observed increase in coercivity.
    No fundamental ch anges were observed by means of X-ray analysis or infrared absorption spectroscopy of (NaPO3), coated onto the iron oxide particles compared with nonheated (NaO3). The coercivity increased in the same manner with addition of Ca ion, which is likely to be linked to the site of the terminal position in the side chain of (NaPO3). This suggests that Fe ion is linked to the site of oxygen at the terminal position of main chain in (NaPO8) n. The coercivity tends to approach a maxmium when the acicular iron oxide pa rticle are coated in (NaPO3)7, solution of pH range from 7 to 9. However, the effect of pH was not so great. The increase in the coercivity was more significant when the iron oxides were coated with preheated hydrous (NaPO3)n, at 150°C under a reduced pressure than with unpreheated one. The coerciv i ty also increased by coating with P2O5. Therefore, it is considered that chain like phosphate (HPO3)n, formed by hydrolysis and condensation of P2O5 improves the coercivity.
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  • Soichiro YAMAMURA, Wasaburo KAWAI
    1982 Volume 1982 Issue 8 Pages 1287-1293
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Using an n-type semiconductor(SnO
    or In2O3) and a platinum electrode, photoelectrochemical study was carried out in water containing tetrakis(4-sulfophenyl)porphyrin as photosensitizer and L-ascorbic acid as electron donor. Under photoirradiation, photocurrent was observed, as a result of electron injection into the semiconductor electrode. Zn, Mn and metal free porphyrins were investigated, but photoreduction of them occurred. Subsequetly, porphyrin was immobilized on the surface of In2O3 electrode by poly(vinyl alcohol) cinnamate. As the result, porphyrin was protected from decomposition to a certain degree, and stabilization of photocurrent was observed. It was found that Zn and Mn porphyrins were particularly effective photocatalysts.
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  • Chiaki IWAKURA, Masato NISHIOKA, Hideo TAMURA
    1982 Volume 1982 Issue 8 Pages 1294-1298
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The electrodes of solid solutions with spinel-type structure, Pt/CozFe3_x04, Pt/MnxFe3-x04and Pt/NizFe8, 04, were prepared by thermally decomposing metal nitrate mixtures on a platinum substrate at 1150°C in air, and the relationship between the oxygen overvoltage and magnetic property of the resulting electrodes was investigated. The effective Bohr magneton which corresponds directly to the number of unpaired d electrons per molecule was calculated from the saturation magnetization measured at room temperature. In the case of the Ptl CosFe3_x04 electrodes, both the overvoltage and effective Bohr magneton decreased wi th increasing X value up to 2.0. On the other hand, in the case of the Pt/MnxFe3_x04 and PtiNizFe, 0, electrodes, \ he x dependencies of oxygen overvoltage and effective Bohr magnton were reverse to each other. That is, the oxygen overvoltage increased in the case of the former electrodes whereas it decreased in the case of the latter two kinds of electrodes as the effective Bohr magneton increased. From the kinetic studies, it was presumed that the ratedetermining step was the second step or the chemical reaction of OH radical with 0H ior in the former electrodes but it was the first step or the discharge reaction of OH- ion at the latter two kinds of electrodes. The above relationship between the oxygen overvoltage an effective Bohr magneton was therefore explained from a point of view that the rate of the first step increased but that of the second step decreased with an increase of the number oi unpaired d electrons due to the increase of the stability of the reaction intermediate or OF radical.
