Analysis of (CrKβ+MnKα) overlapping peak curves for varying Cr% and Mn% was undertaken for the determination of Mn in stainless steel, and it revealed that their apparent shapes could be classified into three types only by the ratio of Cr% to Mn%, not by their sample type, as low alloy steel of stainless steel.
The method of eliminating overlapping Cr intensities by equivalent cps measured on Cr Kα peak curve was derived, giving different Mn calibration curves for stainless steel and low alloy steel, respectively, and resulting in an accurate method for the determination of Mn in both steels. Relations between 3 calibration curves for Mn determination, one in the author's previous paper {this journal, 10, 34 (1961)} and two in this paper, were discussed.

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An application of the same Mn calibration. curve, using measured overlapping intensities at. 2θ=62°58' and the same Cr correction terms, as for low alloy steel {this journal, 10, 34 (1961)}, was failed for the determination of Mn in stainless steel, because the overlapping intensities were weakened remarkably, compared with those in low alloy steel.
The decrease of overlapping Cr intensities. were estimated from the Cr Kα calibration curve under a suitable measuring condition to give consistent Cr correction terms for the determination of Mn in stainless steel with the author's previous method for low alloy steel.

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Non-destructive X-ray fluorescence analysis ofcopper-nickel alloy for Cu and Ni was studied. The spectrum of CuKα or NiKα was recorded on a chart, and the intensity of the spectrum was measured as the peak height, followed by a necessary correction with the corresponding spectrum on the standard sample. Variation of the primary-ray intensity did not give any significant effect for corrected intensity. The working line obtained by plotting I_CuKα on Cu% was straight, but the line for I_NiKα on Ni% was a convex curve. The cause of these characteristics of working line was discussed.
Correction for iron content was needed in case of determination of nickel in monel metal which contained higher quantities of iron. The other minor elements did not interfere. The main error was apt to come from the intensity measurement itself, and the standard deviation (σ) was 0.5% for both Cu and Ni when the intensity measurement was carried out on a cutting face by lathe. It seemed that finishing of the surface of specimen should follow the regular course, because the state of the surface was very much improved by means of simple finishing by sandpaper, by which the variation of the corrected intensity was reduced.

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A nondestructive analysis with the measurement of X-ray fluorescence intensity from its spectrum taken on the recording paper has been investigated. Throughout the experiment, the calibration curves were drawn from the X-ray fluorescence intensity and the content of each component.
Determination of cobalt : Independent calibration curve was necessary for estimation of cobalt in cupronickel and of it in monel metal. In case of cupronickel, the intensity was not affected by the difference in the ratio of copper and nickel, and a simple determination of 0.060.34% of cobalt with an error of σ=0.006% was possible. In case of monel metal, however, the difference in copper content affected greatly the fluorescence intensity and it was necessary to prepare each calibration curve for each range of copper content of the alloy.
Determination of iron : A simple and rapid determination of iron was possible by using a calibration curve for cupronikel and monel metal. 0.43.3% of iron could be estimated with an errorσ=0.04%, and even below 0.14% could be estimated an error σ<0.005%.
The limit of determination by use of the recording method was about the same both in the case of cobalt and iron, and seemed to be 0.010.005%. The variation of X-ray fluorescent intensity due to instability of the apparatus was so little that any correction was unnecessary for micro-analysis with sufficient accuracy. In the nondestructive analysis of cobalt and iron, the effect of pulse height analysis was extremely small.

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The author recognized that, when the briquetting electrode method was used for the quantitative spectral analysis of borosilicate, some extraneous elements gave an effect on the determined values of the subjected elements. In order to make clear the effect of extraneous elements, the author studied the conditions using a method as follows.
1.0 g of borosilicate sample was dissolved inhydrochloric acid (1:1). After 10 cc of a cobalt internal standard solution was added, the solution was diluted to 250 cc.
The equipment used were A. R. L. Quantometer, Multisource excitation unit and reservoircupped centerpost reformed electrode.
As the results, some effect of Pb, Zn and Cd on the value of fixing Ca, Mg, Al, Fe and Mn in borosilicate were recognized by the briquetting electrode method, while there was no such effect of the extraneous elements by the solution method.

