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Volume 24, Issue 1
Displaying 1-16 of 16 articles from this issue
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Rokuro KURODA, Koichi OGUMA, Makoto SUZUKI, Yuichi FUSHU1975 Volume 24 Issue 1 Pages 1-6
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSIon-exchange adsorption behavior of a number of metals on a quaternary ammonium anion exchange cellulose(TEAE-cellulose) has been surveyed in hydrochloric acid {(0.0016)M} and hydrochloric acid (0.5 M)-ammonium thiocyanate {(0.0031)M} media. The distribution coefficients are measured either by a column or batch equilibrium method. From dilute hydrochloric acid, V(V), Mo(VI), W(VI), Re(VII), platinum metals, Au(III), Hg(II), Se(IV) etc. are strongly adsorbed (Kd>100), their adsorption generally decreasing rapidly with increasing concentration of hydrochloric acid. Ca, Sr, Y, La, Ti(IV), Zr, V(IV), Mn(II), Fe(III), Co(II), Ni, Cu(II), Zn, Cd, Al, Ga(III), In(III), Ge(IV), As(III), Te(IV) and U(VI) do not favor the cellulose exchanger phase to any great extent over the acid concentration range tested. Therefore, unlike strong base resin, TEAE-cellulose exhibits a high selectivity for a limited number of metals. The adsorption of Pd(II) and Mo(VI) can be improved greatly by introducing thiocyanate to hydrochloric acid media, providing a basis for their selective separations. Favorable differences in the distribution coefficients allow many useful separations such as As(III)-W(VI), V(IV)-Mo(VI), Zn-Mo(VI)-Pd(II), Cu(II)-Au(III)-Pd(II) to be achieved.View full abstractDownload PDF (884K) -
Selective gas-chromatographic detector by use of ion-selective membrane electrode. VTsugio KOJIMA, Mitsunojo ICHISE, Yoshimitsu SEO1975 Volume 24 Issue 1 Pages 7-12
Published: January 10, 1975
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA selective gas-chromatographic detector has been built which is equipped with two ion-selective electrodes, and allows the simultaneous and selective determination of chlorine-and fluorine-containing compounds through two channel operation. Components eluted from a G. C. column are passed through a platinum tube, where they undergo hydrogenolysis, and chlorine compounds and fluorine compounds are converted into hydrogen chloride and hydrogen fluoride, respectively. The decomposition gases are dissolved in a slow stream of an absorption solution, and the chloride ion and fluoride ion concentration in the resulting solution are monitored by a chlorideion and fluoride ion electrode, respectively. The potentiometric output of each electrode is converted into a signal, proportional to the concentration of each ion by an antilogarithmic converter, and recorded by a dual pen recorder. When a mixture is chromatographed, the dual ion electrode detector gives two chromatograms simultaneously, one specific to the chlorine compounds and the other to the fluorine compounds. Since the detector monitors the same effluent, the response ratio, defined as the peak area of the chromatogram of chlorine channel divided by that of the fluorine channel for the same compound, can be precisely determined. Data obtained with eight compounds containing chlorine and fluorine showed that the atomic ratio (Cl/F) in a molecule eluted from a G. C. column can be determined accurately from the response ratio.View full abstractDownload PDF (1039K) -
Hideo AKAIWA, Hiroshi KAWAMOTO, Hitoshi KONDO1975 Volume 24 Issue 1 Pages 12-17
Published: January 10, 1975
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSThe extraction behavior of nickel(II) with acetylacetone and the salt effect of alkali halides on this extraction were studied. The experimental procedure was as follows: Ten ml of the aqueous 0.025 M Ni(II) solution (pH=6.5) containing a given amount of salting-out agent was equilibrated with the equal volume of 0.487 M acetylacetone (Hacac) in isoamyl alcohol (IsoAA) by shaking the mixture for 150 minutes.
The distribution ratio of nickel(II) in the absence of a salting-out agent was found to be 0.45 at pH 6.5. An average molecular weight of nickel(II) acetylacetonate in isoamyl alcohol over the concentration range of 5.83×10-3M to 1.17×10-2M was determined to be 686 by the vapor pressure method. The maximal wavelength of visible spectra of the organic phase after the extraction was found to shift to lower region by diluting the solution with isoamyl alcohol (Fig. 3). From the above facts, the extracted species was estimated to be the mixture of [Ni(acac)2]3 and [Ni(acac)2]2 (IsoAA).
