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Volume 19, Issue 3
Displaying 1-24 of 24 articles from this issue
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Hiromi ARIMOTO, Shigehiko HATTORI1970 Volume 19 Issue 3 Pages 313-317
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSThe authors applied gas chromatography to the determination of oxygen in iron and steels by composing a special equipment for it. The sample was fused with graphite crucible under atmosphere of helium gas in a high frequency combustion furnace of 2 kW and 450 kilocycles. Carbon monoxide and others gases extracted from the molten metal were swept with helium and were separated mutually by gas chromatography. The amount of oxygen was obtained from the amount of carbon monoxide. When 1 g of a metal specimen was supplied for analysis, the detection limit of oxygen gas was about 10 ppm. Standard deviation of the result was about 6%.
The method and the apparatus were effectively applied for the determination of oxygen in iron and steels.View full abstractDownload PDF (696K) -
Hiroto ISAGAWA, Eiji NIKI1970 Volume 19 Issue 3 Pages 318-324
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSA photoelectric spectrophotometer was utilized as a double beam spectrometer by dividing the exit slit into two portions, upper and lower, and the intensity of a spectral line was measured without scanning the wavelengths.
A quartz plate was placed slantly in front of the upper half of the exit slit to shift the wavelength of the beam arriving at this portion. The spectrophotometer was set so that the photocurrent due to one beam might show Ib (background intensity)+IL(line intensity) and the photocurrent due to the other beam might show Ib. The light was passed alternately through the upper and lower parts of the slit, and the a.c. component of the photocurrent was synchronously rectified. The d.c. cutput then indicated IL.
The advantages of this method are as follows.
(1) The line intensity can be measured regardless of fluctuation of Ib.
(2) As it uses only one photomultiplier, the change of the sensitivity of photomultiplier need not be considered seriously.
(3) By integration of output signal, we can reduce the influence of the noise of spectrophotometer and light source. By three minutes' integration, the detection limit was 1/30 of that by the single beam method, and IL as small as 1/250 of Ib was measurable.View full abstractDownload PDF (3136K) -
Kenjiro HAYASHI, Yoshiaki SASAKI, Hiroyoshi NOJIMA1970 Volume 19 Issue 3 Pages 325-330
Published: March 05, 1970
Released on J-STAGE: May 25, 2010
JOURNAL FREE ACCESSIn the chloroform extraction of zinc ethylxanthate the extracted species is found to be Zn (EtX)2 and the predominant aqueous species are Zn2+ and/or Zn(EtX)2 in the pH region below 7.5. At higher concentration of ethylxanthate the important aqueous species is Zn(EtX)3-.
The distribution ratio of zinc (D) is therefore given as
D=[Zn(EtX)2]0/{[Zn2+]+[Zn(EtX)2]+[Zn(EtX)3-]}a
The distribution coefficient of Zn(EtX)2 (Kp) and the over-all formation constants of zinc-xanthate complexes were determined by using equation (2). Results obtained are given in Table II.
The intrinsic solubility and the solubility product of Zn(EtX)2 were calculated from Fig. 5 (see Table III).
Zn(OH)42- seems to be the predominant species in aqueous phase at high pH. The over-all formation constant of this complex (β4) was found to be logβ4=20.7.
Beer's low is obeyed, the molar extinction coefficient at 300 mμ being 2.03×104 (see Figs. 1 and 4).View full abstractDownload PDF (917K) -
Taketoshi KAJITA, Mitsugi SENDA1970 Volume 19 Issue 3 Pages 330-339
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSBoth L-ascorbic acid (AA) and erythorbic acid (EA) gave two oxidation waves in basic solutions of pH about 9 to 11. In more basic solutions, the two waves of L-ascorbic acid coalesced into a single step, whereas the two steps of erythorbic acid remained unaltered ; -in 0.5N NaOH the half-wave potential of L-ascorbic acid was -0.31V (vs. SCE) and those of erythorbic acid were -0.25V and -0.39V. The oxidation waves were diffusioncontrolled and rather stable in deaerated solution.
