BUNSEKI KAGAKU
Print ISSN : 0525-1931
Volume 34, Issue 1
Displaying 1-17 of 17 articles from this issue
  • Haruki SHIRAISHI, Reiji TAKAHASHI
    1985 Volume 34 Issue 1 Pages 1-5
    Published: January 05, 1985
    Released on J-STAGE: January 15, 2010
    JOURNAL FREE ACCESS
    It was found with a glassy carbon electrode that, by preelectrolyzing the adenine and guanine solution containing copper(II) ion at +0.05V (vs. SCE), the anodic peak currents of these bases were remarkably enhanced. The same phenomenon was also found in the presence of either the adenine or the guanine containing copper (II) ion. The anodic peak potentials of adenine and guanine were ca. +1.15 V and +0.82 V (vs. SCE), respectively. Using the differential pulse staircase voltammetry (DSV), this phenomenon was applied to the electrochemical determination of the bases. The solution of the bases containing 1×10-3 mol dm-3 copper(II) acetate and 0.4 mol dm-3 acetate buffer (pH 4.0) was electrolyzed at +0.05 V (vs. SCE) for 3 min with stirring, and then the anodic DSV peaks of the bases were recorded without stirring. The relationships between the peak currents and the concentrations of the bases were linear in the concentration range from 5×10-7 to 8×10-6 mol dm-3. The slopes of the calibration curves for adenine and guanine were 1.3 and 3.1 (10-6 A/10-6 mol dm-3), respectively. The preelectrolysis time of 5 min made it possible to detect 2×10-7 mol dm-3 bases. It was considered that the effect of the copper(II) ion, by which the anodic peak currents of the bases were increased, was due to the adsorption of copper (ionic or metallic) compound of the bases on the electrode.
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  • Masahiko YABUUCHI, Masako MAEDA, Akio TSUJI
    1985 Volume 34 Issue 1 Pages 6-10
    Published: January 05, 1985
    Released on J-STAGE: January 15, 2010
    JOURNAL FREE ACCESS
    A sensitive bioluminescence enzyme immunoassay for the determination of 17-α-hydroxyprogesterone (17-OHP) in dried blood samples spotted onto filter paper has been developed. 17-OHP was conjugated to glucose dehydrogenase by activated ester method. Separation of free and bound fractions after immune reaction was done by using polyacetal beads coated with purified second antibody. The enzyme activity was determined by using bacterial bioluminescence system. The sensitivity of the present method was 2.5 pg/assay tube for 17-OHP. The relative standard deviations of the intraand interassay were 3.9 % and 5.17.1 %, respectively.
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  • Yoshihito SUZUKI, Toshihiro INOUE
    1985 Volume 34 Issue 1 Pages 11-15
    Published: January 05, 1985
    Released on J-STAGE: January 15, 2010
    JOURNAL FREE ACCESS
    Determination of trace water in organic solvents was investigated by high performance liquid chromatography as its di(α-naphthyl)urea derivative. A sample solvent (1 ml) was injected to a screw-capped vial through a silicone rubber septum. α-Naphthyl isocyanate (30μl) and triethylamine (30 μl) were added, and the mixture was heated to 100 °C for 90 min. Pentanol (50 μl) was then added and the heating was continued for further 30 min. All the procedures were carried out in a drying box protected from moisture. By this treatment water in the sample was converted to di(α-naphthyl)urea, and the excess reagent was transformed to pentanol α-naphthylurethane. Dimethylformamide (1 ml) was added to the mixture to give a homogeneous solution, which was then analyzed on a reversed phase column with THF/water (60/40) as mobile phase. Dimethyl phthalate was used as internal standard. The chromatograms were monitored at 280 nm. The calibration cuve was linear from 2 to 250 ppm water in carbon tetrachloride. The reproducibility of determination was 4.5 % at five runs. Similar results were obtained in the determination of water in benzene.
