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Volume 26, Issue 3
Displaying 1-17 of 17 articles from this issue
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Ryozo NAKASHIMA, Shozo SASAKI1977 Volume 26 Issue 3 Pages 145-149
Published: March 05, 1977
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSOn the introduction of sample aerosol into the UHF-plasma torch, heating in a high-frequency induction furnace was utilized for silver and copper salts doped in a graphite powder (Nippon Carbon Co. SP-2). High purity nitrogen gas was supplied into the furnace at a rate of 100 ml/min, and produced aerosol was premixed with 3.0l/min argon gas, then introduced into the torch. The sample was heated in a graphite crucible. The measurements were made at 328.1 nm for silver and 324.8 nm for copper.
Constant peak areas were obtained at >1100°C for silver nitrate, >1300°C for silver chloride, bromide, iodide, and sulfate, respectively. For copper salts, similar results were obtained at >1900°C for nitrate, and >1800°C for cupric chloride. Peak area for silver nitrate was the highest among various kinds of silver salts examined. On the contrary, in copper salts, the peak area of chloride was higher than that of nitrate. Those signals of silver chloride in the range of (0.7100)ng and of cupric chloride in the range of (102000)ng copper were calibrated. The linear relations were obtained above 5 ng silver and 100 ng copper, with a slope of 45° on the log-log plots. Below 5 ng silver and 100 ng copper, another linear relation with a slope less than 45° was obtained, which was considered to be responsible for the trace oxygen remaining in the system. The detection limits of silver chloride and cupric chloride were 0.5 ng as silver and 10 ng as copper, respectively. The coefficients of variation for several measurements were in the range of (1530)% for (0.10.2)μg of silver and (1.02.0)μg of copper.
The efficiencies of introducing silver or copper salts were examined and the introduced species in the torch were discussed with reference to the peak areas.View full abstractDownload PDF (968K) -
Chikao TSURUMI, Keiichi FURUYA1977 Volume 26 Issue 3 Pages 149-153
Published: March 05, 1977
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESS2-(2-Thiazolylazo)-5-dimethylaminophenol(TAM)reacts with titanium to form a reddish-violet complex, which can be extracted quantiatively from the aqueous solution into benzyl alcohol in the presence of 1, 3-diphenylguanidine (DPG) in the pH range from 4.2 to 5.2. The titanium complex is stable for 2 hours and shows an absorption maximum at 583 nm. The molar extinction coefficient at this wavelength is 3.59×104 l mol-1 cm-1. Beer's law is obeyed up to 1.2μg/ml of titanium. The molar ratio of titanium to TAM in the complex was confirmed to be 1:2 by both the continuous variation and mole ratio methods. A number fo ions which interfere with the determination can be masked by the addition of various masking agents. Tantalum zirconium, iron(II), cobalt, citrate and oxalate ions seriously interfere with the determination of titanium.View full abstractDownload PDF (785K) -
II. Colorimetric determination of 17-hydroxycorticoidsHiroshi TOKUNAGA, Toshio KIMURA, Jiro KAWAMURA1977 Volume 26 Issue 3 Pages 154-158
Published: March 05, 1977
Released on J-STAGE: May 07, 2010
JOURNAL FREE ACCESSThe present authors have reported the colorimetric determination of 17-desoxycorticoids by convertion to the coresponding 21-aldehydes with cupric acetate, followed by condensation with pyrrole. This paper describes modification to the previous method and its application to the determination of prednisolone(PSL), methylprednisolone (MPSL), prednisone (PS), hydrocortisone (HCS), cortisone(CS) and tetrahydrocortisone (THCS). The procedures were as follows: To each (2.530)μg of PSL, MPSL, PS, HCS, CS and THCS dissoloved in 0.5 ml of methanol, 0.2 ml of the cupric acetate-methanol solution(1→4000)was added. After kepy at room temperature for 30 minutes, the solution was mixed with 2 ml of the hydrochloric acid-methanol mixture (3:7) and then with 0.4 ml of the