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  • Yohtaro YAMAZAKI, Tatsuru NAMIKAWA, Minoru SATOU, Yasuhiro AYABE
    1982 Volume 1982 Issue 8 Pages 1299-1304
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Continuousγ-Fe2O3 thin films have been synthesized through an oxidation, a reduction and a mild oxidation processes. Iron thin films of 1100 A thick, starting material, were prepared. by evaporating iron on sapphire substrates and oxidized at 400°C in oxygen gas. The reduction was carried out at 320-400°C in argon gas, which was saturated with methanol at room temperature, and the mild oxidation in air at the temperature of 210-300°C. After the oxidation and the reduction processes, pure a-Fe2O3 and Fe3O4, were formed on the substrates, respectively. By adjusting the condition of the mild oxidation process, intermediary films with composition of Fe3O4 and Fe2O3 were obtained. The coercivities of the Fe3O4 and rFe2O3 films were 250 Oe and that of certain intermediary films were above 1000 Oe. The intermediary films were stable at room temperature and the gradual coercivity change was not detected, although the variation of it was reported for the fine particles of the same intermediate state. The thickness of the formed T-Fe2O3 films was 2900Å.. Irregular patterns of unevenness having a mean width of 1000Å and a mean depth of 450Å were observed on the surface of the films. The surfaces of the prepared films could be improved by removing the irregular surface layers. The mean crystal sizes were 280A for the evaporated iron films, 380Å for ce-Fe2O3, 340Å for Fe3O4, and 270Å for T-Fe2O3 films. The thickness of the iron films was 1100Å and was increased to 2900Å during the oxidation process. No detectable thickness change was observed during the reduction and the mild oxidation processes. The procedure and the equipment used for the film preparation were described in detail to establish reproducibility on the measured value.
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  • Hiroaki YAMADA, Tsuyoshi NAKAJIMA, Nobuatsu WATANABE
    1982 Volume 1982 Issue 8 Pages 1305-1313
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The fluorination film was prepared on the aluminium surface by the anodic polarization in the liquid hydrogen fluoride and by the direct fluorination with the elemental fluorine and their natures were studied by means of X-ray diffractometry and X-ray photoelectron spectroscopy. The fluoride film, made by anodic polarization at 30 V, 1 h in liquid hydrogen fluoride, had the F/C ratio of 3.5. ESCA study suggested that fluoride hydroxide was formed on the surface of the film prepared in the liquid hydrogen fluoride containing more than 0.5 wt%H20. On the other hand, the F/0 ratio of the film prepared by direct fluorination (50 0°C, 24 h, F2: 1 atm) was 9.5. Fluorinated film with high fluorine content showed the good corrosion resistance against moisture in air and aqueous solution. It was found that the diffusion coefficient of fluorine through aluminium fluoride film depended on the fluorine content in the fluoride film and that the order was from 10-15 to 10-14 cm2/s in the temperature range of 150-500°C. It was estimated that the activation energy for diffusion of fluorine was 43.1k T /mol from Arrhenius Dlot.
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  • Kazumasa OHTSUKA
    1982 Volume 1982 Issue 8 Pages 1314-1321
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The kinetics and mechanism of the oxidation of hydroxo(ethylenediaminetetraacetato)chromate (III) (1) and hydroxo[N'-(2-hydroxyl)ethypethylenediamine-N, N, N'-triacetato]chromate(III) (2) by hydrogen peroxide in aqueous ammonia were studied by means of visible, UV and ESR spectroscopy and chemical ananlysis. The results were compared with th ose of previous works dealing with hexaaquachromium(III) and tris(oxalato)chromate(III) complexes. The coordination of H2O2 to the complex (1) or (2) is the primary step and CrO4-2 is the final product. The coordination rates in these complexes are much greater than that in tris(oxalato)chromate(III), suggesting that the lability of these complexes were enhanced by the existence of hydroxyl. These complexes are oxidized to CrO42- via detectable Cr complexes. The Cr v intermediates in this work retain the amino acid ligands of the parent CrIII complexes and do not seem to coordinate H2O2 molecules. The rate-determining step is presumed to be the liberation of ligands from the Cry complexes, followed by the rapid coordination of EH2O2and by further oxidation.
