All issues
Volume 20, Issue 9
Displaying 1-34 of 34 articles from this issue
- |<
- <
- 1
- >
- >|
-
Makoto NOSHIRO, Kiyoshi MATSUMOTO1971 Volume 20 Issue 9 Pages 1069-1075
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSThe CHN analyzer (Yanagimoto MT-2) for organic compounds was applied to inorganic substances as follows.
(1) Determination of inorganic compounds. The element analysis of inorganic compounds having CO32-, HCO3-, NO3-, NO2-, CN-, SCN- and NH4+ was done with high reliability as the elementary analysis of organic compounds.
(2) Determination of water in inorganic compounds. The results of the determination of water of crystallization, the fractional determination of hygroscopic water and fixed water in amorphous silica and the determination of water in clay minerals coincided with the theoretical values or the results by thermogravimetric analysis.
(3) Analysis of carbonates. More reliable and significant informations were obtained for the analysis of limestone and dolomite compared with those from the measurement of ignition loss.
The determination of sodium hydrogen carbonate in sodium carbonate could be carried out more easily and rapidly than the titration method. The carbonates that could not be analyzed by usual procedure because of their high decomposition temperature (>900°C) could be analyzed by the addition of the glassforming oxides.View full abstractDownload PDF (1142K) -
Chozo YOSHIMURA, Kunihiko TAMURA, Kozi KOJYOMA1971 Volume 20 Issue 9 Pages 1075-1079
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSDetermination of terpens (alcohol, aldehyde and keton) and consecutive titration of the mixtures have been developed by conductimetry in DMF with carbonyl reagent or Lewis acids. Terpens can be determined with phenyl hydrazine, silicon tetrachloride, magnesium chloride and aluminum chloride with their reactive ratios as follows; citronellal : phenyl hydrazine=1:1 and 1:2, geraniol : MgCl2=1:1 and 1:2, and menthol : SiCl4=1:1 and 1:2.
Consecutive conductimetric titration of the mixed solution with magnesium chloride gave satisfactory results, whereby the reaction advanced in the order -OH, -CHO and =CO. The limit of determination by this method was about 5×10-5 mol/l.View full abstractDownload PDF (652K) -
Hiroshi NISHIDA1971 Volume 20 Issue 9 Pages 1080-1084
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSBeryllium with Chromazurol S (CAS, H4L) in the presence of zephiramine (tetradecyldimethylbenzylammonium chloride, ZCl) formed a 1 : 2 complex, Be (HLZ)2-, with an absorption maximum at 610 mμ, The absorbance of the complex was increased by warming the solution at pH 34 containing beryllium in the presence of 550 mg of EDTA before an addition of CAS and zephiramine. Its absorbance was highest and invariable in 1.03×10-4M CAS, 1.08×10-3M zephiramine and 1×10-3M EDTA at pH 4.75.5. Beer's law held for 0.0040.08 ppm of beryllium and the molar absorptivity at 610mp was 1.09×105. This complex was applied to the spectrophotometric determination of less than 0.1% of beryllium in steels and aluminum alloys with relative standard deviation smaller than 3%. The procedure was as follows.
Dissolve 0.25 g of a sample in hydrochloric acid and nitric acid and evaporate to dryness. Take up the residue with 3ml of 6M hydrochloric acid by warming, and dilute with water exactly to 100 ml. Take an aliquot containing 0.12 μg of beryllium. Add 11.3 ml of 5% EDTA solution and adjust pH to 34 with 0.5 M sodium acetate solution. After evaporation to 5 ml and adjustment of pH to 5.2, add 0.6 ml of 0.25% CAS solution and 2 ml of 0.5% zephiramine solution. Dilute exactly to 25 ml with water and allow to stand for 30 min. Measure the absorbance at 610 mμ against a reagent blank obtained by the same procedure. The concentration of hydrochloric acid in the sample solution had to be held constant.View full abstractDownload PDF (576K) -
Isotope dilution and spectrophotometric methodsMasao TAKAHASHI, Yuji MATSUDA, Yukio TOITA, Misao OUCHI, Takuji KOMORI1971 Volume 20 Issue 9 Pages 1085-1091
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSA study was made on the determination of traces of uranium in sodium metal by isotope dilution-mass spectrometry or by Arsenazo III spectrophotometry after the vacuum distillation of sodium using a stainless steel crucible. In the isotope dilution method, 5 g of sample was taken into the crucible containing a known quantity of enriched isotope as a spike and distilled at 350°C under vacuum. Uranium in the residue was separated by tri-n-octylamine extraction and the isotopic ratio was measured mass-spectrometrically. It was confirmed by this method that uranium was not lost at all during the distillation. In the spectrophotometric method, after the distillation of sodium and removal of iron by ethyl ether extraction, uranium was reduced to uranium (IV) with zinc and determined spectrophotometrically. The limit of detection of uranium was about 1 ppb in the isotope dilution method and about 100 ppb in the spectrophotometric method. The content of uranium in a sodium metal determined by the former method was lower than 2 ppb.View full abstractDownload PDF (1249K) -
Pulverization methods by the sudden temperature change of the samples. IYasuo AZUMA, Yukito YOSHIDA1971 Volume 20 Issue 9 Pages 1092-1096
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSThe grinding is a primary and indispensable step to prepare the are samples suitable for the chemical analysis, but it is often laborious and timeconsuming to crush the hard ores. A new procedure for facilitating the pulverization of the ores is proposed in the present report.