A method of simultaneous polarographic determination of these two acids was proposed on the basis of the application of matrix algebra to the resolution of overlapping polarographic waves. The method_ was successfully applied to the analysis of canned foods.View full abstractDownload PDF (1431K) -
Precipitation of metal ions with thenoyltrifluoroacetone and either pyridine or its analogues. I.Koichi TANINO1970 Volume 19 Issue 3 Pages 339-343
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSA method was proposed for gravimetric determination of nickel, based on the fact that nickel formed a precipitate with thenoyltrifluoroacetone (TTA) and either pyridine or picoline. The molecular formula of the precipitate was considered to be Ni(tta)2(py or pico)2, where tta, py and pico represent, respectively, univalent anion of TTA, pyridine molecule and picoline molecule. The precipitation of nickel was quantitative with pyridine, picoline and methylethyl pyridine but was not quantitative with ammonia and trimethylamine.
The recommended procedure is as follows : the picoline or pyridine (preferrably β- or γ-picoline) solution of TTA is mixid with nickel solution, and the mixture is diluted with water, adjusted to pH 59, allowed to stand overnight to settle the precipitate. It is then filtered through a weighed sintered-glass filter, washed, dried and weighed.
The method was sensitive, although it was neither selective nor specific. Less than 10 mg of nickel was successfully determined.View full abstractDownload PDF (736K) -
Kiyoharu ISAGAI1970 Volume 19 Issue 3 Pages 344-349
Published: March 05, 1970
Released on J-STAGE: May 25, 2010
JOURNAL FREE ACCESSN-Salicylidene-thiosemicarbazone is insoluble in cold water, but its copper complex is soluble and green.
This reagent has been employed for the determination of Cu(II), as the chelate formation is selective and sensitive. The chelate compound gives the colored solution by adding powder of the reagent as much as 56 times of Cu(II) in mole to sample solution adjusted to pH 2.53.5 and allowing to stand the subsequent turbid solution at 60°C for 30 min1 hr.
Excess of the reagent is filtered and the absorbance of the filtrate was measured at 630 mμ. From 1.0 to 7.0 mg of Cu(II) could be determined by the above procedure.View full abstractDownload PDF (1168K) -
Kenzo HIRAOKA, Hiroshi JIN, Shohei ODA, Hirohide EGUCHI, Hitoshi KAMAD ...1970 Volume 19 Issue 3 Pages 349-355
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSMolecular oxygen was subjected to a radiofrequency discharge at a few mmHg, and organic materials were oxidized outside of the plasma glow region by the atomic oxygen. The concentration of atomic oxygen was measured by varying the distance between plasma and organic materials, and from the results, the recombination of oxygen atoms was found to be consistent with the following mechanism.
O+O2+M k1=O3+M
O+O3 k2=2O2
O+wall kw=1/2O2+wall
The rate constant k1 was 5.5×1014 or 1.1×1015cc2/(mol2 sec), respectively, when sugar or charcoal was used as the organic material.
It was found that nearly perfect combustion was attained when charcoal or many of polymers were oxidized at outside of the plasma glow region. The decomposition of organic materials which is one of the essential operations for the elemental analysis of ash can be attained under moderate condition, i. e. at room temperature by using atomic oxygen generated by electrodeless discharge.View full abstractDownload PDF (1284K) -
Hiroshi HASHITANI, Kazuo KATSUYAMA1970 Volume 19 Issue 3 Pages 355-361
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSThiothenoyltrifluoroacetone (STTA) was synthesized according to the procedure of Berg and Reed and purified by washing the benzene solution with an alkaline solution.
The use of STTA as an extractant and a photometric reagent for determination of metals was investigated, but the determination of metals was difficult unless the excess STTA was removed from the extract because of the absorption of the reagent (λmax=370mμ, ε=1.60×104). Mercury was the only metal among 30 metals investigated for which suitable conditions for the determination were available.
Mercury (II) (280 μg) is quantitatively extracted with exactly 10 ml of 2× 10-4M STTA-xylene from a solution of a wide range of acidity (18N H2SO4pH 5) by shaking for a minute. After removal of the excess STTA by washing the extract with a basic solution (pH 10.512), mercury is determined by measuring the absorbance at 370 mμ (ε=3.0×104).Anions such as chloride and thiocyanate which form stable mercury complexes and the oxidizing or reducing substances which decompose STTA interfere with the determination. Many metals (1 g level) do not interfere. The ratio of mercury(II)-STTA was 1:2. Mercury (I) is extracted (ε=1.5×104 at 370 mμ) under the same condition as that for mercury(II), and both ions in a solution can be determined consecutively.