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  • Kunihiro WATANABE, Izuo AOKI
    1985 Volume 34 Issue 1 Pages 16-20
    Published: January 05, 1985
    Released on J-STAGE: May 25, 2010
    JOURNAL FREE ACCESS
    This procedure can be carried out in aqueous or water-methanol medium. In aqueous media, the Besalicylidene-2-aminophenol (SAPH) complex is quantitatively formed in the range of pH 8.18.6. This complex has an excitation max. at 345 nm and fluorescence max. at 440 nm. The fluorescence intensity is enhanced remarkably under the addition of ethylenediamine (en) as a buffer with 1 ml of 0.04 % SAPH, 0.0054 μg Be/25 ml can be determined in the presence of 1 ml of en. The relative standard deviation(R. S. D.) was 3.5 % for 0.019 μg beryllium. In the water-methanol media, the formation of the complex at pH 10 is highly reproducible. The complex is stood for 25 min before measurements. Here, 0.014 μg Be/25 ml can be determined. The R. S. D. was the same as the case of aqueous media. The Be complex was more stable in the water-methanol media than in the aqueous media. The fluorescence of the complex formed in the mixed medium (H2O : MeOH=2 : 3) keeps the intensity constant at least for 30 min. Although cobalt, chromium, and others interfere with the determination, they can be masked with EDTA. The proposed procedure was applied to the analysis of berylliumcopper alloy.
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  • Keiichi FUKUSHI, Kazuo HIIRO
    1985 Volume 34 Issue 1 Pages 21-25
    Published: January 05, 1985
    Released on J-STAGE: January 15, 2010
    JOURNAL FREE ACCESS
    Simultaneous determination of tripolyphosphate, pyrophosphate, and orthophosphate ions in sea water was developed with a capillary type isotachophoresis applying coprecipitation enrichment method. Using a capillary tube with 200 mm in length and 0.5 mm in inner diameter, optimum pH of leading electrolyte was studied for the separation of 3 phosphate ions. The best result was obtained by using the leading electrolyte containing 0.01 M hydrochloric acid, histidine, and 0.1 % Triton X-100 (pH 4.0) and the terminating electrolyte containing 0.01 M hexanoic acid. To enhance sensitivity in isotachophoresis, a PTFE tube with 225 mm in length and 1.0 mm in inner diameter was connected to the capillary tube in order to increase the sample injection volume to 150 μl. The effects of migration current on the zone length and the analysis time were examined with the modified system. After the optimization of procedure, the migration current was adjusted at 100μA for about 18 min and then it was reduced to 25 μA. Under these conditions, low concentrations of tripolyphosphate, pyrophosphate, and orthophosphate ions could be determined successfully. A solution of 0.2 ml of 10 M sodium hydroxide was added to 200 ml of artificial sea water sample and phosphate ions were enriched by coprecipitation with magnesium hydroxide. To prevent the interferences of high concentration anions in isotachophoresis, centrifuged precipitate was washed with 10-3 M sodium hydroxide solution and dissolved by adding 2.0 g of Dowex 50 W X8 ion exchange resin. The total volume was filled up to 5.0 ml with distilled water after filtration. A 1.0 ml aliquot of that solution was passed through a lanthanum type ion exchange resin column to remove fluoride ion. A 150 μl aliquot of the treated solution was injected into the isotachophoresis apparatus. The linear working curves were obtained for the phosphate solutions of 100, 200, and 500 ml in volume. The proposed method was applied to the determination of phosphate ions in the coastal sea water samples in Osaka Bay collected in April, 1984. In the sea water samples, orthophosphate ion could be detected, while tripolyphosphate and pyrophosphate ions could not.
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  • Soichi NADAHARA, Tadashi KIKUCHI, Keiichi FURUYA, Shiro FURUYA, Tatsuo ...
