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Volume 28, Issue 1
Displaying 1-16 of 16 articles from this issue
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Chozo YOSHIMURA, Kiyoshige MIYAMOTO1979 Volume 28 Issue 1 Pages 1-4
Published: January 05, 1979
Released on J-STAGE: January 19, 2010
JOURNAL FREE ACCESSColorimetric determination of nitrobenzene with lithium hydride in dimethylsulfoxide was studied. Lithium hydride reacts with nitrobenzene in dimethylsulfoxide to form reddish violet solution in the presence of acetone (about 1%) and the colored compound has an absorption maximum at 540nm. The molar ratio of nitrobenzene and lithium hydride was found to be 1 : 2 by colorimetry. An absorbance of the solution did not change after 6h elapsed. The sensitivity limit of this determination was as low as 2×10-5M. The reaction was assumed to proceed as follows :
2_??_-NO2+4(CH3SOCH2-·Li+)→
[(CH3SOCH2-_??_-N=O-N=O-_??_-CH2SOCH3)2-
·2Li+]+2LiOH+2DMSO
The determination procedure is following; take 10ml of DMSO solution of nitrobenzene. Add 5ml of DMSO-lithium hydride (1×10-3M) and acetone to yield 1.0v/v% final concentration and dilute to 25ml with DMSO. Measure the absorbance at 540nm after 50min at 25°C. Calibration curve of nitrobenzene was linear from 2×10-5M to 8×10-5M. An absorbance was not affected by coexistence of a large amount of aniline because it did not react with lithium hydride, but water, inorganic acids and carboxylic acids interfered with the determination.View full abstractDownload PDF (553K) -
Keiichiro HOZUMI, Kumiko KAWAKAMI, Naoshige AKIMOTO1979 Volume 28 Issue 1 Pages 5-9
Published: January 05, 1979
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA method for the microdetermination of organic halogens involving the oxygen flask combustion and the subsequent potentiometric titration of the neutral or weakly acid absorption liquid using a sodium ionselective glass electrode and 0.005M silver nitrate solution is described. The end point of the titration was marked as a sharp inflection at the vicinity of the equivalence point for which an interpretation was made that the electrode potential was sustained by the hydrogen ion activity before the end point but was suddenly raised with a small increment of the silver ion activity after it, because the electrode was responsive extraordinarily to the silver ion activity. Regression analysis with some standard organic samples ranging (15)mg resulted in acceptable reproducibility given as the standard deviation around 0.01(ml) along the regression lines, while the sampling error was assumed to be negligible. Coexistence of sodium and potassium ions seriously interfered with the end point detection when their molar concentration exceeded five times as high as that of halogenides, while ammonium, lithium, calcium, magnesium, copper (II), and barium ions gave practically no effect until (50200) times higher concentrations. High interference from the potassium ion in spite of its 1/1000 low selectivity to the electrode relative to sodium ion was also elucidated. The ion-exchange phenomena of the two cations at the alumino-silicate anionic sites dispersed within the surface gel layer were supposed to be nearly the same degree whereas the mobility of the potassium ion in the dry glass bulk was significantly lower than in the case of sodium ion. The former reason seemed to function as the cause of higher interference from the potassium ion while the latter reason characterized the electrode in low selectivity to the same ion. Transportation of the silver ion through the electrode membrane after the equivalence point seemed to be interrupted by the metal-exchanged gel layer. Removal of the metal ions was simply achieved by an addition of 1g of wet cation-exchange resin into the test solution and the solution with the floating resin was titrated after 10min standing.View full abstractDownload PDF (995K) -
Yukio SAKAI1979 Volume 28 Issue 1 Pages 10-14
Published: January 05, 1979