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  • Tsugikatsu ODASHIMA, Sadako SATO, Hajime ISHII
    1982 Volume 1982 Issue 8 Pages 1322-1327
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Nickel( II) ion reacts with 5-chloro-2-thiophenecarbaldehyde 2-benzothiazolylhydrazone (CTBH)to form a 1: 3 yellow complex (λmax=427 nm, ε = 7.4X 104mol-1 dm-3ecm-1 in a micellar solution of Triton X-100, and Amax= 425 nm, v=8.7x 104m o1-' dm3. cm-' in isobutyl methyl ketone (MIBK) and an adduct complex (λmax= 435 nm, ε=5.2x 104m ol-1dm3cm-1 in benzene) by the synergistic effect of pyridine base when it is present. The ratio of three components in the adduct complex is estimated to be nickel(III): CTBH: pyridine =1: 2: 2. On the basis of these results and the analysis of far infrared spectra, it is assumed that the nickel( 10complexes have the octahedral structure in the media studied. The complex, extracted into MIBK, was applied to the determination of trace amounts of nickel. The proposed procedure is as followsTake the sample solution containing up to 6 pg of nickelin in a 50 cm3 separatory funnel, add 1 cm3 of a 2.5 X 10-3 mol. dm-8 CTBH solution in ethanol and 2 cm3 of ammonium buffer solution (pH 9.0), and dilute to about 30 cm3 with water. Then add 10.0cm3 of MIBK and extract the complex by shaking for 5 min. Measure the absorbance of the organic phase at 425 nm against a reagent blank. Beer's law was confirmed over a range of 0.2-6.2 pg Ni2+/10 c m3 MIBK and the sensitivity which gave the absorbance of 0.001 wa s 0.00079 μg Nicm-2. Among sixteen kinds of diverse metal ions tested, chromium (E) and vanadium(V)V ) ions seriously interfered with the determination of nickel. The procedure was applied to the determination of nickel in iron and steel. Satisfactory results were obtained.
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  • Yoshikazu INOUE, Makoto MUNEMORI
    1982 Volume 1982 Issue 8 Pages 1328-1332
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The formation of hexachloroantimonate is a crucial step in the spectrophotometric determination of antimony by the Rhodamine B method. In the proposed method, antimony is quantitatively converted with cerium (IV) to hexachloroantimonate in the presence of the chloride mixture containing 1 moll/ hydrogen ion and 5 mol/l chloride ion and the hexachloroantimonate is directly extracted from aqueous phase to diisopropyl ether. A colored complex of hexa chloroantimonate and Rhodamine B is subsequently formed by shaking organic phase with the aqueous solution of Rhodamine B. Plots of the absorbance at 550 nm against the concentration of antimony follows Beer's law in the region from 0.1 to 1 ppm. At 0.2 ppm antimony level, the relative standard deviation (n =6) is 6.2%. Iron (III) gives litte or no interference with the determination of antimony by the proposed method.
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  • Akira KAWASE, Akira UCHIUMI, Kuniko TERAJIMA
    1982 Volume 1982 Issue 8 Pages 1333-1336
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    2-(2-Benzoxazolylazo)-1-naphthol(a-BOAN) was synthesized as the new reagent for the determination of trace amounts of metals and the analytical properties ofa-BOAN was quantitatively compared with those of 1-(2-pyridylazo)-2-naphthol(α-PAN), 1-(2-benzothiazolylazo)1-naphthol(α-BTAN) and 2-(2-quinolylazo)-1-naphthol(α-QAN).
    Spectrophotometrically det ermined acid dissociation constants of α-BOAN (pKa1 and pKa2)in various aqueous dioxane concentration were 0.4689-8.237 n+19.38 n2 and 6.317+3.566 n, respectively, where n is molar fraction of dioxane. Replacement of pyridine ring in α-PAN by benzoxazole ring resulted in a decrease in pKa values of the reagent which accompanied by decrease in metal chelate formation constants. The proton displacement constants of the reagent, however, were found to be higher than those of the other analogous compounds refered above. A study has been made of the extraction of copper and zinc into carbon tetrachloride by α-BOAN. Copper and zinc formed extractable chelates containing a 1 to 2metal-ligand ratio. The extraction constants of the chelates have been determined. The analytical advantages of the use ofα-BOAN in the determination o f metals are outlined.