It consists of the rapid heating of ores at a definite, high temperature and the subsequent quenching with cold water prior to crushing.
The results are summarized as follows:
(1) For the silicate samples, the time needed for the grinding is reduced to about 1/4 as compared with the grinding without prior heat-treatment.
(2) The effectiveness of the pretreatment is increased with increasing temperature of heating.
(3) Repetition of the same pretreatment has only little effect on the grain-size distribution of the crushed samples.
(4) For the variety of are samples, the effects become larger with increasing hardness of the samples.
This pretreatment is very useful for the cases where the loss by heat of the elements to be determined would be negligibly small.View full abstractDownload PDF (755K) -
Shinji TAKAGI, Kazuhiko ENDO, Kazuma KUMAI1971 Volume 20 Issue 9 Pages 1097-1102
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSImprovements were made on the West-Gaeke method on the basis of examination on the errors in the result of the conventional procedure.
The reproducibility of the conventional West-Gaeke method was 6.4% in coefficient of variation, but improvements in sampling and spectrophotometric processes reduced this value to 2.0%.
Results on a standard gas sample by using absorbing solution of 30°C indicated that values by the conventional method were approximately 9% lower than the calculated values. The collection efficiency of sulfur dioxide was 100%, and the difference was due to the oxidation of sulfur dioxide by aeration in the absorbing solution. Effect of nitrogen dioxide, chlorine, hydrogen chloride, iron or copper was removable.
Sulfur dioxide in atmosphere was determined by the improved field method with errors of 1.3%. Improvements in the procedure were:
( a ) elimination of bias with calibration using standard gas,
( b ) precise measurement of gas volume with a wet-type gas meter, and
( c ) precise control of temperature in the spectrophotometric analysis.View full abstractDownload PDF (836K) -
Analysis with triethanolamine and metal-ion. IMorihisa SUZUKI1971 Volume 20 Issue 9 Pages 1103-1107
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSThe stable color of catechol with triethanolamine and iron (III) in an ethylalcohol solution (99.5 v/v%) has been studied spectrophotometrically for its determination in a triethanolamine buffer. The molar ratio of catechol and iron (III) in the chelate in a triethanolamine buffer was 1 : 1. Beer's law was obyed for up to 60 ppm of catechol at 595600μm The absorbance did not change at least for 24 hours, and the apparent molar extinction coefficent was 1830. The method is rapid, simple and accurate. The amount of water, less than 10% to solvent, did not interfere. Hydroquinone and resolcinol also did not interfere up to 1170 and 25 in molar ratio to catechol, respectively.View full abstractDownload PDF (678K) -
Toshiaki KUROHA1971 Volume 20 Issue 9 Pages 1107-1111
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSGlue has been widely used as an addition reagent for the acid copper plating baths. The situation of the glue in the plating baths are devided into decomposed glue and remained glue, and the results of their rational analysis were represented by three values of (1) total glue, (2) remained glue and (3) decomposed glue. The three methods of determination are different only in the preliminary treatment of the sample and the sample solutions with appropriate pretreatment are subjected to Kjeldahl digestion and Nessler photometry for determination of total nitrogen amounting to about 10% in glue. The recommended procedures are as follows pretreatment: (1) Total glue. Two milliliters of sulfuric acid, 35 mg of mercuric oxide and 0.5 ml of 30% hydrogen peroxide are added to the sample solution. It is evaporated to fumes and transferred to a 50 ml distillation flask with a small amount of water. (2) Remained glue. The sample solution in a 100 ml Erlenmeyer flask is neutralized with 50% (w/v) sodium hydroxide and then 2 ml in excess. It is kept on a boiling water bath for 90 min. with aeration to remove the decomposition product. After cooling and neutrarization with sulfuric acid, the procedure (1) for total glue is carried through. (3) Decomposed glue. The sample solution is directly placed into the distillation flask.
Distillation and color development: Connect the distillation flask with a steam distillation apparatus. Place a receiver containing 1.0 ml of water. The height of the end of the delivery tube is adjusted to dip into the surface of the water. Add 20 ml of 30% (w/v) sodium hydroxide solution to the flask from funnel and carry out the steam distillation. Remove the receiver when the distillate amounts to 9.5 ml. Add 0.2 ml of Nessler reagent and make up to 10 ml with water. Allow to stand for 15 min. and measure the absorbance at 420 nm against a reagent blank.