    1985 Volume 34 Issue 1 Pages 26-31
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    Laser microprobe mass analysis(LAMMA) offers the possibility of investigation of various kinds of samples with a high lateral resolution and a high sensitivity. Nevertheless, a mechanism of desorbed ion formation and its fragmentation has not been fully clarified. In this paper, the effects of laser power density on atomic and molecular ion formation were examined. A series of negative carbon cluster ions corresponding to Cn- and CnHm- were observed for organic samples at high laser power density. Characteristic molecular fragment peaks became observed at a reduced power density just over a threshold value. Pyrene and benzo [α] pyrene showed large molecular ion peaks in the positive ion spectra. On the other hand, nitropyrenes did not give positive molecular ion peaks but showed weak molecular ion peaks in the negative ion spectra. Nitropyrenes showed intense peaks of (M-NO)- and (M+O-H)-. The characteristic peaks of (M-NO)-, (M-2NO)-, and (M-3NO)- were observed for mononitropyrene, dinitropyrene, and trinitropyrene, respectively. Sodium dodecyl sulfate was readily detected from their characteristic negative ions, C12H25OSO3-, SO3-, and HSO4-. Pyrite gave peaks of Fe+ and S+ at high power density, while FeS2+, FenSn-1+, and FenSn+ cluster ions were observed when irradiated with low power density. Nonmetallic inclusions on the electroetched surface of a steel gave typical peaks of manganese oxide in the positive ion spectra under low power conditions.
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  • Kei TODA, Isao SANEMASA, Toshio DEGUCHI
    1985 Volume 34 Issue 1 Pages 31-35
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    Rapid and simple methods have been developed for the determination of fluoride ions by means of flow injection analysis based on the catalytic reactions, where fluoride ions act as catalyst on complex formation of polymerised zirconium with xylenol orange (XO) or methylthimol blue (MTB). Respective solutions (flow rates : 0.5 ml min-1) of 1.0×10-4 M XO (0.6 M HCl) or MTB (0.5 M HCl) and 2.0×10-4 M zirconium tetrachloride (0.06 M HCl), which had been allowed to stand overnight, were mixed in a mixing tube (1 mm i.d., 1 m). On the other hand, a sample solution (235 μl) was injected into a carrier stream of water (flow rate : 2.0 ml min-1), and it was allowed to flow together with the premixed reagent stream. After passing through a reaction tube (1 mm i.d., 3 m), absorbance due to the formation of zirconium-XO or -MTB complex was measured at 550 or 586 nm by a spectrophotometer equipped with a flow cell (light path 10 mm). Under these conditions, 0.012 ppm of fluoride ions can be determined. The detection limit (S/N=2) was 0.01 ppm, and the sampling rate was 40 samples/h. The effect of diverse ions was studied, and the existence of aluminium(III), copper (II), iron(III), sulfite, sulfate, silicate, and organic acids was found to interfere to a great extent in determining fluoride ions. So, it is necessary to distil fluoride ions as hexafluorosilicic acid before determination. The method was applied to samples of natural water, and the applicability of this method was confirmed from the comparison with the results by lanthanum-alizarin complexone method and ion chromatography.
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  • Takeshi KATO, Kiyoshi KANO
    1985 Volume 34 Issue 1 Pages 36-39
    Published: January 05, 1985
    Released on J-STAGE: May 07, 2010
    JOURNAL FREE ACCESS
    A new spectrophotometric method for the determination of cobalt(II) with 2, 2'-dipyridylketone-2-picolylimine(DPPI) in the presence of sodium L-ascorbate is proposed. DPPI is prepared by heating an equimolar mixture of 2, 2'-dipyridylketone and 2-aminomethylpyridine in methanol. DPPI reacts with cobalt(II) to form a water soluble complex which has an absorption maximum at 580 nm. The calibration curve obeys Beer's law over the concentration range from 0.05 to 2.5 μg/ml of cobalt(II). The apparent molar absorption coefficient of the complex is 4.42 × 104 dm3 mol-1 cm-1. The recommended procedure are as follows ; To a sample solution, 1 ml of 10 % sodium L-ascorbate and 5 ml of 10-2 M DPPI solution are added. pH is adjusted to 8.511.1 with ammonia buffer solution, and the solution are heated gently to boil. After cooling the solution to room temperature, it is made up to 50 ml with water. The absorbance is measured at 580 nm against reagent blank. DPPI solution is stable for 50 d in a refrigerator. It is considered that DPPI acts as a tridentate ligand for cobalt(II), from the results of the color reactions of cobalt(II) with DPPI and other Schiff bases similar to DPPI.