Although no serious change in the degree of salt effect was found in the series of halogen ions, the extraction of nickel(II) acetylacetonate was largely affected by the addition of alkali ions and the degree of the salting-out effect increased with the following order: Rb+<K+<Na+. In contrast, the salting-in effect was observed in the case of lithium ion.View full abstractDownload PDF (1018K) -
Toshiyasu KIBA, Kikuo TERADA, Takaharu HONJO, Ken MATSUMOTO, Kiyoshi A ...1975 Volume 24 Issue 1 Pages 18-25
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSChemical analyses of geochemical or environmental samples get useful when generic relationships among the samples are discovered, as the latters tell the mechanism participating in the flow of a stream as well as the transfer of materials in the environment.
The present study concerns the river bottom sediments for which a technique of the concentration correlation matrix is applied to discover the origin of various trace elements.
The investigators collected the river-sediment samples from the rivers running through the mountains of the middle Japan area. The water-suspended materials of the samples were submitted to the chemical analyses for ten elements, Cu, Pb, Zn, Cd, Ni, Co, Bi, Ag, As, and Sb. Experimental data based on 53 samples of river-sediments are presented. Among ten examples eight show the relatively high generic correlations between the samples at the confluence of the main course of the river and the feeders. Relatively low correlations found in the other two examples could be interpreted in terms of the geographical and geological reasons.View full abstractDownload PDF (1109K) -
Shigeru TAGUCHI, Mitsuhiko TAGA, Hitoshi YOSHIDA, Seiichiro HIKIME1975 Volume 24 Issue 1 Pages 26-30
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSCoprecipitation of cobalt with magnesium ammonium phosphate was studied in relation with the degree of supersaturation of the salt. Magnesium ammonium phosphate was precipitated from homogeneous solution (pH 9.5) in the presence of cobalt ion by means of hydrolysis of p-nitrophenylphosphate with an alkaline phosphatase. Degree of supersaturation (φ) during the precipitation process can be expressed as the root of the product of total concentration of metal ions and that of phosphate ions.
φ=[{C(Me)×C(PO4)}/({C(Me)}eq×{C(PO4)}eq)]1/2
Concentration of phosphate ions was obtained by measuring the absorbance of p-nitrophenol generated from p-nitrophenylphosphate. Although cobalt didn't precipitate as phosphate salt under the experimental conditions without magnesium ion, coprecipitation of cobalt was caused by precipitating magnesium ammonium phosphate. There was a tendency that the magnesium salt precipitated in high degree of supersaturation (91.4). On the other hand, coprecipitation of cobalt salt was caused in nearly saturated state. The degrees of supersaturation of these salts were not influenced remarkably by amounts of the alkaline phosphatase, i.e. by the precipitation rate. Coprecipitation of cobalt with the magnesium salt obeyed the law of logarithmic distribution.View full abstractDownload PDF (826K) -
Masatoshi SYOYAMA, Yuzo MIYACHI, Jinsaku SAKAKIBARA1975 Volume 24 Issue 1 Pages 30-35
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSA colorimetric method has been developed for the determination of carbamate insecticides and their constituent phenols with 2, 6-dibromoquinone chloroimide.
Carbamates were hydrolyzed to their constituent phenols and reacted with 2, 6-dibromoquinone chloroimide in borate buffer(pH 8.0 for ο-isopropoxyphenyl N-methylcarbamate (PHC), pH 9.4 for 1-naphthyl N-methylcarbamate(NAC), m-tolyl N-methylcarbamate (MTMC), ο-isopropylphenyl N-methylcarbamate (MIPC), ο-sec-butylphenyl N-methylcarbamate(BPMC) and 3, 5-xylyl N-methylcarbamate(XMC), respectively). Two hours after the color developed, the absorbance was measured at 580 nm in NAC, 608 nm in MTMC, 592 nm in MIPC, 593 nm in BPMC, 625 nm in XMC and 591 nm in PHC. The calibration curves showed conformity to Beer's law over the range 110μg/ ml in NAC, PHC, MIPC, BPMC and XMC, and 0.57μg/ml in MTMC. They could be used also for the determination of phenols.
For the criminological sample, 1 mg each of carbamate and its constituent phenol, added in miso-soup, were extracted with ethyl acetate. The extracts were purified by washing with borate buffer(pH 9.4) and distributing between hexane and acetonitrile, and then the carbamate and phenol were separated from other impurities by thin-layer chromatography. The recoveries were about 75% for carbamate and 60% for phenol.View full abstractDownload PDF (961K) -
Mitsuru FUJIMURA, Yoshikazu HASHIMOTO1975 Volume 24 Issue 1 Pages 36-41
Published: January 10, 1975
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA method of data treatment for size distribution of aerosol is proposed. An intuitively understandable size distribution curve is prepared by differentiation of a cumulative distribution curve.