The sensitivity is 59 μg glue/cm2 for an absorbance of 0.1. The ingredients in common plating baths including H2SO4, Cu, Ni, Bi, As, Sb, Sn and Zn do not interfere.View full abstractDownload PDF (751K) -
Morio TSUGE, Shigeyuki TANAKA1971 Volume 20 Issue 9 Pages 1111-1116
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSThis investigation reveals that the most available cure index for socalled B-stage phenolic and cresolic resol resins in laminating materials is the ratio of the absorbance at 1000 cm-1 and the absorbance at 1610 cm-1 as a parameter.
B-stage resins in laminating materials containing paper and glass fiber fillers are extracted with anhydrous acetone. The sample concentration is about 100 mg per 1 ml acetone and a rock salt cell with a 0.1 mm path length is used. The peak intensity method and the baseline method are used for the calculation of the absorbance.
The reproducibility is about 3 per cent.
The apparent activation energy of the curing reaction determined by this cure index method is about 17 kcal/mole and is in good agreement with that obtained by a chemical method. This cure index is not applicable to the determination of the curing of A-stage resins because of the absorption interference at 1610 cm-1 by a free monomer.View full abstractDownload PDF (692K) -
Studies on hydrazone derivatives in fluorometric analysis. IToyozo UNO, Saburo NAKANO, Hirokazu TANIGUCHI1971 Volume 20 Issue 9 Pages 1117-1123
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSFluorescence reaction of pyridoxal (PAL) and pyridoxal-5-phosphate (PALP) with hydrazides (Table I) was examined. PAL and PALP reacted with iso-butyric acid hydrazide (IBH) to form hydrazones in an acetate buffer solution which gave green fluorescence in an alkaline medium. IBH was suitably used for the determination of PAL and PALP. By the proposed method, 0.011.0 μg per ml of PAL hydrochloride and 0.11.0 μg per ml of PALP could be determined. Ten fold amount of pyridoxine hydrochloride and equal amount of pyridoxamine hydrochloride did not interfere.
Separatory determination of PAL and PALP has been done by the combination of the proposed method with an enzymatic method using acid phosphatase.View full abstractDownload PDF (940K) -
Studies on the hydrazone derivatives in fluorometric analysis. IIToyozo UNO, Hirokazu TANIGUCHI1971 Volume 20 Issue 9 Pages 1123-1128
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSFour derivatives of 2-hydroxy-1-naphthaldehyde hydrazones (from acetic acid hydrazide, phenylacetic acid hydrazide, benzoic acid hydrazide and isonicotinic acid hydrazide) were synthesized.
The spot test on the fluorescence due to the reactions between these hydrazons and various metal ions indicated that they were useful for the analysis of aluminum. 2-Hydroxy-1-naphthaldehyde benzoic acid hydrazone (HNBH) gave the strongest fluorescence and a fluorometric method for the determination of aluminum was established by using HNBH. The recommended procedure was as follows. To a sample solution of 4 ml were added 1 ml of acetate buffer solution (pH 4.6), 6ml of mixed solvent (CH3OH: DMF = 2 : 1) and 2 ml of 0.004% HNBH in ethanol. The solution was then warmed at 4042°C and was diluted to 20 ml with 50% methanol. Blue fluorescence with the maximum at 475 mμ was measured, From 0.1 to 1.0 μg of aluminum per ml was successfully determined.View full abstractDownload PDF (782K) -
Shigeyuki TANAKA, Tomoko MATSUI1971 Volume 20 Issue 9 Pages 1128-1132
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSKRS-5 crystals were designed and prepared for ATR method utilizing large incidence angles. By using these crystals, samples with high refractive indices or thin coating samples were analyzed successfully. For example, the rubbers with high carbon black contents which were difficult to be measured by usual ATR method because of their high refractivity were possible to be measured by applying the incidence angle 70°. In the same way, changing the incidence angle from 45° to 72°, several informations were obtained about thinner surface layers than those having been measured by usual ATR method.View full abstractDownload PDF (751K) -
Toshio OZAWA1971 Volume 20 Issue 9 Pages 1132-1136
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSStilbazo reacts with zirconium to form greenish blue complex. Its absorption spectrum had an isosbestic point at 585 mμ between pH 2.4 and 5.0, and the determination of zirconium was done by utilizing wavelength 585 mμ and pH 3.0.
The Beer's law held for 01.2 μg Zr/ml. The molar extinction coefficient was 5.65×104, and the sensitivity for log (I0/I)=0.001 was 1.6×10-3μg Zr/cm2.
Beryllium, hafnium, indium, molybdenum, manganese, titanium, thorium, tungsten, vanadium(IV, V), phosphate, oxalate, citrate and EDTA interfered seriously with the determination.