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  • CHOZO YOSHIMURA, Kazunori MATSUMURA
    1982 Volume 1982 Issue 8 Pages 1337-1340
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    We have previously reported the elimination of interferences and deoxidation effects with carbon black in flame atomic absorption spectrophotometry of metals. This report deals with the enhancing of absorbance and atomizing effect in 19a m eless atomic absorption spectrophotometry of molybdenum and vanadium by the addition of carbon black. By dispersing carbon black in the sample solution, the absorption, curves of molybdenum and vanadium became sharp. The absorbance was about 6 times for molybdenum and 1.6 times for vanadium higher than without carbon black. Further, the life of the graphic cuvette was increased by the addition of carbon black. It appears that the enhancement of absorbance is due to the deoxidation effect of carbon black to the formation of oxide, and the increasing of the atomization efficiency.
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  • Kenichi NAKAZATO, Klichi SUZUKI, Yoshio WATANABE, Yoshio MATSUMOTO
    1982 Volume 1982 Issue 8 Pages 1341-1346
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Chelating resins containing thiosemicarbazido groups as pendant was prepared by the condensation of spherical porous copolymer with thiosemicarbazide and adsorption of metal ions on these resins was studied.
    By suspending 30 g of N- (hydroxymethyl) acrylamide and 3.7g of N, N'-methylenediacrylamide in the petroleum hydrocarbon in the presence of water as diluent, the copolymers with the excluded molecular weight of 2 x 104 and the degree of swelling (wet-m//dry-ml) of 2.67were obtained. Chelating resins with the sulfur content of 15.0 wt% were obtained by the condensation of the spherical porous copolymers with thiosemicarbazide in water. For the prepared resins, the pH, the temperature, the ionic strength, and the metalic ion's concentration did not affect the adsorption of Cu2+, Ni2+, and Pb2+within the given limits of experimental conditions. The order of the adsorption was Cu2+> Ni >Pb2+ under all conditions studied. At the concentration range of 1 x 10-4mol//, the percentage of Cu2+and Ni2+ adsorbed on the resins were more than 99% and 94%, respectively. The resins will be utilized for removing trace amounts of heavy metal ions in the presence of a relatively large amount of light metal ions, such as Na+ and K+.
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  • Toshio TSUCHIDA, Kentaro YODA
    1982 Volume 1982 Issue 8 Pages 1347-1351
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    A rapid, specific, and simple enzyme electrode method for the analysis of uric acid was developed. A cellulose acetate membrane with asymmetric structure which has the permeability toward hydrogen peroxide was prepared. Uricase (EC 1.7.3.3) was immobilized onto the porous side of the membrane by entrapping with chitosan. The enzyme electrode was constructed with combination of the immobilized uricase membrane and a polarographic electrode sensing hydrogen peroxide. The enzyme electrode responded linearly to concentration of uric acid over zero to 50 mg/d/. Response time was within 20 s. The enzyme electrode was applied to the analysis of uric acid in human blood. Only 25 μl of human serum or human whole blood was required for analysis. Analytical precision was O.6% at 6.4 mg/dl on human plasma and 2.2% at 2.3 mg/dl on human whole blood. Analytical recovery was 99.9% on controlled human serum. Correlation was established with enzyme colorimetric method; r = 0.985, y=0.977 x + 0.05 (x: Enzyme colorimetric). The immobilized uricase membrane was sufficient ly stable to perform 1000 assays (17 days operation) for the determination of uric acid in human blood. The storage shelf life of dried membrane was more than 14 months at 4°C. The present enzyme electrode method offers an excellent assay procedure for uric acid in clinical analysis.
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  • Kiyoshi NOMURA, Yusuke UJIHIRA
    1982 Volume 1982 Issue 8 Pages 1352-1356
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The various compositions of hureaulite, (Mn1-x, Fex)5H2(PO4)44 H2O, were synthesized by adding 1 mol/l solutions of manganese sulfate and iron(II) sulfate to a 0.3 moll/ solution of disodium hydrogen phosphate (pH 5) at higher temperature than 95°C in the stream of nitrogen to prevent the samples from the oxidation of iron(II). The chemical states of substituted iron were investigated by means Of the MOssbauer spectrometry.