The proposed method is less sensitive but more selective than the dithizone method.View full abstractDownload PDF (1027K) -
Voltammetric studies using complexing agent. III.Toyokichi KITAGAWA, Yasuhiro MARUYAMA1970 Volume 19 Issue 3 Pages 362-365
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSPolarographic determination of Tl (III) using 1M KNO3+350 mM EDTA (pH 11.012.3) as supporting electrolytes is described. Half-wave potentials of Tl(III)-EDTA to Tl(I)-EDTA and Tl(I)-EDTA to Tl amalgam were -0.10 and -0.62V (vs. SCE), respectively. The diffusion current constant of the first wave was 2.93 under the same condition at 25°C. The first wave was diffusion controlled and its temperature coefficient was +1.8%. Tl(III) in the range of 0.050.4 mM was determined successfully by measuring the diffusion current at -0.35V (vs. SCE). Small amounts of Pb(II), Co(II), Cu(II), and Cd(II) do not interfere, but Pd(II) interferes. The presence of most organic amines and hydroxy compounds such as p-phenylenediamine and pyrocatechol interfere with the determination of Tl(III).View full abstractDownload PDF (642K) -
Toyokichi KITAGAWA, Yasuhiro MARUYAMA1970 Volume 19 Issue 3 Pages 366-370
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSPrecipitation of Tl(III) from aqueous solution with 8-hydroxyquinoline is quantitative at pH above 5.5 and provides bases for the gravimetric determination of Tl(III). Not all the combined water, however, could be removed without decomposition of the compound at 110 to 120°C. The recommended procedure for accurate determination of Tl(III) is as follows. Dissolve Tl2O3 with dilute HNO3 and add 2% 8-hydroxyquinoline-acetic acid solution. Adjust the pH to 5.5 with ammonium acetate solution. Digest the solution for 1 hour at 50 to 60°C. Wash with dilute ammonium acetate solution and dry at 40 to 60°C for 2 hours, and finally at 95°C for 1 hour.
The composition of the precipitate was Tl(C9H6-NO)3·2H2O. Tl(III) in the precipitate was reduced to Tl(I) at the temperature above 130°C and was converted to Tl2O3 at the temperature above 420°C. Free 8-hydroxyquinoline was also sublimed at the temperature above 160°C. These results were confirmed by thermogravimetry, polarography, spectrophotometry and elemental analysis.View full abstractDownload PDF (827K) -
Studies of Calcichrome as a spectrophotometric reagent. X.Hajime ISHII, Hisahiko EINAGA1970 Volume 19 Issue 3 Pages 371-375
Published: March 05, 1970
Released on J-STAGE: May 25, 2010
JOURNAL FREE ACCESSThe reaction of vanadium(IV and V) with Calcichrome to form complexes has been studied spectrophotometrically, and a new spectrophotometric method for the determination of vanadium has been established based on the formation of vanadium(IV)-Calcichrome complex.
Vanadium(IV) forms a 1 to 1 complex with Calcichrome having an absorption maximum at about 592 mμ in a pH region between 3 and 7. Vanadium(V) forms, on the other hand, two or more kinds of 1 : 1 complexes with the reagent differing in the addition number of protons at pH above 2. In case of applying the vanadium(IV)-Calcichrome complex formation at pH 5.3 to the determination, Beer's law was obeyed up to 4 ppm of vanadium. The apparent molar absorptivity at 634 mμ was 10000, and the sensitivity for log(I0/I)=0.001 was 5.1×10-3 μg V/cm2. Copper(II), aluminum, titanium(IV), zirconium(IV), iron(II and III), nickel(II), chromium(VI), nitrate and citrate interfered with the determination.View full abstractDownload PDF (650K) -
Takeshi ISHII, Sôichirô MUSHA1970 Volume 19 Issue 3 Pages 376-381
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSA method for the alternating current polarographic determination of lead in commercial Wood's alloy was established.
Lead in commercial Wood's alloy can be determined polarographically after dissolving the sample in ethyl acetoacetate (EAA)-methyl isobutyl ketone (MIBK). Calibrating solutions can be prepared by dissolving commercial lead metal of sp. grade (99.999%) in EAA-MIBK.