The interference due to manganese and titanium could be removed by masking with sulfosalicylic acid, and the interfering molybdenum was masked with thioglicollic acid and tungsten with potassium thiocyanate solution including ascorbic acid.View full abstractDownload PDF (691K) -
Toshiaki KUROHA, Iwao TSUKAHARA, Seiji SHIBUYA1971 Volume 20 Issue 9 Pages 1137-1142
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSAn atomic absorption spectrophotometric method for the determination of cadmium and zinc in copper, nickel, aluminum and uranium metals has been presented. This method involves the extraction of cadmium and zinc with methyl iso-butylketone (MIBK) solution of tri-n-octylamine and the measurements of absorbances of the extract. Ten milligrams of Be2+, Bi3+, Co2+, Cr3+, Mg2+, Pb2+, Sn4+, and Zr4+, 1 mg of As(III), Fe3+, Ga3+, In3+, Mn2+ and V (V) and 6 N of SO42- do not interfere. More than 1 mg of Fe3+, 0.01 N of NO3- and 0.0001 N of CrO42- interfere. More than 1 mg of Zn2+ and Te(IV) interfere with the determination of cadmium, and more than 0.1 mg of Cd2+ and Te(IV) interfere with the determination of zinc. As little as 0.5 ppm of cadmium and zinc in copper, nickel, aluminum and uranium metals can be determined by this method. The recommended procedures are as follows.
(1) Determination of Cd and Zn in copper and nickel metals: 1.0 g of sample is decomposed with 10.0 ml of HNO3(1+1). Ten milliliters of H2SO4 (1+1) is added and evaporated to fumes. It is transferred with 20 ml of HCl (1+1) into a separatory funnel and made up to 50 ml with water. It is shaken vigorously with 5.0 ml of 2 vol% tri-n-octylamine-MIBK solution for 5 minutes. The aqueous phase is transferred into another separatory funnel and shaken again with 5.0 ml of 2 vol% tri-n-octyl-amine-MIBK solution for 5 minutes. The two organic phases are combined and subjected to the atomic absorption spectrophotometry. The absorbances of Cd and Zn are measured, and the amounts of Cd and Zn are determined by referring to their calibration curves.
(2) Determination of Cd and Zn in aluminum metal: 1.0 g of sample is decomposed with 20.0 ml of HCl (1+1), 7.0 ml of H2SO4 (1+1) and several ml of H2O2 (30%) {High purity aluminum metal is decomposed with 10.0 ml of NaOH solution (20%) and made acidic with 10.0 ml of H2SO4 (1+1) and 20.0 ml of HCl (1+1) }. It is transferred into a separatory funnel and made up to 50 ml with water, Cd and Zn are determined in accordance with above mentioned procedure (1).
(3) Determination of Cd and Zn in uranium metal: 1.0 g of sample is decomposed with 12.0 ml of HCl (1+1), 3.0 ml of H2SO4 (1+1) and several ml of H2O2 (30%). It is transferred into a separatory funnel and made up to 50 ml with water. Cd and Zn are determined in accordance with above mentioned procedure (1) using 3 vol% solution in place of 2 vol% tri-n-octylamine-MIBK solution in the procedure (1).View full abstractDownload PDF (913K) -
Rokuro KURODA, Toshio ONO, Koji ISHIDA1971 Volume 20 Issue 9 Pages 1142-1145
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSMany metals do not favor the DEAE-cellulose to any great extent from aqueous nitric acid solutions. However, thorium exhibits an enhanced adsorption on DEAE from mixed methanol-nitric acid media. This behavior of thorium on DEAE allows to develop a highly selective method for the separation of thorium. Even barium, bismuth (III), the rare earths and lead (II), which are adsorbed tightly on a strongly basic anion-exchange resin Dowex 1 from the methanolic acid media, do not show any marked adsorption on DEAE. Thus, as little as 100 μg thorium can be separated quantitatively from a hundred times as much other metal ions on a small column containing 1 g DEAE in methanol-nitric acid (20 : 1, v/v) media. The concentration of nitric acid may be allowed to vary in a wide range of 1 to 13 M.Increasing amounts of DEAE should be used with increasing amounts of thorium to be loaded on the column. Quantitative separations of thorium from thirty metals were reported.View full abstractDownload PDF (620K) -
Tetsuro MURAKAMI, Toshiaki YOSHINAGA1971 Volume 20 Issue 9 Pages 1145-1151
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSA thin-layer chromatographic method for the separation and identification of organomercury compounds has been investigated and applied to the examination of industrial waste water. To 100200ml of waste water adjusted to 0.10.2 N HCl are added CHCl3 equal to 1/3 volume of aqueous phase and KMnO4 solution dropwise until the solution turns pink. After shaking the mixture, the CHCl3 layer is separated and the extraction with CHCl3 is repeated twice more. Organomercury compounds in combined CHCl3 solution are reversely extracted into ammonia, and it is treated with an anion exchange resin, Amberlite IRA-400, to remove anions such as propionate, valeriate, oleate, stearate, oxalate, succinate, adipate, anthranilate, naphthionate and tartrate, each of which interferes with the separation of organomercury compounds in thin-layer chromatography. The ammoniacal effluent is made acid and extracted with CHCl3, and the resultant CHCl3 layer is then chromatographed.