pyrrole-methanol solution (1→40). After 30 minutes at 40°C, 4 ml of benzene and 2 ml of 10% hydrochloric acid were added to the reaction mixture, and the mixture was well sitted. The benzene layer was dehydrated with anhydrous sodium sulfate, and the absorbance was measured at each absorption maximum. The absorption maxima of PSL, MPSL, PS, HCS, CS and THCS, were 590, 594, 590, 587, 600 and 590 nm, and their apparent molar extinction coefficents were 29100, 29500, 35000, 26600, 28400 and 27500, respectively. Prednisolone acctate, cortisone accetate, hydrocortisone acetate, betamethasone and triamcinolone were all inactive for this reaction. This method was also successfully applied to the determination fo PSL containing in presonisolone preparation.View full abstractDownload PDF (766K) -
Yoshinori KIDANI, Shizuo UNO, Kenji INAGAKI1977 Volume 26 Issue 3 Pages 158-162
Published: March 05, 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSSchiff's base-Cu(II) chelates of acidic and basic amino acids are little extractable with MIBK even in the presence of bathophenanthroline (bathophen) in alkali, while they are well extracted in acidic media. The separation and determination of a mixture of L-methionine and L-histidine by atomic absorption spectrophotometry were done. One ml each of 4.0×(10-510-4)M aqueous L-methionine and aqueous L-histidine solution, 30μl of salicylaldehyde, 1.0 ml of 2.0×10-3 M aqueous cupric acetate solution and 7.0 ml of boric acid buffer solution of pH 10.0 were taken into a 30 ml centrifuge tube and mixed. After standing for 5 minutes, the mixture was shaken twice with 10.0 ml of chloroform for 10 minutes and centrifuged for 5 minutes. Then, 7.0 ml of upper aqueous phase was transfered to a 30 ml centrifuge tube. To this was added 10.0 ml of 1.0×10-4M bathophen-MIBK solution. Being shaken well for 5 minutes, it was centrifuged for 5 minutes. The copper amount in the organic phase were determined by atomic absorption spectrophotometry, relative to a reagent blank (Determination of L-methionine). Another 5.0 ml of the upper aqueous phase was transfered to a 30 ml centrifuge tube and was adjusted at pH 4.5 by adding 0.5 M aqueous acetic acid solution. To this was added 10.0 ml of 1.0×10-4 M bathophen MIBK solution. After being shaken well for 5 minutes, the mixture was centrifuged for 5 minutes. The copper amount in organic phase were determined by atomic absorption spectrophotometry, relative to a reagent blank (Determination of L-histidine). The pH optima of L-methionine and L-histidine were found to be 10.0 and 4.5, respectively. There were linear relationships between the absorbance and the concentration in the range of (3.030.0)μg/ml of L-methionine and (3.131.0)μg/ml of L-histidine. The recovery test was favourable. Deviations for L-methionine and L-histidine were determined to be 0.84 and 0.84, and coefficients of variation were 1.86% and 2.29%, respectively (Table 1).View full abstractDownload PDF (856K) -
Takatoshi KONO1977 Volume 26 Issue 3 Pages 162-168
Published: March 05, 1977
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSIn flame atomic absorption spectrophotometry benzene, toluene, xylene, hexane, cyclohexane, chloroform and carbon tetrachloride are hardly usable as solvents for extraction because of the appearance of white flame, the blow-out of flame or unstable burning.
In the present study, a new type of burner was designed of which the flame is sandwiched with oxygen. The determination of copper was examined with it. Sodium diethyldithiocarbamate was added to a sample solution of pH 5.0 and copper was extracted with above solvents. Effect of acetylene-oxygen flow rate and optimum condition of burner were examined at air flow rate of 13 l/min. In each case, no appearance of white flame, blow-out of flame and flash back were observed, and the determination was satisfactory.
When the organic solvents were used, the sensitivity (μg/ml/1%) were 0.0340.008 and the detection limits (μg/ml) were 0.0040.001. Using hexane, the sensitivity was 0.008 and it was about twenty times higher than in the case of aqueous solution.