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSA sensitive and selective spectrophotometric method was developed for the determination of nickel based upon the reaction with 2-(5-nitro-2-pyridylazo)-1-naphthol (5N-α-PAN) at pH 8.5 in the presence of Triton X-100. Interference from foreign ions can be avoided by the use of masking agents and EDTA. Iron does not interfere if oxidized to Fe (III). Mn (II) and Cu (II) are masked with tartrate and 1, 2-diaminopropane (1, 2-DAP) respectively. The 5N-α-PAN chelates of Zn (II), Cd (II) and Pb (II) are completely decomposed by the addition of EDTA after the color development of the Ni chelate. Interference from Co (II) (<50μg) are eliminated by the combined use of 1, 2-DAP and EDTA. When larger amounts of Co (II) (<450μg) are present, the influence can be corrected by measurement of the absorbances at 595nm and 632nm. A recommended procedure is as follows : An aliquot of sample solution containing up to 35μg of nickel is transfered to 50ml volumetric flask and a few mg of ammonium persulphate, 2.0ml of 20 (w/w)% Triton X-100, 2.0ml of 0.1M tartrate and 1.0ml of 0.1M 1, 2-DAP are added successively. After the addition of 2.0ml of 0.05 (w/w)% 5N-α-PAN in dioxane, the solution is adjusted to pH 8.5 with boric acid buffer (pH 8.5) and allowed to stand for 30 minutes. Then 1.0ml of 0.05 M EDTA is added and the resultant solution is diluted to the mark with water. After 20 minutes, the absorbance at 632nm is measured against a reagent blank. Beer's law is obeyed over the concentration range (535)μg Ni/50ml and the molar absorptivity is 7.4×104l mol-1cm-1. For the determination of 26μg of Ni, the following amounts of foreign ions are tolerated : Co (II) 50μg (450μg by correction method), Zn (II) 60μg, Cd (II) 110μg, Cu (II) 400μg, Mn(II) 480μg, Pb(II) 2mg, Fe(III) 14mg, Al(III) 13.5mg, Mg(II) 12mg, Ca(II) 20mg.View full abstractDownload PDF (775K) -
Application of controlled potential coulometry to the automatic recording of liquid chromatography. IXYoshinori TAKATA, Giichi Muro1979 Volume 28 Issue 1 Pages 15-20
Published: January 05, 1979
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSA method for the coulometric detection of silicate, phosphate, and germanate ions with the molybdoheteropoly acids after the separation with anionexchange chromatography was investigated. The size of the separation column used was 9mm in inside diameter and 80mm in length, and strong base anion exchange resin was packed in the column. Good results was obtained when 0.4M NaOH was used as the eluent for the separation of silicate and germanate ions, and 0.4M NaOH-0.02M Na2SO4 for silicate and phosphate ions. The optimum conditions for the coulometric detection of these ions are the following : the working electrode potential kept at 0.10 V vs. ferri-ferrocyanide, H2SO4 concentration in (0.4±0.1) N, and reaction time for 5min at 40°C. The detection limit was 0.2ppm (0.1μg, as Si and P) for silicate and phosphate ions. The linear dynamic range was (0.2250)ppm (as P) for phosphate and (0.250)ppm (as Si) for silicate. And the coefficient of variation at 50ppm {ca. 200ppm (as Ge) for germanate} was less than 2% for these three ions. Alkaline earth and heavy metal ions more than 1000ppm interfered the determination because of their co-precipitation. Ions of As (V), Sb (V) and Cr (VI), however, did not interfere the detection. The method is useful for the determination of ppm level of these ions in water.View full abstractDownload PDF (943K) -
Ken MATSUMOTO, Sadayuki KOIZUMI, Toshiyasu KIBA1979 Volume 28 Issue 1 Pages 20-25
Published: January 05, 1979
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSA 40ml of phenol was put in 100ml two neck round-bottom flask equipped with a conventional distillation device and a ground glass stopper, and heated to the boiling point of phenol, 180°C. During this treatment, a slight amount of water contained in phenol was eliminated from phenol as the azeotropic vapor mixture of phenol and water at 99.5°C, and phenol was thoroughly dehydrated. After the distillation device was replaced by a reflux condenser, a piece of magnesium metal sample was put quickly into the flask through the side neck. Then the content was heated under stirring at 180°C, until magnesium metal diminished completely in phenol, forming magnesium phenoxide, while magnesium oxide remained as residue. The reaction mixture was cooled to (5060) °C, and anhydrous methanol was added to keep phenol and magnesium phenoxide in dissolving form. The residual magnesium oxide was caught on a sintered glass filter (1G5) and dissolved in 50ml of 2M hydrochloric acid. The solution was diluted to a definite volume and magnesium in the solution was determined by the atomic absorption spectrometry. All the experiments were carried out in a glove box in dry nitrogen atmosphere to avoid the influence of oxygen and water from air. By the above procedure a minute amount of magnesium oxide could be determined precisely with high reproducibility. To clarify the behaviors of magnesium metal and magnesium oxide in this separation process additional experiments were also done.View full abstractDownload PDF (1006K) -