The alternating current polarogram in the region of applied potential from -0.1 to -0.7 volt vs. mercury pool anode after bubbling for 15 min with nitrogen is recorded, and lead is determined by referring to a calibration curve.
The method is rapid and has accuracies nearly comparable to those attained by the conventional ashing method followed by JIS.View full abstractDownload PDF (829K) -
Shojiro GOTO, Makoto NOSHIRO1970 Volume 19 Issue 3 Pages 382-385
Published: March 05, 1970
Released on J-STAGE: May 07, 2010
JOURNAL FREE ACCESSA device for the micro analysis in GC-MS system (Hitachi K53 GC and Hitachi RMU-6E single focussing MS) was given to keep the pressure within the vacuum chamber less than 1×10-5 torr., by pumping off unnecessary major component from a splitter at the column exit.
With this device, the injection of 10 μl of sample to GC using 3 mm column was possible, and the lower limit of detection was 0.050.002% about 100 times smaller than those in conventional method (about 1%).
Additional advantages such as the reduction of the dirt of ion source due to the elimination of unnecessary major component were noticed. Disadvantage such as peak distortion of chromatogram was not observed.View full abstractDownload PDF (633K) -
Takeichi SAKAGUCHI, Taeko TAKAHASHI, Hiromi NOGUCHI, Katsu TAKEUCHI, Y ...1970 Volume 19 Issue 3 Pages 386-393
Published: March 05, 1970
Released on J-STAGE: May 25, 2010
JOURNAL FREE ACCESSRelationship between Diabetes mellitus and blood sugar have been discussed very often, but only few reports have been given concerning the relationship of Diabetes mellitus and organ sugar, especially skin sugar. For this purpose, a small amount of living skin must be subjected to a chemical investigation.
The informations available at present in literatures are insufficient since they depend on the macro method using more than 50 mg of skin. The object of the present investigation is to determine skin sugar clinically with a higher accuracy, and the authors have established a micro procedure of skin sugar determination by glucose-oxidase method, which is applicable to about 10 mg or less of skin sample.
The methods and technics for taking skin samples of rat, guinea pig and human, and the procedure for determination of their glucose contents are given in detail.
The authors have employed a new method for pretreatment of skin involving cold infusion of refrigerated pieces of skin specimens more conveniently than the conventional homogenation.View full abstractDownload PDF (1174K) -
Atsuko ITO, Keihei UENO1970 Volume 19 Issue 3 Pages 393-397
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSSuccessive titration of calcium (pH 13) and magnesium (pH 10) using single indicator "Hydroxy Naphthol Blue" is proposed. Although HNB gives a very sharp end point in the titration of calcium at pH 13, an earlier end point color change is experienced at pH 10.
On the other hand, magnesium can be titrated accurately at pH 10 with HNB indicator, if the photometric titration technique is employed. Thus, the sample containing calcium and magnesium is at first titrated for calcium with EDTA at pH 13 using HNB indicator to the visual end point. After neutralizing the resulting solution to dissolve magnesium hydroxide, pH of the solution is made to 10, and it is titrated for magnesium using the same indicator to the photometric end point. In spite of the drawback that the proposed method needs a photometric titration assembly, the successive determination of calcium and magnesium can be done with single indicator by simple procedure. The method is applied to the analysis of natural water such as sea or river water with satisfactory result.View full abstractDownload PDF (849K) -
Tsuyoshi NOMURA, Genkichi NAKAGAWA1970 Volume 19 Issue 3 Pages 397-402
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSComplexometric titration of various metal cations by a potentiometric end-point detection with metallic bismuth indicator electrode was studied.
Bismuth electrode was prepared by electrodeposition of bismuth on a spiral wire platinum electrode from an acidic tartrate solution. The potential of the bismuth indicator electrode is expressed by the equation,
E=E°+ 0.0197 log[Bi3+]
Bismuth ion is easily hydrolyzed and the upper limit of the electrode potential is limited with the solubility product of BiOOH and/or Bi2O3 above pH 3.
Because of the formation of a stable complex by bismuth and EDTA and a very small interference from chloride ion with the electrode potential, the titration is done in a fairly acidic medium as compared with various other electrodes.