    It was found that the iron( III) ions fill the three m anganese sites [M( 1 ), M( 2 ) and M( 3)]of octahedra of hureaulite structural unit to the degree up to 100%, and that the distribution coefficient of iron (II) ion to the M( 2 ) site of hureaulite structure increases with the increase of iron contents. The relationship between the ratio of peak intensity of the Mössbauer spectra, y=IM(2)/(IM(1)+IM(2) + IM(3)), and the fraction of iron and manganese in hureaulite, x =Fe/(Fe+Mn), is found to be expressed approximately by the equation, x=4.7 y-1.2, sugges ting a possibility of estimating the iron contents in iron(II) substituted hureaulite. Finally, the distribution diagram of iron and manganese in hureaulite was shown with regard to each site of octahedra in Fig.5.
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  • Toshihide Suzuki, Kiyoshi KUDO, Nobuyuki SUGITA
    1982 Volume 1982 Issue 8 Pages 1357-1362
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Synthesis of glycolaldehyde from formaldehyde and syn-gas under various conditions in DMF solution has been studied kinetically in the presence of a catalytic amout of RhCl(CO) (PPh3)2. Glycolaldehyde was obtained in high yield (85%) and selectivity (97%) under the conditions: P2= 7O k gcm-2, Poo= 70 k g cm-2, 100°C and 5 h. By postulating a reaction scheme which could explain the experimental results satisfactorily, the rate equation has been derived as shown below;
    _??_
    The equilibrium constants and rate constant at 100°C have been determ ined as K1= lx 10-4 m ol, K2=-3X10-3 kg-1cm2, K3=4 moll-1, K4=-1 X 10-2 k g-2cm2 and k=0.5-1
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  • Norimitsu SHIMANOUCHI
    1982 Volume 1982 Issue 8 Pages 1363-1370
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Bisphenol A was obtained in about 80% yield by stirring a mixture of 1.2 mol of phenol, 0.3 mol of actone, 82.0 g of conc. hydrochloric acid and O.0 6 g of 3-mercaptopropionic acid at 70°C for 5 h. The yield of bisphienol A was investigated in various organic solvents with gaseous hydrogen chloride as an acidic condensing agent. Bisphenol A was obtained in 82.0and 88.0% yield at a low temperature in the presence of organic solvent such as hexane and o-dichlorobenzene, respectively, which did not dissolve bisphenol A. The solvent effect on the yield of bisphenol C was also investigated. The reacion mechanisms for the formaion of bisphenol A and C were proposed based on the analysis of the products by thin layer chromatography and gas chromatography.
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  • Takanao MATSUI, Teruaki SUGAHARA, Mitsuru NAKAYAMA
    1982 Volume 1982 Issue 8 Pages 1371-1375
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    13C-NMR spectra of 2, 2- and 2, 3-dimethyl-4-chromanone derivatives have been examined. The latter was prepared from 2-methyl-2-butenoic acid and the corresponding phenols in the p r e s ence of polyphosphoric acid. The NMR signals were assigned by comparing the spectra of closely related compounds and on the basis of the comparison between the calculated an d observed chemical shift values for the aromatic ring carbons. The 3-methly carbon resonanc e at significantly high field (δ 9.4-10.5) in 2, 3-dimethy1-4-chromanones seems to be usefu for their conformational assignment.
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  • Yukitami SAHEKI, Nobumasa SATO, Kenji NEGORO
    1982 Volume 1982 Issue 8 Pages 1376-1381
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The hydrolysis of r-phenyl-r-butyrolactone in 20% aqueous acetone solution has been examined in the presence of sodium dodecyl sulfate (SDS), dodecyltrimethylammonium chloride (DTAC) and polyethyleneglycol-(p-nonylpheny1)-ether (PONPE) at O.0, 2.5 and 5.0°C.