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  • Yoshinori NAKAGAWA, Toshiko SUDA, Hiroshi TERADA
    1985 Volume 34 Issue 1 Pages 40-43
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    The cyanine dye Platonin, which has two quarternary ammonium moieties, was found to form a 1 : 2 complex with tetraphenylborate. This complex is scarcely soluble in water and alcohols, unlike Platonin and tetraphenylborate themselves, and is precipitated quantitatively. Thus Platonin can be determined by titration with tetraphenylborate by recording the conductivity of the solution under conditions where Platonin and tetraphenylborate are completely soluble and the complex is insoluble : titration of a solution of Platonin in 60 %(v/v) aqueous methanol with aqueous tetraphenylborate solution at a rate of about 1 ml/min was found to give the best results. Iodide contained as counter ions and a contaminant in Platonin had no effect on the titration. This method is simple and accurate for determination of Platonin.
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  • Akio SAKURAGAWA, Tadao OKUTANI
    1985 Volume 34 Issue 1 Pages 43-47
    Published: January 05, 1985
    Released on J-STAGE: May 07, 2010
    JOURNAL FREE ACCESS
    A new and rapid spectrophotometric method for the determination of a micro amount of nitrite ion was established. Bromide was found to be oxidized by micro amounts of nitrite in the presence of sulfuric acid, and the resulting species had an absorption maximum at 268nm and the absorption increased with an increase in reaction period. Nitrite ion ranging from 0.5 to 5ppm could be determined using this kinetic reaction. Addition of Bindschedler's Green Leuco base(BGL) as oxidation-reduction indicator to the system gave a remarkable increase in sensitivity (λmax=715nm). By the aid of BGL, a more sensitive method has been developed for the determination of micro amounts of nitrite ion based on the above reaction system. The analytical procedure was as follows. One cubic centimeter of 6.0 mol dm-3 sulfuric acid and 3 cm3 of 6.0 mol dm-3 sodium bromide solution were placed in a test tube fitted with a stopper. Then 5 cm3 of sample solution containing less than 0.4 ppm of nitrite was added to the above solution. After 1 cm3 of 0.1 (w/v) % BGL was added, the test tube placed in a water bath at 25 °C. The absorbance was measured at 715 nm with 10mm cell against water at 10min after the addition of the sample solution. By this method, nitrite ion ranging from 0.05 to 0.40ppm can be determined. The relative standard deviation was 1.7% (n=5) at the nitrite ion level of 0.3ppm. Copper (II), iron(III), iodide, and sulfite showed interferences in this method. The proposed method was applied to the determination of nitrite ion in samples of river-water.
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  • Shigehiko HAYASHI, Kinuyo AOYAMA, Naomi KANEGAMI, Keiya KOTSUJI
    1985 Volume 34 Issue 1 Pages 48-52
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    A new ion exchanger named "xanthogenized Sepharose" (X-Sepharose) was prepared by the reaction of Sepharose CL-6B with carbon disulfide in aqueous sodium hydroxide solution. Mercury(II), copper(II), lead(II), cadmium(II), zinc(II), and nickel(II) could be collected quantitatively from 50 ml of 1×10-5 mol 1-1 solution of each metal salts over the pH range of 1.110.2, 1.910.1, 4.25.4, 5.19.7, 6.18.2, and 6.19.2, respectively, by stirring the solution with 0.1g of X-Sepharose for 30 min at room temperature. Collection of mercury and copper from 1 mol 1-1 solution of sodium nitrate, sodium chloride, and sodium bromide were quantitative, but those of other metals were not. Collection of metals were interfered in the presence of EDTA. Metals except for mercury could also be collected quantitatively from 500 ml of 1×10-8 mol 1-1 metal solution by batch method with 0.1 g of X-Sepharose or by passing the solution through the column packed with 0.3 g of X-Sepharose, and could be recovered from the X-Sepharose by dissolving it in concentrated hydrochloric acid or concentrated nitric acid by heating.