Quantitative treatment of size distribution cannot be made by a simple histogram of particle size. An approximation by logarithmic normal distribution is of convenience for quantitative treatment of size distribution, but fitting of all the data to logarithmic normal distribution could not be correct.
The proposed method is first to draw a cumulative distribution curve F(D) by plotting the percentages of cumulative weight on a semi-logarithmic graph paper. Then the F(D) curve is differentiated to get a frequency distribution curve f(D) by plotting the gradient dF(D)/d(log D) of the F(D) curve. The f(D) curve thus obtained can be treated quantitatively and it is suitable to get intuitive image of size distribution spectrum of the aerosol.
The size distribution curve is prepared by the proposed method refered to two peaks, at around 4 μm and at a smaller size. The aerosol sample was extracted and analyzed by atomic absorption, the peak of iron is at around 4μm and that of zinc is at around 0.9μm; which is broader than that of iron.
Another example of the application of the proposed method is shown by the data of a published paper.Each of iron and zinc has a single peak and the total aerosol have two peaks; one of which appears to be correlated with iron.View full abstractDownload PDF (965K) -
Toyokichi KITAGAWA, Akio ICHIMURA1975 Volume 24 Issue 1 Pages 41-44
Published: January 10, 1975
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSThe organic reagent 8-quinolinol has been used for the extraction and the spectrophotometric determination of many metal ions. Since most of the extracted chelates give rise to almost identical absorption maxima, it is difficult to differentiate one chelate from another. On the other hand, the polarographic method is very useful because of the characteristic reduction potentials of the chelates. The diluent, methyl isobutyl ketone (MIBK), serves as a nonaqueous solvent for the polarography after the addition of tetrabutylammonium perchlorate(TBAP) as the supporting electrolyte. The potential range of the reagent blank of 0.01 M 8-quinolinol is 0 to -1.2 V vs. SCE.
Copper(II) is quantitatively extracted from 0.05 M phosphate or borate buffer solution into MIBK solution of 0.01 M 8-quinolinol in the pH range of 5.5 to 10.0. After TBAP was added and deoxygenated, the extract is analysed polarographically. The diffusion- controlled reduction wave whose diffusion current constant is 2.35 μA mg-2/3 S1/2 mM-1 appears at -0.65 V vs. SCE, which coincides with the wave of bis(8-quinolinolato)copper(II) in the reagent blank solution. The diffusion current is proportional to the copper(II) concentration in aqueous phase, and thus copper(II) in the concentration range 3×10-6 to 1×10-4M in aqueous phase can be determined by this method.
Fluoride, chloride, nitrate, sulfate, citrate and tartarate do not interfere with the copper(II) determination, but acetate gives rise to a maximum wave. The extracted tris(8-quinolinolato)iron(III) and bis(8-quinolinolato)lead(II) in MIBK also show the reduction waves with the half-wave potentials of -0.45 and -1.03 V vs. SCE, respectively. Iron(III) chelate interferes with the copper(II) determination because the reduction potential of iron(III) is more positive than that of the copper(II) chelate. The interference can be removed with the use of masking agents such as citrate. Lead(II) chelate causes no interference because of the more negative reduction potential than copper(II) chelate.
Direct polarographic determination in MIBK following solvent extraction is sensitive and simple compared with the spectrophotometric method. Most problems in spectrophotometric determination may be avoided.View full abstractDownload PDF (685K) -
Yozaburo YOSHIKAWA, Atsuko SHINOZAKI, Kimiko ARITA1975 Volume 24 Issue 1 Pages 45-48
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSDeuterium concentration in heavy water was determined gas chromatographically. Heavy water was decomposed by using LiAlH4. Heavy water reacted with LiAlH4 in short time and both H2 and HD were generated. D2 was not formed in this reaction. When hydrogen was used as a carrier gas, only a peak corresponding to HD was observed and therefore deuterium concentration in heavy water was determined as HD.