    The results obtained were as follows.1) The kinetic and thermodynamic parame ters of the reaction were evaluated for each surfactant. The reaction was found to be accelerated in micellar systems. Linear relationships are present between EA and SA and between kObB and concentration of surfactants.2) In gel filtration on a Sephadex LH-20 column, samples of SDS, DTAC and PONPE at concentrations above the CMC behaved similarly to polymerizing systems. From the gel filtration data, partition coefficients of solutes in micellar and bulk phases were calculated.3) γ-Phenyl-r-butyrolactone was strongly partitioned in micellar phases of the surfactants, especially in those of PONPE and DTAC. NaOH was weakly partitioned especially in micellar phases of SDS. This is because there is a repulsion between the negatively charged micelle of the anionic surfactant and the hydroxide anion.4) From the kinetic data for bulk and micelle phases (kb and km), it was found that the reaction was accelerated principally due to lowering of the entropy of activat ion.
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  • Takayuki HAYASHI, Takao TOKUMITSU, Takako ISHIBASHI, Mitsue NISHIYAMA
    1982 Volume 1982 Issue 8 Pages 1382-1385
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    2-Benzoy1-3-methy- and 2-benzoyl-6-methylbenzoic acid [ 2 ] in polyphosphoric acid gave 3, 3-diphenyl-7-methylphthalide [4 ]and 3, 3-dipheny1-7-[(1, 3-dihydro-4-methy1-3-oxoisobenzofuran1-yl)methy]phthalide [5] along with 1-methylanthraquinone 3 at 90-120°C, but gave only [3] at 140°C. The structure of 5 was determined by means of its MS, IR, NMR and UV spectra, and its chemical behavior. Mechanisms for the formation of [4]and [5] are discussed.
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  • Masakazu TATSUMI, Seika YAMAMOTO
    1982 Volume 1982 Issue 8 Pages 1386-1393
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Styrene popcorn polymer (St-PCP) was obtained by the polymerization using divinylbezene, ethylene glycol diacrylate, and ethylene glycol dimethacrylate as the crosslinking monomer. Vinyl polymerizations using the St-PCP as the seed were carried out PCP-formations were observed for styrene and methyl methacrylate (MMA) but not for vinyl acetate and acrylonitrile. Activities of the seeds toward styrene and MMA were influenced by the concentration of the crosslinking monomer in St-PCP regardless of the content of crosslinking monomer. The seed containing a low concentration of the crosslinking reagent exhibited a great activity toward MMA, whereas a high concentration of the crosslinking reagent was favorable to styrene. Though the high concentration of radicals was detected in these polymerization systems, popcorn polymerization did not proceed to completion. These results o f the popcorn polymerizations initiated with the seed could be explained considering living radical-like graft polymerization in the seed.
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  • Akira KAI, Jiro KOGUSURI, Yasuji KOBAYASHI
    1982 Volume 1982 Issue 8 Pages 1394-1399
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The fibrilzation of cellulose gel biosynthesized by Acetobacter xylinum was studied by means of electron microscopy. Acetobacter xylinum was incubated in O.0 2 wt% glucose solution (pH 6.8 ) with and without added 0.2 w t% sodium tungstophosphate on the sheet mesh cove red collodion membrane for a given time at 28.0°C. The fibril obtained from the latter culture medium was stained with 0.2 wt% sodium tungstophosphate solution before drying. The cellulose fibril after the biosynthesis was homogeneous and amorphous. The amorphous state of the fibril was kept for about 30 min. In course of time, the inhomogeneous distribution of cellulose took place perpendicular to the long axis of the amorphous fibril. Finally many microscpic fibrils with the width of about 40-50Å appeared simultaneously in the amorphous fibril in about 5 h after biosynthesis. The bacterial cellulose microfibril was found to be composed of these microscopic fibrils. The negative staining-stuff contained in the culture medium scarcely influenced the fibrilzation of cellulose gels. It is not clear whether the appearance of the microscopic fibril found in this study is due to the crystallization or the biosynthesis of the amorphous fibril. The fact that the microscopic fibril always appears in all amorphous fibrils seems to indicate that there are cellulose chains not randomly but regularly oriented in the amorphous fibril.