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  • Yoshihito SUZUKI, Toshihiro INOUE
    1985 Volume 34 Issue 1 Pages 53-55
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    Trace amounts of cyanide ion in aqueous solution were determined by flow injection analysis as its fluorescent derivative with p-benzoquinone. A small amount of the cyanide solution was injected onto the reaction coil which was set in a thermostat, and then mixed with reagent solution. It was found that 2, 3-dihydrobenzoquinone yielded from cyanide ion had strongly fluorescence at 488 nm. The calibration curve was linear over the concentration from 0.1 to 10 ppm and the relative standard deviation was 2.13 % for 10 runs at 0.1 ppm solution by this method.
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  • Yoshihito SUZUKI, Kazue TANI
    1985 Volume 34 Issue 1 Pages 55-58
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    Trace amounts of aliphatic aldehydes reacted with acetylacetone and ammonium acetate to give its 1, 4-dihydrolutidine derivatives. The separation of derivatives from each aldehyde was investigated by high performance liquid chromatography equipped with a fluorescence detector and completely achieved under the operating conditions as follows. Column was 25 cm×4.6 mm stainless steel tube packed with Zorbax ODS, mobile phase was 50 % MeOH and its flow rate was 0.8 ml/min. Consequently, trace amounts of formaldehyde could be determined by high performance liquid chromatography even in co-existence of each aliphatic aldehyde.
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  • Toru NOZAKI, Minoru MAENO, Raizo HIGAKI, Shohei KAMISAKA, Osamu KAMEI
    1985 Volume 34 Issue 1 Pages 58-60
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    Ion flotation of gold(III), platinum(II), palladium (II), and mercury(II) in hydrobromic acid solutions with cationic surfactants, tetradecyldimethylbenzylammonium chloride(TDBAC), cetylpyridinium chloride(CPC), and cetyltrimethylammonium chloride(CTMAC) was investigated. A 0.023.0 M hydrobromic acid solution (12 ml) containing (4.145.15)×10-4 M of metal and (0.8941.39)×10-3 M of surfactant was subjected to flotation in a 2.7(diameter)×20 cm, cell for 20 min with nitrogen bubbles. Gold(III), platinum(II), palladium(II), and mercury(II) were separated from the respective metal solution in 9499.5 % yield, while (2.277.93)×10-4 M of Cu(II), Zn(II), Ni(II), Co(II), Mn(II), Fe(III), Al(III), Ga(III), In(III), Cr(III), and Sn(IV) were not floated from 0.1 M hydrobromic acid solution. The analysis of the relations between n (the mean number of the ligand Br- per each metal) and the concentration of bromide by means of the mole ratio method, suggested the existence of the species such as AuBr4-, PtBr3-, PtBr42-, PdBr3-, PdBr42-, PdBr53-, HgBr3-, and HgBr42- in hydrobromic acid solution used for the flotation experiments.