The CHCl3 solution of the mixture of methylmercury, ethylmercury, propylmercury, amylmercury and hexylmercury, in the form of their chloride, and phenylmercury in the form of its acetate is spotted on thin-layer of silica gel B5 containing 7.5% of NaCl, and developed simultaneously by using cyclohexane-acetone-ammonia mixture (120 : 80 : 2) as the solvent. Rf value of each compound is in the order of methylmercury<phenylmercury<ethylmercury<propylmercury<amylmercury+hexylmercury, and spot of each compound is distinctly separated. The addition of NaBr, instead of NaCl, in thin-layer is not advantageous and the use of methylamine, instead of ammonia, in developing solvent increases Rf value of alkylmercury chloride and decreases Rf value of phenylmercury acetate. By the use of the proposed method, organomercury compounds in industrial waste water were separated and identified with satisfactory results.View full abstractDownload PDF (1092K) -
Shigehiko HAYASHI, Keiya KOTSUJI, Ryuichiro HAYASHI, Mikio HARA, Koji ...1971 Volume 20 Issue 9 Pages 1152-1157
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSA method for the spectrophotometric determination of germanium, based on a solvent extraction of an ion-association pair formed between 4-nitrocatechol germanate anion and 2, 2'-bipyridyl-iron (II) chelate cation with 1, 2-dichloroethane, is described.
The absorbance maximum of the ion pair in the organic phase is at 526 mμ. When the concentrations of 2, 2'-bipyridyl-iron (II) chelate cation and 4-nitro-catechol in the aqueous phase are kept to 2.96×10-4 M and 4.80×10-4 M, respectively, the constant extraction is obtained in the range of pH 3.04.5. Beer's law is obeyed over the range of 3.83×10-61.34×10-5M.
The procedure for the construction of the calibration curve is as follows.
Four milliliters of 3.0×10-3 M 4-nitrocatechol solution, 2 ml of 10% hydroxylamine hydrochloride solution, 2 ml of monochloroacetate buffer solution, varying amounts of the germanium standard solution and 2 ml of 3.7×10-3 M 2, 2'-bipyridyl-iron (II) chelate cation solution are mixed. The solution is adjusted at pH 3.54.0 and diluted to 25 ml with water. It is then shaken for 4 min. with 10 ml of 1, 2-dichloroethane. The absorbance of the organic phase is measured at 526 mμ against the reagent blank extract.
Germanium can be separated from a 50-fold molar excess of arsenic, and, in the presence of EDTA, ferric iron, aluminum, cadmium, lead, zinc, calcium and magnesium do not interfere.View full abstractDownload PDF (935K) -
Influence of solvent vapor in thin-layer chromatography. IIIYoshihito SUZUKI, Yutaka YAMAZAKI, Tsugio TAKEUCHI1971 Volume 20 Issue 9 Pages 1158-1163
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSA new type of thin-layer chromatography (vapor pre-adsorption TLC) in which a silica gel thin-layer pre-adsorbing the vapor of organic solvent is used as the stationary phase and a non-polar organic solvent as a developer has been presented.
Sample: 2, 4-dinitrophenylhydrazones of aliphatic aldehydes. Solvent for pre-adsorption : acetone, benzene, carbon tetrachloride, ethyl acetate. ethanol etc. Solvent for development : n-hexane, cyclohexane and petroleum ether.
A 500 ml round-bottomed flask containing 50 ml of pre-adsorption solvent is placed in a thermostat and a stream of nitrogen is introduced. The evaporated vapor of the solvent is introduced to the developing chamber and is pre-adsorbed on the surface of the thin-layer. After 1530 minutes, the developing solvent is made to flow through the layer descendingly.
As an increase in the flow volume (flow rate×time) gives larger Rf values, desired Rf values for the separation of various substances are obtained by the experimental conditions.
It is generally believed that the Rf value of a substance depends on two factors, i. e., (1) adsorptivity of the layer and (2) eluting power of the developing solvent. The author's experimental data shows that the third factor, the effect of pre-adsorption of vapor, is critically important to decide the Rf value.View full abstractDownload PDF (770K) -
Shigeo YAMAMOTO, Masao SETO, Masami MAKITA1971 Volume 20 Issue 9 Pages 1164-1167
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESS3-(1, 2, 3, 4-tetrahydro-1-naphthyl)-4-hydroxycoumarin (Endrocide) reacts with p-nitrobenzenediazonium chloride at pH 3.13.6 to give a yellow pigment which is extractable with benzene. This color reaction has been successfully applied to the determination of small amounts of Endrocide without interference from Warfarin. The pigment in benzene has an absorption maximum at 425 mμ. The sensitivity is very high, the standard deviation for each test sample being less than 1.2%. The molar absorptivity is 2.8×104 and the Beer's law is obeyed over 220 μg of Endrocide/ml.
The recommended procedure is as follows. Prepare the test solution containing 220 μg Endrocide/ml in 0.01 N sodium hydroxide. Take a 5 ml aliquot of this solution into a 30 ml glass-stoppered test tube. Add 5 ml of p-nitrobenzenediazonium chloride solution and adjust pH to 3.13.6 with 1 N sodium hydroxide. Extract the pigment formed with 10 ml of benzene after standing for 40 minutes at room temperature, and measure the absorbance at 425 mμ against the reagent blank solution.