Copper in aluminum alloy was determined with good results by this procedure.View full abstractDownload PDF (1132K) -
Fundamental studies on the extraction of uranium(VI). IVYasumasa SHIGETOMI, Takehiro KOJIMA, Mutsuaki SHINAGAWA1977 Volume 26 Issue 3 Pages 168-173
Published: March 05, 1977
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSStudies have been made on the separation of uranium (VI) from various metals with a column, packed with the gel containing titanium hydroxide. Gel particles as carrier were prepared with acrylamide, N, N-methylenebisacrylamide and titanium hydroxide. Uranium (VI) was able to be eluted almost quantitatively from the gel column, which consisted of the gel particles {(20100) mesh}, by 0.1 M sodium carbonate solution. On the other hand, dilute hydrochloric acid {(0.10.2) M} was employed as eluting agent for nickel (II) and iron (III). It was observed that uranium (VI) was able to be separated from nickel (II) and iron (III), but could not be separated from barium (II) and lanthanum (III). Uranium (VI) could be recovered more than 90% when the solution containing 93μg of uranium (VI) as well as 200μg each of nickel (II) and iron (III) was used.View full abstractDownload PDF (961K) -
Masahiro KUDO, Yoshimasa NIHEI, Toru MACHIYAMA, Keiichi FURUYA, Hitosh ...1977 Volume 26 Issue 3 Pages 173-178
Published: March 05, 1977
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSSurface compositions of binary alloys were investigated by means of X-ray photoelectron spectroscopy (XPS) in the cases of copper-nickel and palladiumsilver alloys. The relationship between atomic ratio and peak intensity ratio was not linear in the calibration curves which were obtained assuming that the surface compositions of samples polished mechanically were approximately the same as those of bulk alloys. Using Henke's intensity equation and supposing that the reciprocal of an electron mean free path can be expressed as a linear combination of inelastic cross sections and atomic densities, some parameters which affect peak intensities were calculated by a least square curve-fitting method. Some of them, however, did not seem suitable when considering their physical meanings, so it might not be sufficient to use mean free pathes according to this type of approximation for these binary alloy systems. In spite of all these problems the calibration curves obtained were very useful for the evaluation of relative changes of surface compositions of these alloys after heating in vacuum. In the case of copper-nickel alloy, it was observed that surface nickel concentration decreased after heating for samples of all composition range and it is a reasonable tendancy according to the theory of bulk thermodynamics. On the contrary, in the case of palladium-silver alloys containing palladium mole fractions of 59.9% and 40.0%, it was observed that surface concentration of palladium was enriched abruptly by heating at 350°C for 10 minutes and recovered by heating at 500°C for 100 minutes. This phenomenon cannot be explained by the theory of bulk thermodynamics.View full abstractDownload PDF (985K) -
Yoshihiro YOSHII, Akiyoshi ITO, Osamu MANABE1977 Volume 26 Issue 3 Pages 179-182
Published: March 05, 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSThe column (1m×2.1mm I.D.) packed with Zipax-strong anion exchange resin was equilibrated and eluted with 0.03 M NaNO3 solution at 40°C. The flow rate was adjusted to 0.50 ml/min, and the column effluent was monitored at 280 nm.
Under these conditions, the isomers of sodium phenolsulfonates were fully separated. The elution times were 5.4, 8.4, 11.3 and 26.0 min for sulfanilic acid, p-, m-, and o-phenolsulfonate, respectively. Sulfanilic acid was the best internal standard for the determination of each isomer of phenolsulfonate.
The limit of detection was 0.1μg.
The coefficient of variations in the determination of o-, m- and p-phenolsulfonate, were 1.68, 0.96 and 0.80, respectively.View full abstractDownload PDF (516K) -
Toshiyuki MITSUI, Tsugio KOJIMA1977 Volume 26 Issue 3 Pages 182-186
Published: March 05, 1977
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSAldehydes were determined satisfactorily by atomic absorption spectrophotometry (AAS).