The plot of HD peak height against deuterium concentration in heavy water was found to be linear in the range of deuterium concentration from 0 to 42 atom%. The relative error was below 6.9%. This method can be applied to a small amount of water sample. It is relatively simple, and can work as a conventional method of analysis.View full abstractDownload PDF (631K) -
Hiroshi HASHITANI, Takeo ADACHI1975 Volume 24 Issue 1 Pages 49-52
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSA simple method using oxine was established for the determination of 0.12% of aluminum in nickel-and iron-base alloys. A sample (0.1 g) was dissolved in 10 ml of the mixed acid (nitric acid : hydrochloricacid:water=1:1:1) by heating. Ten ml of 18 N sulfuric acid was added to the solution and the solution was evaporated untill fumes were observed. To aliquots of the solution containing 10 to 100μg of aluminum 5 ml of 5% oxalic acid solution and 5 ml of 2.5 % oxine solution were added. Then pH of the solution was adjusted to between 5.6 and 5.8. The resulting solution was first shaken with 10 ml of chloroform and then it was shaken three times successively with 10 ml of 1% oxine-chloroform solution to extract the oxinates of iron, nickel and other metals. After the solution was washed with chloroform, 3 ml of 1% oxine solution and 1 ml of 1 M potassium cyanide solution were added and pH of the solution was adjusted to between 9 and 10. The aluminum oxinate was extracted by shaking the mixture vigorously for 1 minute with 20 ml of chloroform. The chloroform solution was washed with 50 ml of 1% hydroxylamine hydrochloride solution by shaking for 10 minutes to remove manganese. Aluminum is determined by measuring the absorbance of the extract at 390 nm. If more than 0.5 mg of niobium and/or titanium are present in the sample, they should be removed by precipitation with cupferron prior to the extraction of aluminum.View full abstractDownload PDF (703K) -
Hyoichiro SAKURAI1975 Volume 24 Issue 1 Pages 52-55
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSMicro amounts of rhenium (525μg/mL) were extracted with ammonium pyrrolidine dithiocarbamate (APDC)-methyl isobutyl ketone (MIBK) and analyzed by atomic absorption spectrometry. The effects of concentration of hydrochloric acid, amount of APDC, reaction time, and temperature on the extraction of rhenium were examined. The experimental conditions for atomic absorption spectrometry were as follows: the analytical line used was 3460 Å and the combustion gas flow rate was 12 l/min for nitrous oxide 7 1/min for acetylene. The solution of 1.2 N hydrochloric acid gave the optimum extraction of rhenium. At room temperature, more than 99.0% of rhenium was extracted into 20 ml of MIBK from 100 ml of 1.2 N hydrochloric acid solution containing 0.2 g of APDC by shaking the sample for 2 min after standing for 40 min.
The influence of molybdenum on the extraction and atomic absorption spectrometry of rhenium were examined. In the presence of 75 to 3000 mg of molybdenum, rhenium was completely extracted into MIBK, but in the presence of 5000 mg of molybdenum, the extractability of rhenium fell down to 75%. About two percent of original molybdenum was found to be extracted into MIBK together with rhenium. When the amount of molybdenum in the original solution was from 75 to 3000 mg, the absorbance of rhenium in the extract increased by about 30%. The influence of 21 other ions on the rhenium determination was examined by adding from 2 to 20 mg of each metal ion. Only Sn2+ caused a significant decrease in rhenium absorbance. The sensitivity of the extraction method is increased by a factor of about 14 compared with that of a non extraction method. Detection limit of rhenium is 1.3lig/ml/1% absorption.View full abstractDownload PDF (744K) -
Hiroshi EBIHARA, Hiroshi KAMIOKI1975 Volume 24 Issue 1 Pages 56-60
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSA rapid and accurate TLC method for the determination of 51Cr of non-chromate form in radiochromate solution has been developed as a routine procedure for examination of radiochemical purity of the commercial radioactive sodium chromate in isotonic solution.
Since a typical radiochemical impurity in the product was 51Cr of reduced form, several combinations of the inorganic solutions and silica gel or alumina plates were attempted to find out the best separation condition of the two species in comparison with the paper chromatography laid down in the Japanese pharmacopoeia. The counting of the radioactivity in the chromatograms was carried out with a well-type scintillation counter (Aloka, model JDC-701) by cutting the plate or paper in strips of 5mm or 10mm in width. Separation of Cr(VI) and Cr(III) was accomplished by using a silica gel plate (Eastman, No.6061) and a mixed solution of 10% sodium carbonate and 10% ammonium molybdate (1:1 v/v) as a developing solvent. Ascending time of 90 minutes was sufficient for clear-cut of Cr(VI). The Rf value of Cr(VI) was 0.71, whereas Cr(III) remained at the starting point.