The structure of the isolated pigment is 2, 3, 4-trioxochroman-3-(p-nitrophenyl) hydrazone.View full abstractDownload PDF (525K) -
Shigeki ABE, Tsutomu MATSUO1971 Volume 20 Issue 9 Pages 1168-1172
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSCopper (II) and manganese (II) catalysed the oxidation of phenolphthalin by hydrogen peroxide in an alkaline (pH12) medium and in ammonium carbonate solution, respectively, and the reaction was used to indicate the end point of titration in the determination of Cu and Mn with EDTA. This catalytic titration method was also applied to determine zinc, cadmium and lead by back-titration of excess EDTA with standard copper solution. The results were in good agreement with those by titration using PV or MX as metal indicators.
The recommended procedures for copper and manganese were as follows: to an about 50 ml portion of solution containing known amount of EDTA and either phosphate buffer (for Cu) or ammonium carbonate (for Mn), add 1 ml of 0.2% phenolphthalin and 0.5 ml of 0.3% hydrogen peroxide. Titrate the solution with copper or manganese solution. At the end point, the solution turned red immediately by the formation of phenolphthalein.
The catalytic effect of metal ions on the oxidation of cresolphthalin was also investigated.View full abstractDownload PDF (927K) -
Polarographic study of artificial food colors. IIYasuhisa MIZUNOYA, Mitsuaki OMORI1971 Volume 20 Issue 9 Pages 1172-1177
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSThe anomalous waves in the polarographic reduction of Eosine (Food Red No. 103) and Phloxine (Food Red No. 104) appeared in acidic aqueous solutions as previously reported, and these phenomena were unfavourable for the polarographic method to be applied to the analyses of these coloring materials. The purpose of the present study was to eliminate these phenomena and to be able to use the polarographic method for microdetermination of these two xanthene-type food colors.
The electrolytic solution was prepared by adding 4 ml of buffer solution, 1 ml of 1M tetramethylam-monium chloride as a supporting electrolyte and 4 drops of 1% gelatin solution as a maximum suppressor to 5 ml of the solution of Eosine or Phloxine dissolved in dioxane-water (3 : 1) mixture. In the case of Eosine, the polarographic measurements were performed at pH 1.014.0, while in the case of Phloxine, they could not be performed at less than pH 3.8 because of precipitation of Phloxine. Eosine and Phloxine in this electrolytic solution at pH 3.8 showed the well defined polarographic reduction waves without any anomalous waves, and their halfwave potentials were -0.61 and -0.65 V vs. SCE, respectively. When pH of electrolytic solution became higher in the acidic range, their half-wave potentials shifted remarkably to negative, while in the alkaline range, they were almost constant and the second and third waves appeared with the rise of pH value.
For analytical application of the polarographic reduction of these compounds, the fundamental investigations were carried out at pH 3.8. The polarographic reduction waves of these two xanthene-type food colors could be considered as the reduction of their quinoid forms, but it could not be concluded that their reductions were reversible electrode reactions because their relationships of log [i/(id-i)] to E did not show the exchanges of two electrons as expected. It could be concluded that the limiting currents of these two food colors were diffusion currents, because their temperature coefficients from 15°C to 35°C were both 2.1% per degree and their limiting currents were proportional to square roots of bights of mercury reservoir. Moreover, the diffusion currents of Eosine and Phloxine were proportional to the concentrations from about 10-3 to 10-4M of their two compounds, and their diffusion current constants were 1.46 and 1.60, respectively.
By this polarographic procedure, micro-amounts of Eosine and Phloxine can be determined.View full abstractDownload PDF (914K) -
Sôichirô MUSHA, Makoto MUNEMORI, Hirokazu MATSUOKA1971 Volume 20 Issue 9 Pages 1177-1182
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSAbout 20 μl of sample solution was taken on a platinum coil simply by dipping it into the sample solution. The coil was brought close to, but not into, the flame to evaporate the solvent and then introduced into the flame. Atomization of the sample was immediately taken place and sharp absorption peaks were recorded for cadmium, zinc, lead, and mercury (II). The peak height was linearly proportional to the concentration of the element. The present method gave a 15-, 5-, 4-, and 12-fold enhancement in the sensitivity for cadmium, zinc, lead, and mercury (II), respectively, compared with the ordinary method, but gave a decrease in the sensitivity for calcium, copper, and iron on account of the broadening of absorption signals.
Eleven measurements for 0.2 ppm of zinc gave a relative standard deviation of about 3%. Various acids and co-existent elements remarkably interfered with the determination by this method, but by applying the standard addition method, zinc in aluminum and copper alloys was determined satis factory.View full abstractDownload PDF (882K) -
Toshiyuki SHONO, Masayuki GODO, Koichiro SHINRA1971 Volume 20 Issue 9 Pages 1183-1186
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSA study of nuclear magnetic resonance spectra of two ω-hydroxy aldehydes from 20100°C has disclosed that pure 5-hydroxy pentanal exists predominantly as the cyclic hemiacetal at 20°C, but contains an estimated 50% of free aldehyde at 100°C. In dimethylsulfoxide-d6 solution (5%), 6-hydroxy hexanal exists as an equimolar equilibrium mixture of cyclic hemiacetal and free aldehyde independent of the temperature.