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  • Sanae IKEDA, Hiromu SATAKE, Hiroaki SEGAWA
    1985 Volume 34 Issue 1 Pages 60-62
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    A method for the successive determination of sulfide and hydrogen sulfide ions in a mixed solution in the absence of buffer substance such as sulfite was studied by argentimetric potentiometric titration using a sulfide ion-selective electrode as the indicator electrode and a silver-silver chloride electrode (the reference electrode). Sulfide, hydrogen sulfide, and the total sulfide ions could be rapidly titrated with silver nitrate standard solution or hydrochloric acid standard solution at room temperature. The mixtures(total sulfide concentration of about 2.5×10-3 M) of sulfide ion [(3×10-42×10-3)M] and hydrogen sulfide ion [(2×10-42.5×10-3)M] were determined with a relative standard deviation less than 0.3 %. Halide, thiosulfate, and sulfate ions did not interfere with the titration. The recommended procedure is as follows : Place 10 ml of the sample solution (mixed solution containing sulfide and hydrogen sulfide ions) in a titration cell containing 1-cm-thich liquid-paraffin layer. Add water 80 ml, which should be gently poured along the wall of the titration cell so that air bubbles are not entrained. Titrate the resultant solution with 0.1 M silver nitrate standard solution or 0.1 M hydrochloric acid standard solution potentiometrically. The titration times needed is less than 10 min.
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  • Kunikazu IDE, Takeshi KOBAYASHI, Emiko SUDO
    1985 Volume 34 Issue 1 Pages T1-T5
    Published: January 05, 1985
    Released on J-STAGE: May 29, 2009
    JOURNAL FREE ACCESS
    Dinitrogen oxide-acetylene flame atomic absorption spectrometry of hafnium, molybdenum, and vanadium in niobium and niobium-based alloys was studied. The analytical procedure is as follows : Weigh 1 g of a sample and put it into a 100 cm3 PTFE beaker. Add 5 ml of distilled water and 5 ml of hydrofluoric acid, and then heat the solution on a hot plate, adding 3 ml of nitric acid dropwise. Dilute the solution to 100 cm3 with distilled water. When hafnium is determined, add 2 g of diammonium titanium hexafluoride {(NH4)2- TiF6} before dilution. Working standard solutions are prepared by adding the stock standard solutions of hafnium, molybdenum, and vanadium into niobium solutions. When hafnium is determined, add 2 g of (NH4)2TiF6 and the alloying elements in amounts corresponding to those in sample solutions into the working standard solutions. The tolerable amounts of hydrofluoric acid were 2.9 M, 2.1 M, and 3.1 M and those of nitric acid were 1.0 M, 1.6 M, and 1.6 M for hafnium, molybdenum, and vanadium, respectively. It was found that (NH4)2TiF6 greatly increased the sensitivity for hafnium determination. Niobium showed minus effect for hafnium and plus effect for molybdenum and vanadium. The atomic absorption of molybdenum and vanadium were not influenced by the presence of 20 % of each alloying element, while the atomic absorption of hafnium was given plus effect by 20 % of zirconium, iron, cobalt, nickel, manganese, chromium or vanadium and minus effect by 20 % tungsten. The analytical values of hafnium, molybdenum, and vanadium in niobium-based alloys by this method showed a good agreement with those by X-ray fluorescence analysis. The lower limits of determination (S/N=2) were 0.05, 0.001, and 0.002 % and the relative standard deviation were 3, 1, and 1.5 % for hafnium, molybdenum, and vanadium, respectively.
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  • Kiyoshi NOMURA, Yusuke UJIHIRA
    1985 Volume 34 Issue 1 Pages T5-T11
    Published: January 05, 1985
    Released on J-STAGE: January 15, 2010
    JOURNAL FREE ACCESS
    Thin proportional counter for scattering Mossbauer spectrometry (GEMS and XMS) was constructed and the working characteristics were studied to find the optimal condition for the effective detection of the resonant scattered X-ray. The variation of energy spectrum of scattered X-ray was analyzed as a function of the distance between γ-ray source and the sample and the distance between two wire anodes stretched parallel inthe detector. Although photo peaks of resonant X-ray reemitted from the sample surface did not appear clearly in the photon spectrum, the photo peak and escape peak due to resonantly reemitted X-ray and continuous X-ray were observed. The most strong resonant X-ray was found at energies lower than that of Fe X-ray. With the newly designed proportional counter, scattering Mossbauer spectra of iron+silicon (3%) steel and chromium coated steel were measured and the magnetism and chemical composition of the steel surface layers were analyzed.
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