Yasuo IWAMIYA, Takao NISHISHITA1979 Volume 28 Issue 1 Pages 26-31
Published: January 05, 1979
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA concentration equilibrium sampling-gas chromatography (CES-GC) was studied to measure the content of phenols in atmosphere. After the sample air is drawn through a sampling tube packed with suitable partition material until the concentration equilibrium of the measured components between the gas and liquid phase is reached, the tube is heated and the expelled concentrated components are introduced to GC. Mixed standard gas consisting of phenol, p-cresol and p-ethylphenol in ppb order was prepared using a diffusion cell. As the intra- and interday variations of the concentration of phenols in the standard gas checked by GC were both in the range of 4 to 7% as coefficient of variation, the standard gas was able to be used for the fundamental investigation of the CES-GC. The outline of the procedure was as followed; The standard gas was drawn through the sampling tube, packed with OV-17 stationary phase on Chromosorb G, at 60°C and a flow rate of 100 ml/min for more than 20min. After the sampling process, the tube was heated at 200°C in nitrogen flow (60ml/min), desorbed phenols were transferred to GC. It was found that reproducibilities of peak area ( W) of phenols in the chromatograms obtained by the CES-GC, were 5 to 10% in coefficient of variation. The relationships between W and concentration (C) of standard gas showed linear plots in the range of 0400ppb. The interference of moisture in air on equilibrium was found to be negligible. The method was applied to the determination of phenols in air of pilot plant area; Phenol, p-cresol and p-ethylphenol were 030, 05 and (4585)ppb, respectively. Lower limit of quantitative determination was about 5ppb. This method is easier to handle and more suitable for field practice than other methods such as cryogenic one.View full abstractDownload PDF (1036K) -
Tadao TAMURA, Jiro HIRAISHI, Kazutoshi TANABE, Shinnosuke SAËKI1979 Volume 28 Issue 1 Pages 31-35
Published: January 05, 1979
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSThe use of correlation coefficient is one of the good methods for searching infrared spectra. As the method requires collections of the spectral pattern and needs a large storage area in a computer for the reference collection, it is important to study the maximum sampling interval for digitizing a spectrum. Half value widths of 515 infrared absorption bands of liquid or solid samples are measured. Most of them have a value between 3 and 12cm-1. The result indicates that the resolution of a spectrometer is sufficient to be 1cm-1 and the sampling interval to be 0.5cm-1 when the infrared spectra of a large number of compounds are compiled into a file in a computer for the purpose of qualitative analysis. It is desirable for the search program not to consume a long computation time. A sift is useful for shortening the computation time before computing the correlation coefficients. The frequencies of the strongest absorption band are also studied for 1333 IRDC cards. It is concluded that they can be used as one of the sifts for identifying a spectrum of an unknown sample by comparing with the spectra accumulated in a computer.View full abstractDownload PDF (850K) -
Hidehiro DAIDOJI, Noboru ISHIDA, Masayasu KOBAYASHI1979 Volume 28 Issue 1 Pages 36-40
Published: January 05, 1979