The recommended procedures are as follows: The Tollens' reagent is prepared by mixing 5 ml of 13.06 mg-Ag/ml, 2 ml of 39.95 mg-NaOH/ml, 0.4 ml of conc. NH4OH and water (final volume 25 ml). To each sample solution is added 1 ml of Tollens' reagent and the resultant solution is diluted to 10 ml with water. After standing for 1 hour, the precipitates of silver are filtred off. (I), filtration method: To one ml of the filtrate is added 2 ml of 12.6 N nitric acid and it is diluted to 50 ml with water, and the silver content is measured by AAS. (II), precipitation method: The precipitate is dissolved in 6 ml of 12.6 N nitric acid and it is diluted to 100 ml with water, and silver content is measured by AAS.
The limit of identification for 12 aldehydes are as follows: acetaldehyde (0.025 mg by filtration method, 0.025 mg by precipitation method), propylaldehyde (0.760, 0.760), n-butylaldehyde (0.052, 0.025), crotonaldehyde (0.015, 0.015), benzaldehyde (0.042, 0.025), cinnamaldehyde (0.051, 0.051), phenylacetaldehyde (0.004, 0.004), p-tolualdehyde (0.201, 0.120), o-chlorobenzaldehyde (0.231, 0.231), p-chlorobenzaldehyde (0.110, 0.110), m-nitrobenzaldehyde (0.144, 0.144), and glyoxal (0.025, 0.005). Presence of (5080) times of acetone, ethyl alcohol and acetic acid and (3.087.28) times of phenol, aniline, benzoic acid, nitrobenzene and m-aminophenol doesn't interfere. The metal ions, o-, p-aminophenol, resorcinol, benzoin and benzil give remarkable ferences, but the interference of the metal ions can be eliminated successfully by removing aldehydes with chloroform.View full abstractDownload PDF (797K) -
Tsuyoshi NOMURA, Genkichi NAKAGAWA1977 Volume 26 Issue 3 Pages 186-190
Published: March 05, 1977
Released on J-STAGE: January 18, 2010
JOURNAL FREE ACCESSo-Aminophenol is oxidized very slowly with dissolved oxygen in a pH range from 6 to 8. On the other hand, silver ion oxidizes it rapidly. The oxidation product, 3-aminophenoxazin-2-ones, gives a very sensitive tensammetric wave from which the amounts of silver ion can be determined. The recommended procedure for the determination of silver is as follows: Take 2 to 40μg of silver into a 25-ml measuring flask, add 5 ml of 1 M sodium borate-1M acetic acid buffer solution and 0.5 ml of 5 × 10-3 M EDTA, and adjust the pH to 7.58.0. Add 1.5 ml of 10-3 M o-aminophenol as quickly as possible, and dilute to 25 ml with water after shaking. Place the measuring flask in a water bath at (40±0.1)°C for 2 hours. Transfer an aliquot of the solution into a polarographic cell and record the a. c. polarographic wave between -0.2 and -0.6 volt vs. SCE. Ce (IV), Mn (VII), CN- S2O32-, SCN- and large amounts of Cu, Hg and Fe (III) interfere. For the determination of silver in crude copper and aluminum alloy, the precipittaion of silver with p-dimethylaminobenzylidenerhodanine was applied for the separation of silver from large amounts of copper or aluminum.View full abstractDownload PDF (648K) -
Masuo KOJIMA, Fumio UEHARA, Hideo TOMIOKA, Toichi TERAOKA1977 Volume 26 Issue 3 Pages 191-195
Published: March 05, 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSAccording to the fact that lithium is selectively precipitated by a strongly alkaline potassium periodate solution, authors investigated the method of quantitative precipitation of lithium periodate.
At first, a definite amount of sample solution which contains lithium ion up to 20 mg is taken, concentrated up to 2 ml. To this 5 ml of strongly alkaline potassium periodate solution is added, and the solution is warmed on a water bath at about 70°C. After cooling, precipitate is filtered by Millipore filter FA (Teflon 1 μ) and washed 4 times with saturated lithium periodate aqueous solution. Then the precipitate is dried for 20 minutes in a vacuum drying oven at 50°C. The precipitate obtained by this procedure is supposed to be Li5IO6.