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  • Masaki SHIMBO, Mitsukazu OCHI, Takashi NAKAYA
    1982 Volume 1982 Issue 8 Pages 1400-1406
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Bisphenol A diglycidyl ether was cured with 4, 4'-diaminodiphenylmethane in the presence and absence of salicylic acid as an accelerator at 80°C. The curing process of these systems was followed by determination of the molecular weights and their distributions in the products and by chemical analyses of their functional groups. The structures of the intermediates isolated from the cured resin using salicylic acid as an accelerator were also studied. By the addition of the accelerator, the reaction of the epoxy group with the amino groups was activated and the formation of the ether linkage was suppressed. The products of the accelerated system had a broad distribution of the molecular weight and a high conversion of the epoxy group, The intermediateshaving molecular weights in the range 340-1400 were isolated and their structures were estimated by GPC, VPO, NMR, and titrational analyses. The molecular chain of the reaction products was suggested to be made up of the alternate arrangement of the diepoxide and 4, 4'-diaminodiphenylmethane.
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  • Tohru SUETAKA, Makoto MUNEMORI
    1982 Volume 1982 Issue 8 Pages 1407-1411
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    The rate of combustion reaction either of triethylamine or of dimethyl sulfide was investigated. The reactor was a quartz pipe packed with a bundle of quartz capillary and a reactant gas was prepared by inserting a small amount of liquid triethylamine (or dimethyl sulfide)into a N2-O2 mixed gas.
    The efficiencies of comiustion of each substance were observed under various conditions: ( 1 ) the initial concentration of triethylamine (or dimethyl sulfide) (700, 2700p pm); ( 2 ) the content of oxygen gas (21-100 mole percent); ( 3 ) temperature (500-610°C). Based on the temperature distribution within the reactor, which was well expressed by a cubic equation with respect to the distance, experimental results were analyzed by the nonlinear least squares method. The following overall rate equations were finally obtained: r=kc'C0.2O2C1.3A for triethylamine from Fig.8 and Table 2, and r-=kc'CmO2C1.1A for dimethyl sulfide from Table 3.
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  • Etsuro KOBAYASHI, Kitoshi UEMATSU, Yoshinobu NAGAWA, Minoru Sucm
    1982 Volume 1982 Issue 8 Pages 1412-1418
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    A complex was prepared from zirconium(W) oxide hydrate (ZrO2⋅x H2O) and active carbon, and the adsorptive power of the complex to phosphate ion and organophosphorus compounds was investigeted. A mixture of an aqueous solution of ZrOCl2⋅8H2O (3-7 g) and granular active carbon (10 g) was heated at 160°C with the evolution of hydrogen chloride. The solid thus obtained was washed with water in order to hydrolyze the deposited substance on the active carbon to ZrO2⋅x H2O, and then dried. The complex obtained had a much greater adsorptive power to orthophosphate ions than that of commercially avilable zirconium oxide hydrate; for example, the amount of phosphate ion adsorbed by ZrO2⋅x H2O present in the complex was about 5 times as much as that by the same amount of commercially avilable one. Though surface area and pore volume of the adsorbent thus obtained became smaller than the active carbon itself, the complex was able to adsorb organophosphorus compounds such as tributyl, triethyl phosphates, dibutyl hydrogen phosphate and sodium glycerophosphate. It was believed that tributyl and triethyl phosphates are chiefly adsorbed by active carbon, dibutyl hydrogen phosphate by both ZrO2⋅x H2O and active carbon, while water-soluble compounds such as sodium glycerophosphate by ZrO2⋅x H2O deposited on active carbon. Effective removal of phosphate ions was also carried out through a column charged with the complex. It was found that the adsorbent could be regenerated by an aqueous solution of sodium hydroxide and hydrochloric acid, and no reduction in adsorptive capacity was observed in repeated 10 runs.