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSAlthough presently available hollow cathode lamps are more than adequate for the determination of most elements by atomic absorption, brighter, more stable sources are still desirable for arsenic and selenium. Arsenic and selenium hollow cathode lamps cooled with water have been designed for this purpose in addition to being optimized for ease of use. They were 5 to 7 times more intense than conventional hollow cathode lamps, yielding stable emission signals with an about 5 min warm-up time. They had a low noise, 0.2% at 40 mA lamp current for arsenic and 0.3% at 50 mA for selenium. Another improvement in performance is an increased sensitivity (concentration μg/ml for 1% absorption), 1.3μg/ml for arsenic and 0.74 μg/ml for selenium in air-acetylene flame being attained. With a carbon tube atomizer, the aqueous solution containing arsenic and/or selenium was transferred to the furnace using 20μl pipet and heated. The sensitivities attained were 1.1 ng/ml (22 pg) for arsenic and 2 ng/ml (40 pg) for selenium. The detection limits were 6 pg for arsenic and 16 pg for selenium.View full abstractDownload PDF (753K) -
Hidehiro DAIDOJI, Noboru ISHIDA, Masayasu KOBAYASHI1979 Volume 28 Issue 1 Pages 40-43
Published: January 05, 1979
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSIn the previous work hollow cathode lamps cooled with water have been designed for arsenic and selenium, which yielded brighter and more stable intensities. A new hollow cathode lamp of arsenic was developed. In this lamp were confined neon and hydrogen gases in a cooled hollow cathode tube, and the hydrogen was allowed to be reacted with arsenic vapor produced by sputtering. The arsenuretted hydrogen became dissociated at high current in hollow cathode, giving a more intense atomic spectrum of arsenic. Another improvement in performance is an increased sensitivity with the new lamp. Carbon tube atomizer employed was a Jarrell-Ash FLA-100. Atomizing temperature was 2560°C. Sensitivity (concentration μg/ml for 1% absorption) of arsenic was as low as 1.1ng/ml (22μg) in carbon tube atomizer.The detection limit was down to 0.2ng/ml (4pg).View full abstractDownload PDF (615K) -
Takashi TANAKA, Kazuo HIIRO, Akinori KAWAHARA1979 Volume 28 Issue 1 Pages 43-47
Published: January 05, 1979
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSOrthophosphate in water is effectively condensed on anion exchange resin of molybdate form, and phosphomolybdate is formed on the resin. The resin is treated by reducing agent to develop a blue color. This color intensity is proportional to the concentration of the phosphate originally present in the water. The anion exchange resin of molybdate form is prepared by immersing Dowex 1 X8 {chloride form, (100200) mesh} in ammonium molybdate solution, and drying under reduced pressure. Procedure; Add 0.5 g of the resin into 25 ml of water sample (neutral or 0.2 M hydrochloric acid concentration), and stir for 20 min. Discard the supernatant solution and add 10 ml of reducing agent solution (ascorbic acid; 0.3%, antimonyl potassium tartrate; 0.01%, sulfuric acid; 0.25 M) to the resin, and stir for 10 min at 25°C. Discard the solution and wash the resin with water. Transfer the colored resin slurry into a 1 mm cell with water, and measure the absorbance at 705 nm against the resin as a reference. When 25 ml of the phosphate solution is treated by 0.5g of the resin, (0.11.0) ppm of phosphorus can be determined. When 1000 ml of the solution is treated, several ppb of phosphorus is detectable. Constant absorbance is obtained from the phosphate solution of pH 29 and (0.11)M hydrochloric acid concentration. 1000 ppm of chloride, nitrate, sulfate and acetate do not affect the determination of phosphate in neutral or acidic solution. Silicate produces blue color as like phosphate in neutral solution, but it produces only slight blue color in 0.2 M hydrochloric acid solution.View full abstractDownload PDF (733K) -
Epoxy acrylate resinsToshio KOIKE, Akira OKAMOTO, Kimitaka SATO, Ryutaro MATSUMOTO1979 Volume 28 Issue 1 Pages 48-51
Published: January 05, 1979