As a result of the titration of the lithium periodate with sodium thiosulfate and arsenic trioxide, valency of iodine was found to be +7. Then the quantity of lithium in the periodate was determined by atomic absorption spectrometry. By means of the continuous variation method and the molar ratio method, the combination ratio of lithium to periodate was proved to be 5 : 1.
From the absorption curve of 4×10-4M aqueous solution of lithium periodate, periodate ion was supposed to be H3IO62-.
According to the agreement between the pH value of saturated solution calculated with dissociation constant of H5IO6 and that of measurement, the state of H5IO6 in aqueous solution was determined to be H3IO62-.
The method, using potassium periodate solution, makes it possible to do the semimicro gravimetric analysis of lithium. Small amount of cesium and rubidium does not interfere, while sodium interfere above 40 mg.View full abstractDownload PDF (796K) -
Hiroto WATANABE, Jun'ichiro MIURA1977 Volume 26 Issue 3 Pages 196-198
Published: March 05, 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA simple and sensitive dual-wavelength spectrophotometry for copper was developed by dissolving dithizone and its copper chelate in water with Triton X-100. The free dithizone solution is unstable but the unstability was greatly improved by using the zinc dithizonate as a color developing reagent. Copper(II) reacts with dithizone below pH 2.7 to form the stable chelate. The zinc dithizonate rapidly and completely dissociates to give free dithizone below pH 2.0. Free dithizone is easily oxidised in the presence of iron (III), but iron (III) can be masked with pyrophosphate and hence the oxidation of dithizone due to free iron (III) can be largely prevented. Two wavelengths, 510 and 671 nm, at which a reagent blank shows the same absorbance were selected. The analytical procedure is as follows: take the solution containing less than 2.50 μg of copper in a 50 ml-volumetric flask and add 4 ml of 1 N hydrochloric acid to adjust the pH of the final solution to 11.5, 1 ml of 0.5 M potassium pyrophosphate, and 5 ml of the zinc dithizonate solution (dithizone; 0.008 g, triton X-100; 40 g, water; 160 g, 1.53×10-2 M zinc solution; 1 ml, and pH 5.3 CH3COOH-CH3COONa buffer solution; 10 ml). Dilute to the mark with water and measure the differential absorbance at 510 nm and 671 nm with the full scale range of 0.03. Beer's law is obeyed over the concentration range (02.50)μg Cu/50 ml. The precision (95% confidence) is ±0.06 μg for 1.48μg of copper. The molar absorptivity is 2.8× 104 l mol-1 cm-1. The following amounts of foreign ions are tolerated in the determination of 2.00 μg Cu/50 ml: Fe(III); 1mg, Ni; 0.2mg, Zn; 0.3 mg, Co; 30 μg, Pb; 30 μg, Cd; 30 μg, and Mn; 50 μg. The method can be applied to the determination of copper in river water.View full abstractDownload PDF (542K) -
Hideo NAGAI, Toshio DEGUCHI, Isao SANEMASA, Takanari NAKAMURA1977 Volume 26 Issue 3 Pages 198-200
Published: March 05, 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSWhen a mixture of lanthanoid ions was chromatographed on a filter paper disk impregnated with oxine by dilute acetic acid saturated with phenol and oxine, it was supposed that a oily hydrophobic phase was gradually formed over the surface of the impregnated oxine. Therefore, some extraction chromatographic partition between the oily hydrophobic phase and the developer should be expected. This study was undertaken to confirm the separation mechanism. The result of batch experiments suggested that a mixture of four ions from La to Nd would be successfully separated by 0.5% acetic acid solution saturated with phenol and oxine, a mixture of five ions from Nd to Tb by 1% acetic acid solution saturated with phenol and oxine, and a mixture of seven ions from Tb to Lu by 2% acetic acid solution saturated with phenol and oxine. The results obtained here are consistent with the chromatographic performance of the impregnated filter paper.View full abstractDownload PDF (544K) -
Tsutomu FUKASAWA, Takeshi YAMANE, Takeshi YAMAZAKI1977 Volume 26 Issue 3 Pages 200-202