The variation of the proton chemical shifts of hydroxyl and aldehyde with temperature was studied and the conversion enthalpy of ring-chain tautomerism in 5-hydroxy pentanal was calculated from the relationship between the logarithm of the equilibrium contant and the reciprocal of the temperature.View full abstractDownload PDF (535K) -
Naoshige AKIMOTO, Keiichiro HOZUMI1971 Volume 20 Issue 9 Pages 1186-1191
Published: September 05, 1971
Released on J-STAGE: February 16, 2010
JOURNAL FREE ACCESSA method for microdetermination of potassium by the direct potentiometric measurement using monovalent cation selective electrode has been investigated. As the volume of the test solution was most convenient at the range of 50100 ml for handling in microanalysis, the potassium ion concentration should have been ranging in 10-310-4 M, in that the electrode potential attained its steady-state within several minutes, the reproducibility was practically constant and the calibration curve could have been modified to be linear by a small addition of α as has been indicated in the eq. (3), the value of α being empirically found as 0.08×10-40.10×10-4 using the same unit of [K+].
The method has been further applied to the oxygen flask combustion for microdetermination of potassium in the organic substances. A sample was ignited in a combustion flask containing 10 ml of water as the absorption liquid. The flask was shaken vigorously so that the absorption liquid contact well with platinum basket. The absorption liquid was transferred into 100 ml of volumetric flask using 50 ml water, 10 ml of tris buffer was added to adjust the pH at 8 and the ionic strength at 0.06 M and finally it was made up to 100 ml with water. A combination of the monovalent cation selective electrode and a double junction silver chloride reference electrode was dipped into the test solution and the electrode potential was read after 10 minutes.
It was found that the calibration could be done using either potassium biphthalate or potassium chloride standard solution because practically 100% recovery of potassium after the combustion was attained. Standard deviation of σ=0.20 (%) has been obtained from a series of analytical data using the flask combustion.View full abstractDownload PDF (938K) -
Mikio YASHIKI, Masakazu DEGUCHI1971 Volume 20 Issue 9 Pages 1192-1193
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSThe Formation of the complex between mercury(II) and thiothenoyltrifluoroacetone(STTA) is suppressed by the presence of cyanide ion. This inhibitory effect was applied to the spectrophotometric determination of 0.484.32 μg/10 ml of cyanide ion. The precisions in coefficient of variation were 2.8 and 1.0% for 1.44 and 3.84 μg, respectively, of cyanide ion.
An analytical procedure for cyanide ion was as follows: Several milliliters of a sample solution containing 0.484.32 μg cyanide ion and 2 ml of buffer solution(pH 11.5) were taken into a test tube, and the solution was made up to 10 ml with water. Ten milliliters of mercury(II)-STTA complex {containing 40 μg mercury(II) per 10 ml} in carbon tetrachloride was added to it, and the mixed solution was shaken vigorously for 2 minutes. The absorbance of mercury(II)-STTA complex in the organic phase was measured at 360 mμ against carbon tetrachloride. Many anions did not interfere, but sulfide ion interfered even in the amount less than 1/4 of cyanide ion.View full abstractDownload PDF (309K) -
Norio ICHINOSE1971 Volume 20 Issue 9 Pages 1194-1196
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSA spectrophotometric method with zinc diethyldithiocarbamate (Zn-DDC)-carbon tetrachloride solution has been developed for the determination of a microamount of copper.
Copper is extracted as Cu-DDC complex from 0.5 N aqueous nitric acid solution into the organic phase, and the absorbance of the extract is measured at 436 mμ. Iron(III), cobalt, nickel and bismuth interfered with the determination of copper to give a possitive error, while 100 μg each of the former three was masked with EDTA in 0.5 or 1 N aqueous nitric acid solution.
This method, using 1 cm cell, is applied to the determination of more than 0.04 ppm of copper.View full abstractDownload PDF (493K) -
Sumiko UEOKA, Satoshi OKADA, Soichiro IGA, Hiroshi ISAKA, Kiyoshi YOSH ...1971 Volume 20 Issue 9 Pages 1196-1198
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSVarious titrants and solvents were studied on nonaqueous titration of bemegride using glass indicator electrode, and the following method has been proposed.
Bemegride itself: Bemegride(0.4 meq.) is dissolved is 35 ml of pyridine, and titrated with 0.1N tetrabutylammonium hydroxide in benzene-methanol(9:1) using modified glass-Ag/AgCl electrode system.