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSAnalytical technique using infrared spectra was applied to newly synthesized nine kinds of electron beam curing (EBC) type epoxy acrylate resins having the basic chemical structure of AA-(EpH-BPA)n-EpH-AA. The results obtained are summarized as follows : (1) After EBC process, the infrared spectrum of resin varies only at the characteristic bands of AA; the double bonds in the part is found to disappear. (2) AA, MA (metacrylic acid) and CA (crotonic acid) in the partial structure can be distinguished clearly with each other by their characteristic bands. (3) Although the infrared spectrum of EpH (epichlorohydrin) is almost analogous to that of MEpH (methyl epichlorohydrin), they are able to be distinguished from the difference of the ratio of intensities between the 827 cm-1, band (12μm band of epoxide) and the 810 cm-1one of AA.(4) From their general spectral feature, the resins containing BPA and -OOCC16H32COO- can be distinguished with each other. (5) Linear relation is found between the mole feed ratio and the intensity ratio of D1720/D1605. Thus, the technique shown above gives many informations about the structure of the similar type of unknown samples, and the analytical results thus obtained play an important role in the progress of the study about the EBC type resin coating steel plate.View full abstractDownload PDF (718K) -
Phthalic acid ester resinsToshio KOIKE, Akira OKAMOTO, Kimitaka SATO, Ryutaro MATSUMOTO1979 Volume 28 Issue 1 Pages 52-57
Published: January 05, 1979
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSAnalytical study by infrared spectrometry was applied to newly synthesized 25 kinds of electron beam curing (EBC) phthalic acid ester resins having the basic chemical structure of AA-(diEG-oPHA)n-diEG-AA (AA : acrylic acid, diEG : diethylene glycol, oPHA : o-phthalic acid). The wavenumbers of characteristic bands as well as their intensities were studied in detail, and the data of these resins were compared with each other. The results obtained are summarized as follows : (1) The variation of the infrared spectra of the resin after EBC process appears only at the bands characteristic to the double bonds of AA part. (2) AA and MA (metacrylic acid) in the partial structure can be distinguished clearly with each other by their characteristic bands. For example, AA has two ν(C=C) bands at 1640 and 1620 cm-1, while MA has only one band at 1640 or 1620 cm-1. (3) The relative intensity of the band at 1460 cm-1 varies depending on the change in the partial structure of EG, from mono to di, tri, …….The similar tendency is also observed for their band at 1640 cm-1. (4) The partial structure of oPHA can be identified by its characteristic bands, even when it is substituted with dicarboxylic acid such as tHPA (tetrahydrophthalic acid) or ITA (itaconic acid). (5) Depending on the mole feed ratio, the characteristic band intensities of AA, MA or oPHA varies. Their technique is useful for the qualitative analysis of the sams type of resins with unknown chemical structure, and the analytical results obtained in this study play an important role in the development of the study for the EBC type resin coating steel plate.View full abstractDownload PDF (893K) -
Kunio HIROTA, Yoshinori TAKATA1979 Volume 28 Issue 1 Pages 58-60
Published: January 05, 1979
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA method for splitless injection to capillary column in gas chromatography was examined. A slightly reconstructed oridinary splitting injection port was used. It was enable to supply carrier gas to the both of inlet and outlet of the port during sampling period using three way solenoid valve connected with split resistance and with carrier gas supply. Timer combined with the solenoid valve for switching the splitless path to splitting path was used for the controlling the period of sample introduction to the column. The outline of procedure was as follows : set up splitting path and adjust oven temperature : 30°C, column flow : 1 ml/min, split flow : 100 ml/min; then change to splitless path and immediately introduce a sample; after a certain period, return splitting path by timer and heat oven rapidly to 170°C. In order to get the recovery through the column more than 90%, when a flow control valve or a pressure control valve was used as a regulator for carrier gas, it was necessary for sample introduction to take more than 15 s or 60 s, respectively. However, to lenghten the samling period caused peak broadening for more volatile constituents. It was found that the quantitative analysis of the constituents which boiling point was higher than 195°C was possible without any peak broadening. The linear dynamic range for splitless injection was 05μl and the splitting 01μl. The coefficients of variation for splitless and splitting injection method were (24)% and 8%, respectively. The method was thought to be useful for simply getting high sensitivity and good accuracy.View full abstractDownload PDF (484K) -