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Extractabilities of arsenic (III), bismuth and antimony(III) from sulfuric acid-potassium iodide medium into benzene, carbon tetrachloride and methyl iso-butyl ketone have been investigated.
The extraction percentages of these metals are estimated photometrically as follows ; arsenic as molybdenum blue compound, bismuth and antimony as their iodo complexes.
In the sulfuric acid-potassium iodide medium, arsenic, bismuth and antimony are transformed into co-valent triiodides and iodo metallo acid compounds. Among these iodides, arsenic and antimony triiodides are very extractable species to benzene or carbon tetrachloride. As for 10^-3M of arsenic or antimony, complete extractions are made by benzene in the following combina tions of iodide and acid concentrations ; for arsenic, 0.1M of potassium iodide and more than 9N of sulfuric acid, 0.5M of the iodide and more than 7N of the acid, or 1.0M of the iodide and more than 6.5N of the acid media ; for antimony, 0.01M of the iodide and more than 7N of the acid or 0.05M of the iodide and more than 5N of the acid media. On extracting antimony, the extractability decreases with increasing iodide concentration, owing to the formation of certain iodo antimonate complexes which are not extractable by benzene.
Methyl iso-butyl ketone is a useful solvent for these iodides. Both co-valent and metallo acid compounds are completely extracted by this ketone at a more wide range of sulfuric acidpotassium iodide concentration.

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Water in salt can be determined by its nearinfrared absorptions at 1.45 and 1.92 μ, in which the measurement is carried out on the salt in solid state and/or on it dissolved in solvents. The former procedure utilizes plain tablet method, alkalihalide tablet method and Nujol mull method. Those methods are useful for the determination of water in alkalimetal salts and alkaliearth salts by near infrared spectrometry, but cannot be applied for heavy metal salts since they are opaque in the said near infrared region. The results of estimation for alkali salts are less accurate and precise than the other methods.
The latter procedure utilizes deuterium dioxide for dissolving the sample salts, in which water can be determined with the same accuracy as the determination of water in deuterium dioxide. The latter method gives more simple, rapid and reproducible results than the other methods.

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An attempt has been made to establish a new method for determination of berberine, in which a strong yellow-green fluorescence given off by berberine on the filter paper under u. v. irradiation is utilized. The berberine was extracted from berberine-containing crude drugs, as Coptis and Phellodendron, with diluted acetic acid, and the absorption spectra and the fluorescence spectra were compared for the extract and a number of fractions thereof obtained by thepaper chromatographic separations. The fluorescence characteristics of berberine, the disturbing substances in crude drugs, and the conditions for the measurement of fluorescence intensity were widely investigated.
In the recommended procedure, the extract of berberine fraction after a paper chromatographicseparation of the crude drug extract, or the solution of berberine powder diluted to a suitable concentration was spotted on the filter paper and the relative fluorescent intensity was estimated. As little as 0.11.0γ/spot of berberine was determined by this method.

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The presence of crotonaldehyde in vinyl acetate retards the polymerization, lowering polymerization degree of the polymer, and it introduces carbonyl group into the polymerized product. These disadvantages make it necessary the rapid and accurate determination of crotonaldehyde in vinyl acetate. Although there is a polarographic method of determination of crotonaldehyde by application of its definite partition coefficient in water, the method requires too many hours.
The author presented a polarographic determination of crotonaldehyde in vinyl acetate by using the sample in aqueous methanolic solution. The effects of composition of electrolyte solution, pH, temperature and the time required for replacing dissolved oxygen by nitrogen have been investigated. A good reducing wave was obtained at -1.10 V (νs. S. C. E.) by using the sample in 50 vol% aqueous methanolic solution adjusted to pH 3 by Mcllvaine buffer. The method was not affected by the presence of vinyl acetate, acetic acid, acetaldehyde and acetone, and was confirmed to be rapid and simple.