Analytical results of the synthetic samples showed that the limit of detection for Cr(III) in Cr(VI) was 0.05% and the relative standard deviation was ±5% at the 0.5% of Cr(III) level. This procedure can insure the radiochemical purity of a commercial radiochromate solution product to be more than 99.95%.View full abstractDownload PDF (916K) -
Mamoru TOMINAGA, Akira KIMURA, Akira MIYAZAKI, Yoshimi UMEZAKI1975 Volume 24 Issue 1 Pages 61-65
Published: January 10, 1975
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSTrace amount of cadmium was determined by flameless atomic absorption spectrometry using a heated. graphite atomizer (HGA-70). The following condition was found to be optimum; sample volume 20 μl, drying at about 100°C for 30s, charring at about 230°C for 3060s, atomizing at about 2000°C for 5s, and N2 flow rate 1.6l/min. Calibration curve was linear up to about 7μg/l. The sensitivity (1% absorption) was 3× 10-12g. Interferences of acids were not serious. For the determination of 5μg/l level of cadmium, the presence of 10000-fold of metal as chlorides, nitrates, or sulfates ordinarily caused the error within ± 20% on cadmium absorption. However, chlorides of magnesium, copper, iron, cobalt, and nickel interfered seriously even in the presence of 1000-fold amount. In direct determination of cadmium, therefore, standard addition method should be adopted. The following simplified standard addition methods were proposed as convenient procedures. a) Successive addition method: Five aliquots of 20μl solution taken from 100 ml sample solution were used for washing and measurements, then 100μl of cadmium standard solution (2mg/l) was added to the sample solution. This cycle was repeated until 4 to 5 points were obtained on the graph of standard addition method. b) In-the-tube method: The procedure is standard addition by means of cumulative injections in graphite tube. These two methods and standard one were applied to the determination of cadmium in river water samples. Three methods gave a fairly good agreement. Relative standard deviation was 4 to 18%.View full abstractDownload PDF (800K) -
Shohei ODA, Hideho KUBO, Hitoshi KAMADA1975 Volume 24 Issue 1 Pages 66-68
Published: January 10, 1975
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA radio-frequency spark source mass spectrographic technique was developed for the determination of trace elements in airborne particulates.
The airborne particulates were collected on a silver metal membrane filter (poresize, 0.8μm; 47 mm in diameter) by using a low-volume air sampler with an air-flow rate of 15l/min for 24 hours or 48 hours. The sample filter on which the airborne particulates were collected was cut into two halves. A pair of electrodes (about 2 mm ×1 mm × 13 mm) was prepared by compressing each filter part in a molding devise at about 100 kg/cm2. The sample electrodes were then analyzed by using a radio-frequency spark source mass spectrograph. The coefficient of variation was found to be about 25% by quadruplicate runs. The results obtained by the present method was compared with the values obtained by X-ray fluorescence and, which, showed a good agreement for all analyzed elements except copper.
The proposed method is very simple and rapid, and eliminates the possible contamination and error which may arise from pretreatment of the sample. Since this method enables us to determine not only the metallic elements but also the non-metallic elements such as fluorine, sulfur, and arsenic, this method is assumed to be useful for the analysis of trace elements in airborne particulates.View full abstractDownload PDF (553K) -
Riichiro NAKAJIMA, Hironobu MOTONO, Tadashi HARA1975 Volume 24 Issue 1 Pages 68-71
Published: January 10, 1975
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSThe chemical shifts of iodomethylbenzenes have not been systematically measured by PMR, as the Diehl's additive principle1) does not hold in these molecules. Here, the iodomethylbenzenes such as six monoiodoxylene isomers, iodomesitylene, 4-iodo-1, 2, 3-trimethylbenzene, 4-iodo-1, 2, 5-trimethylbenzene, three monoiodotetramethylbenzene isomers, 2, 5-diiodo-p-xylene, and 4, 5-diiodo-ο-xylene, were synthesized, and the applicability of the extended Diehl's additive principle (Reed's equation2) were taken as the samples and the chemical shifts were measured in 10% CCl4 solutions in which a small amount of TMS was added, using a HITACHI R-24 NMR spectrometer (60 MHz). The chemical shifts of iodomethylbenzenes were calculated by the Reed's equation with the same precision as in the methylbenzenes, and, it was found that the result obtained by calculation based on the additivity law does not fit well to the observed values this may suggest by the additivity law that the parameters for methyl group are not sufficiently free from the effects of the iodo group.View full abstractDownload PDF (622K) -
Michio MARUTA, Kiyotsugu YAMADA1975 Volume 24 Issue 1 Pages 72-74
Published: January 10, 1975
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA curie point thermobalance was newly developed, by applying the curie point pyrolysis techniques of the pyrolysis gas chromatography to the field of the thermal analysis. A thin walled cylindrical heating element (ferromagnetic materials) which holds a sample pan in it is placed on a micro-thermobalance. The element is self-heated instantly up to its curie point temperature by induction, when high frequency power is supplied to the heating coil. After heating, it is held in isothermal state at the point, exactly. It is a benefit of this curie point thermobalance that there is no need to measure and control the sample temperature because the heating element contains only minute sample.
Details of the construction, features and some applications of the curie point thermobalance are thus presented.View full abstractDownload PDF (486K)
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