Bemegride injection(0.5 w/v%) : 10.0 ml of injection in extracted with three 10-ml portions of chloroform. The combined extract is dried with anhydrous sodium sulfate, and evaporated to dryness in vacuum. The residue is dissolved in 35 ml of pyridine, and titrated as above.View full abstractDownload PDF (449K) -
Kiyoshi KIHARA, Yoshihito SUZUKI, Tsugio TAKEUCHI1971 Volume 20 Issue 9 Pages 1198-1200
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSAn absorption of colored substances was found on the upper part of the active alumina packed column which had been passed through with a benzene or petroleum solution of commercially available pale yellow or yellow colored fluorene and developed with the same solvent. The colored portion was cut off and the substances were extracted with benzene. The yellow substances thus obtained were examined by means of IR and UV spectrometry, elementary analysis and gaschromatography, and were identified to be 9-fluorenone and one of it's methyl derivatives.View full abstractDownload PDF (386K) -
Shun ARAKI, Shigetaka SUZUKI, Katsunori WATABE, Yasuyo TAKAHATA1971 Volume 20 Issue 9 Pages 1200-1202
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSIn the series of our investigation on a new countercurrent continuous gas chromatography, a larger scale apparatus has been designed. In this apparatus, dry air was used as the carrier gas. Some of the experimental results were against the expectation. As these were supposed to be due to the deterioration of the liquid (PEG400), partition coefficients of several organic compounds for the used stationary liquid were measured by a gas chromatographic technique. The coefficients thus obtained for the used stationary liquid were definitely defferent from that for the fresh stationary liquid as shown in Table I. Furthermore a significant absorption band attributed to the presence of carbonyl group was observed in the infrared spectra as shown in Fig. 2. These results were concluded to show that an air oxidation of the stationary liquid occured even at low temperatures. An air oxidation of squalane was also observed. On the other hand, when nitrogen has been used as the carrier gas in this apparatus, no deterioration of the stationary liquids occured. The deterioration of the stationary liquid by oxygen in the carrier gas should be considered to be one of the factors which cause changes in the partition coefficient.View full abstractDownload PDF (502K) -
Tsuneko YAMANE, Sumeo MATSUSHITA1971 Volume 20 Issue 9 Pages 1202-1204
Published: September 05, 1971
Released on J-STAGE: February 15, 2010
JOURNAL FREE ACCESSThe analytical sensitivities for various elements which were contained in electrically non-conductive powders have been determined with Laser-Microspectral-Analyser (VEB Carl Zeiss Jena, LMA-1 and Q-24. The maximum output energy is 1 Ws.11).
A laser beam was focused onto a specimen at its microscopically small area, and the vapor thus produced was then excited by an auxiliary spark discharge. A slit image method was used for slit illumination. The laser beam from a Nd-doped glass laser was obtained with normal pulse.
The standard non-conductive powder (Spex Mix, No. 1000) diluted with pure graphite powders was solidified with purified phenolic resin. Craters formed on the specimen were approximately 100 μ in their diameter and its half in depth (_??_10-7 g).View full abstractDownload PDF (498K) -
Shohachiro OKI, Masakazu WATANABE1971 Volume 20 Issue 9 Pages 1204-1206
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSThe vapori zation of mercury from nitric acid solutions containing very small amount of mercuric nitrate has been studied by using 203Hg as the tracer. 5 ml of the mercuric nitrate solutions were put in test tubes (5mm in dia. and 150mm in height), covered with "Saran Wrap" (polyvinylidene chloride synthetic thin film), allowed to stand and the radioactivity measurements were carried out at regular intervals. A remarkable escape of mercury was recognized if the mercury concentration was below 0.1 ppm. The concentration of nitric acid seems to have no effect on the vaporization when it was below 0.6N. On passing air through the very dilute mercuric nitrate solutions, mercury vaporized more rapidly. The vaporized mercury could be collected effectively when the air was then passed through an acid solution of potassium permanganate. No recovery of mercury from the air, however, was observed if the air was passed through a 10 ppm mercuric nitate or water instead of the oxidizing solution. This seems to suggest that the vaporized mercury is in the state of Hg(0).View full abstractDownload PDF (465K) -
Hiroshi UCHIKAWA, Masahiro NUMATA1971 Volume 20 Issue 9 Pages 1207-1208
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSA fluorescent X-ray analysis was applied to determine the oxygen in both organic and inorganic compounds. A Rigakudenki vacuum path single channel X-ray spectrograph (D-9C, SX type) with a sealed Rh target X-ray tube (3 kW) and lead myristate (2d= 80.5 Å) as an analysing element was used for the determination of oxygen. Exited O Kα was measured by a gas flow proportional counter with aluminum coated 1 μ thick polypropylene film window.
Calibration curves were prepared from appropriate standards of both organic and inorganic reagents. Typical conting rate of O Kα spectra for boric acid, lithium carbonate and magnesium oxide were 2326, 145 and 103 counts/sec. and reproducibility expressed as standard deviation of measured intensities were 0.39%, 0.51% and 0.88%, respectively.View full abstractDownload PDF (266K) -
1971 Volume 20 Issue 9 Pages 1209-1219
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSDownload PDF (1943K) -
[in Japanese]1971 Volume 20 Issue 9 Pages 1220-1230
Published: September 05, 1971
Released on J-STAGE: June 30, 2009
JOURNAL FREE ACCESSDownload PDF (1368K)
- |<
- <
- 1
- >
- >|