The titration of Bi, In, Th and Zr with EDTA can be carried out at pH between 0.5 to 2 in a potassium nitrate-nitric acid medium. Cu, Cd, Pb, Zn and Co can be determined in a sodium acetate medium at pH 6, and Cu, Cd, Zn, Co, Ca and Sr can be determined in an ammoniacal medium at pH about 10.View full abstractDownload PDF (917K) -
Hiroshi HASHITANI, Hideyo YOSHIDA1970 Volume 19 Issue 3 Pages 403-406
Published: March 05, 1970
Released on J-STAGE: May 25, 2010
JOURNAL FREE ACCESSComparison of three spectrophotometric methods with hydrogen peroxide, oxine and sulfochlorophenol S and a method by permanganate titration for determining 0.5 to 5% of niobium in zirconium alloys showed that the first spectrophotometric method using hydrogen peroxide in sulfuric acid reported by Wood and Adams [Anal. Chim. Acta, 31, 153 (1964) ] was the most suitable.
By use of a modified procedure as below, the analytical results in 12 laboratories for 4 samples of fluorescent X-ray standards showed that the precisions in coefficient of variation (%) were 1.8, 1.3, 2.1 and 3.9, respectively, for 3.95, 2.63, 1.69 and 1.38% of niobium.
The sample containing 24 mg of niobium was dissolved by heating with ammonium sulfate (10g), sulfuric acid (20ml) and perchloric acid (2ml). After dissolution, perchloric acid was expelled, and the solution was made up to 50ml with sulfuric acid in a volumetric flask. Exactly 25 ml of the solution was transferred to another 50 ml flask, and 5 ml of hydrogen peroxide-sulfuric acid (20 ml of 30% hydrogen peroxide and 480 ml of sulfuric acid) was added. Both solutions in two volumetric flasks were made up to 50 ml with sulfuric acid, and the absorbance of that containing hydrogen peroxide was measured at 365 mμ against the other solution as the reference blank.View full abstractDownload PDF (671K) -
Jun FUJIWARA, Akira KAWASE1970 Volume 19 Issue 3 Pages 407-409
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSCommercial dioxane of special grade reagent contains trace amounts of acetaldehyde and water, and sometimes about 1 % of glycol acetal. The glycol acetal is decomposed readily by hydrochloric acid but scarcely by metallic sodium, and is removed simply by stepwise distillation. The dioxane for ordinary pH titration is prepared by only distilling the commercial product in the presence of metallic sodium, but the refluxing with hydrochloric acid and successive recrystallization are necessary for the purification of dioxane for ultraviolet absorption measurement.View full abstractDownload PDF (445K) -
Comparison of iodine-chloride, iodine-acetone and iodine-cyanide methodsYoshio TAKINO, Naomi SAWANISHI, Chieko SASAKI1970 Volume 19 Issue 3 Pages 410-412
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSThe three methods for determination of potassium iodide by iodatimetry were compared.
The iodine-cyanide method was the most precise and accurate, though it had a disadvantage in generating poisonous hydrogen cyanide in the procedure.
The stochastical comparison of carbon tetrachloride and starch as an indicator in the iodine-cyanide method showed that the former was superior when the amount of potassium iodide was less than 150 mg.View full abstractDownload PDF (578K) -
Tsunenobu SHIGEMATSU, Masakazu MATSUI, Toru AOKI, Masahiko ITO1970 Volume 19 Issue 3 Pages 412-414
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSThe trace amount of perchlorate was extracted as an ion association complex with Zn-phenanthroline (labelled with 65Zn) into nitrobenzene. The activity of 65Zn in organic phase corresponded to perchlorate. The method was more sensitive than the absorptiometric method.View full abstractDownload PDF (483K) -
[in Japanese]1970 Volume 19 Issue 3 Pages 415-423
Published: March 05, 1970
Released on J-STAGE: January 15, 2010
JOURNAL FREE ACCESS -
[in Japanese], [in Japanese]1970 Volume 19 Issue 3 Pages 423-426
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSDownload PDF (605K) -
[in Japanese], [in Japanese]1970 Volume 19 Issue 3 Pages 427-430
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
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[in Japanese]1970 Volume 19 Issue 3 Pages 431-440
Published: March 05, 1970
Released on J-STAGE: May 29, 2009
JOURNAL FREE ACCESSDownload PDF (2024K)
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