Published: March 05, 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSA simple and sensitive method has been developed for the determination of manganese in high-purity selenium. Selenium was expeled mainly as selenium dioxide by being heated in a quartz boat (net volume, ca. 2 ml) in an electric furnace at 600°C in air stream of 150 ml per min. for 35 min. Expeled selenium dioxide was absorbed in a water trap. Combustion of sample at lower temperature (below ca. 500°C) was time-consuming and was liable to product red-selenium. After the complete separation of selenium, the combustion boat was taken out from the furnace and cooled to room temperature. The residue in the boat was dissolved in 0.5 ml of 6M hydrochloric acid and the solution was gently evaporated to dryness on a hot-plate. Then manganese in the residue was dissolved in an acetate buffer solution (pH 3.8) and was determined by the catalytic method based on the oxidation of Malachite Green by periodate, as previously described. The conditions of combustion and others were studied in detail. The proposed method allows the determination of manganese as low as 10 ppb for 1 g of sample.View full abstractDownload PDF (576K) -
Hideo AKAIWA, Hiroshi KAWAMOTO, Yukihiko TSUTSUMI1977 Volume 26 Issue 3 Pages 202-205
Published: March 05, 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSThe extraction procedure for the separation of zinc (II) from cadmium(II) is as follows: Twenty ml of the aqueous solution (pH=5.7) is equilibrated with the equal volume of 5×10-3M 2-thenoyltrifluoroacetone (TTA=Htta) and 5×10-2M 2, 6-lutidine in carbon tetrachloride by shaking the mixture for 5 min. Only zinc is selectively extracted into the organic phase.
The synergistic effect caused by pyridine (py) could be explained through the formation of an adduct, Zn(tta)2(py)2 or Cd(tta)2(py)2. On the other hand, the main synergistic adduct formed by using 2, 6-lutidine was found to be Zn(tta)2(2, 6-lut.). The difference in the composition of adducts in the above cases is attributable to the steric effect of methyl groups in 2, 6-lutidine. The steric effects by the presence of other ortho-substituents of pyridine were also studied.View full abstractDownload PDF (490K) -
Mutsuo ISHIZAKI1977 Volume 26 Issue 3 Pages 206-207
Published: March 05, 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSDetermination of selenium in biological materials by flameless atomic absorption spectrometry using carbon tube atomizer has been impossible, because of the suppression of absorbance of selenium by coexisting materials and of vaporization of selenium itself during ashing in carbon tube. The proposed method will solve the above problems.
Procedure: (1) Drying and combustion of samples: Blood; 1 ml of blood was added to a 70 mg of absorbent cotton which was hung with thread and was dried with a drying oven for 12 hrs. at 60°C. Viscera and flesh; 1 g of the sample was taken on a piece of Japanese paper (5 cm2) and dried with drying oven for 12 hrs. at 60°C. (2) Preparation of test solution: The dried sample was burnt in the oxygen flask. Selenium was taken up in 20 ml of 0.01 N HCl. The solution was passed through a 1 × 10 cm cation exchange resin column (Amberlite IR-120, hydrogen form). The column was rinsed with 20 ml of distilled water. The combined solution was transfered to the separating funnel and 2 ml of 20% hydroxylamine hydrochloride and 10 ml of 12 N HCl were added. Selenium was extracted with 1 ml of 0.01% dithizone carbon tetrachloride. This extracted solution was used as test solution. (3) Analysis: 2μl aliquots of the test solution was injected into the carbon tube with a microsyringe. The carbon tetrachloride in the carbon tube was vaporized by heating for 20 s at 100°C. Then was added 50μl of 0.6% nickel nitrate solution into the carbon tube and the selenium was determined according to the operating condition shown in Table 1.
Under this condition, selenium in biological materials could be determined with a recovery of higher than 93% and with a variation coefficient of about 8%.View full abstractDownload PDF (237K) -
1977 Volume 26 Issue 3 Pages 208
Published: 1977
Released on J-STAGE: June 19, 2009
JOURNAL FREE ACCESSDownload PDF (56K)
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