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  • Masaaki SAITO, Yoshiyuki TANIZAKI
    1982 Volume 1982 Issue 8 Pages 1419-1421
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
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    Time-dependence of chemical composition in groundwater was analyzed by the concentration ratio matching method which provided correlations among chemical compositions. Groundwater samples were collected from a piestic surface water well at 5, -50 days intervals. The correlation number obtained by the concentration ratio matching method decreases with the length of sampling interval, and reaches a constant value at over 100 days.
    Assuming that variations of concentrations depend on the grou ndwater flow, the correlation number, Z, can be expressed as a function of time: Z(t)=b1(a+b)-Fal(a+b)exp(ab)t. Experimental data are explained by the above equation. Therefore, this equation can be used to predict chemical composition change caused by the groundwater flow.
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  • Atsushi CHIBA, Tadahiko OGAWA
    1982 Volume 1982 Issue 8 Pages 1422-1424
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Copper alloys, about 1 or 2 mg, were dissolved with a few drops of 2 moldm-3 nitric acid, and diluted to 10 cm3 with distilled water. An aliquot this solution (4 mm3) was dropped on the center of filter paper (Toyo No.51 A) on a ring oven at 120°C. Copper(II) was separated from coexistent metal ions in an atmosphere of hydrogen sulfide by using ring oven technique. Copper(II) diethyldithiocarbamat (Cu-DDTC) complex was formed with 1% Na-DDTC solution. Determination of copper(II) was made by using the photoacoustic (PA) intensity at 433.0 nm, the maximum wavelength of Cu(II)-DDTC complex spectrum. The calibration curve was obtained by using At= -log{1-(St/SO}2), where At is absorbancy, St is PA signal intensity of the sample and Sb is PA signal intensity of a black filter paper (Toyo No.131-B). The determination range of copper(II) was from 0.1 to 1.4 /μg. The coefficient of variation obtained for ten samples was ±2%.
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  • Hidehiko KITAJIMA, Akira NAKATSUJI, Hiromu YAMAUCHI
    1982 Volume 1982 Issue 8 Pages 1425-1427
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    4, 6-Bis(dimethylamino)-, 4, 6-bis(diphenylamino)- and 4, 6-diphenyl-2-iodo-1, 3, 5-triazines, [2 a], [2 b] and [2 c], were synthesized by the halogen exchange reaction of the corresponding chloro derivative with NaI. The yields of the reaction were good except for [2 a] which was prepared independently from cyanuric iodide and dimethylamine in satisfactory yield. The Ullmann reaction of [2 a]-[2c] with active copper powder gave the corresponding 4, 4', 6, 6'tetrasubstituted 2, 2'-bi-1, 3, 5-triazines [3a]-[3c] in 35, 45 and 20% yields, respectively. UV spectral data of [3a] and [3c] suggest that there may be no appreciable conjugative interaction between the two triazine rings.
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  • Masaaki SUGIURA, Tomohiko YAMAGUCHI
    1982 Volume 1982 Issue 8 Pages 1428-1430
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Some amino acids were transmitted through poly(vinyl chloride) (PVC) membranes containing trialkyl phosphates (e. g. tributyl phosphate (TBP) and tripentyl phosphate (TPP)) against their concentration gradient when the hexafluorophosphate or perchlorate ions were allowed to flow at the same time. The transport of amino acids occurred only under the acidic conditions of the donor aqueous phase. The transport rate was also affected by the pH difference across the membranes.
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  • Yukiho YAMAOKA
    1982 Volume 1982 Issue 8 Pages 1431-1433
    Published: August 10, 1982
    Released on J-STAGE: May 30, 2011
    JOURNAL FREE ACCESS
    Terpenoid compounds (longiforene, dehydroabietane and retene) contained in the sediments from Hiro Bay were investigated. The amounts of the terpenoids were found to be in the following order: alkali-insoluble fraction, humic acid fraction, chloroform-extractable fraction. No terpenoids were found in a fulvic acid fraction. t Behavior of Organic Matter in the Polluted Coastal Area. IV.
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