Norio FUKUZAKI, Toshio SUZUKI, Ryuichi SUGAI, Tatuo OSHINA1979 Volume 28 Issue 1 Pages 60-63
Published: January 05, 1979
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSThe ion-selective electrode method for the microdetermination of iodine in environmental sample was investigated. To isolate iodine from substances influencing on electrode method such as sulfide and large amount of alkali used for alkali fusion of the sample, solvent extraction method was utilized. The recommended procedures are as follows : Add 2 ml of sulfuric acid (1 : 1) and sodium nitrite solution (1%) to 150 ml of sample solution in a 250 ml separatory funnel and mix throughly. After standing for (23) min, add 15 ml of carbon tetrachloride and shake for 1 min. Transfer the organic phase to a 200 ml separatory funnel. Repeat the extraction of iodine once more with 10 ml of carbon tetrachloride and combine with the first extract. After washing with diluted sulfuric acid, transfer the organic phase to a 50 ml separatory funnel containing 10 ml of ( 10-210-4) M sodium bisulfite solution. Shake for 1 min, discard the organic phase, transfer 5 ml of the aqueous phase to a 100 ml polyethylene beaker, add 10 ml of 10% phosphate solution, and then determine the iodide concentration by ion-selective electrode method. The recovery of iodine from the 150 ml of supplying water containing (2150)μg of iodine was examined for above procedure. The sufficient recoveries were obtained in addition of more than 5 μg. This method was applied to the determination of iodine in lowland rice near an iodine manufacturing plant. Results were well agreed with those obtained by the neutron activation analysis.View full abstractDownload PDF (679K) -
Naobumi OI, Hiroo SHIMADA, Osamu HIROAKI, Masao HORIBA, Hajimu KITAHAR ...1979 Volume 28 Issue 1 Pages 64-65
Published: January 05, 1979
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSThe gas chromatographic resolution of enantiomers of organophosphoramidothioate containing an asymmetric phosphorous atom on a chiral stationary phase has been succeeded, and the satisfactory results were obtained. For example, (±)-O-ethyl-O-(2-nitro-5-methylphenyl)-N-isopropylphosphoramidothioate was resolved within about 2.3 h at 180°C on a 60 m × 0.25 mm glass capillary open tubular column coated with N, N'-[2, 4-(6-ethoxy-1, 3, 5-triazine) diyl]-bis-(L-valyl-L-valyl-L-valine isopropyl ester). Consequently, the optical purity of this compound, which is known as a herbicide, can be easily determined from the ratio of the resolved peak areas. It is noticeable that organophosphoramidothioates, containing no asymmetric carbon atoms, have been resolved on an optically active stationary phase containing only asymmetric carbon atoms.View full abstractDownload PDF (306K) -
Toshio IMANARI, Motoichi MIYAZAKI1979 Volume 28 Issue 1 Pages 65-66
Published: January 05, 1979
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSAn electrodialytic apparatus for sample preparation in analytical process was developed. Apparatus I (for extraction of low molecular cationic substances) : This is composed of 4 parts-anode vessel (A), sample chamber (B), extraction chamber (C), and cathode vessel (D) in series. On both sides of B, cellulose membranes are placed, and at the boundary of C and D, an anion-exchange membrane (A-201, Asahikasei Chemical Industry Co. Ltd.) is set up. Apparatus II (for extraction of low molecular anionic substances) : This is composed of A, C, B and D. A cation-exchange membrane (K-101) is used at the boundary of A and C, and cellulose membranes are on both sides of B. In apparatrs I, 0.5 ppm solution of Cu(II) or Zn (II) in 0.05 N CH3COOH was placed in B and the other cells were filled with 0.05 N CH3COOH. Electrodialysis was carried out with the current of 10 mA/cm2 for 20 min. The concentrations of Cu(II) and Zn (II) in C were determined by atomic absorption spectrometry and the recoveries of them were about 80 and 90% respectively. In apparatus II, 0.5 ppm solution of Cu (II) or Zn(II) was electrodialyzed as EDTA complexes. The condition was as follows: 0.05 N NH4OH-1 mM EDTA, 10 mA/cm2, 20 min. The recoveries of Cu(II) and Zn (II) were almost 100%.View full abstractDownload PDF (362K)
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