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The authors have proposed that ν_C=o values in the infrared absorption spectra of carbonyl compounds are expressed by the following equation:
ν_C=oA₀+∑Δν_C=o[ℜ]r (in cm^-1)
where A₀ is a fundamental value (1717), Δν_C=o[ℜ]is the value of the mean shift caused by a structural factor surrounding the carbonyl group.The value of various Δν_C=o[ℜ] (Δν_C=o[R]=0) are listed, and six summation rules are proposed. This calculation method does not contradict with the explanation by the electronic theory, and the ν_C=o values obtained by this method are in good approximation with the experimental values.
An analogous equation (in cm^-1 on ν_P=o's) of phosphoryl compounds is also obtained, and this is equivalent with the equation (in μ) offered by Bell et al.

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Colorimetric determination of silica in the presence of large amounts of phosphate has been investigated with reagents (sulfuric acid, oxalic acid, citric acid and tartaric acid) for decomposition of phosphomolybdic acid. Absorbance measurements of phosphomolybdic acid in the presence of the added reagents showed that the order of strength for decomposition of phosphomolybdic acid was citric acid > oxalic acid > tartaric acid. Citric acid was the most suitable among these reagents.
An analytical procedure has been developed as follows:50 ml of a sample solution is taken, and 2 ml of 3N sulfuric acid and 4 ml of 10% ammonium molybdate solution are added. After the maximum color of yellow silicomolybdic acid developed, 2 ml of 1 M citric acid solution is added. After one minute, absorbance at 420 mμ is measured against a blank solution containing the same amount of reagents.
The method was available for the determination of silica ranging from 2 to 40 mg/l of silica in the presence of 200 mg/l of phosphate ion.
It was supposed that the citric acid decomposed phosphomolybdic acid by formation of 1 : 2 citrate complex (1 citric acid : 2 Mo) with molybdic acid.

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Acid dissociation constants of oxime and thiosemicarbazone derivatives of thiazolylaldehyde and ketone and stability constants for formation of copper chelate were calculated from the results of their pH titrations in 50% dioxane with ionic intensity 0.1 at 25°C. It was found that the acid dissociation constants of the oximes were in the range of 2.612.72 for pK_NH⁺ and 10.3111.45 for pK_OH. The stability constants, log K_av, of their copper chelates were 7.8040.04.
In thiosemicarbazone derivatives, the acid dissociation constants were in the range of 2.60 2.75 for pK_NH⁺ and 10.7341.47 for pK_SH, and the stability constants, log K_av, of their copper chelates were 10.2941.21. The authors supposed that the copper chelate of the oximes consisted in a six-membered ring including O in the oxime and N in the thiazole nucleus, and that of the thiosemicarbazones a five-membered ring including S and =N- in thiosemicarbazone group.

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Acid dissociation constant of thiazolylthiourea derivatives and the stability constant of the copper chelate were determined by the pH titration in 50% dioxane with ionic intensity 0.1 at 25°C.
The acid dissociation constants were in the range of 1.792.86 for pK_NH⁺, and 9.0610.56 for pK_SH. The stability constants, log K_av, of the copper chelate were in the range of 8.2310.93. A linear correlation was found between the acid dissociation constant, pK_a(pK_NH⁺+pK_SH), and the stability constant of the copper chelate, log K_av.

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A spectrophotometric determination of a small amount of thorium in uranium metal using thorin as the reagent has been developed.
As a method for the separation of a large amount of uranium from coexisting thorium, extraction with TBP-benzene from 4.55N. hydrochloric acid solution has been investigated and it was applied in the practical analysis. The separation was carried out efficiently and seemed much simpler than that by precipitation or ion exchange. Taking 1 g sample and making it up to 10 ml of the solution for spectrophotometric measurement at 545 mμ with a depth of 1 cm, 1060 ppm thorium in the sample could be determined.
An investigation on the separation of trace of thorium in uranium was successfully done by using tracers UX₁ and UX₂ originally present in the sample arriving at the radiation equilibrium.

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The uranium metal sample was dissolved in hydrochloric acid and hydrogen peroxide. The sample solution was evaporated to dryness and the salt was taken up with diluted hydrochloric acid. Ammonium citrate was added to the solution and the pH was adjusted to 8.59.0 with diluted ammonium hydroxide. Cu, Pb, Cd, Zn, Ni and Co in the solution were extracted with dithizone-benzene solution and Pb, Cd, Zn were back extracted into 0.3N perchloric acid. Pb and Cd were determined by A. C. polarography and then Zn was determined also polarographically after an addition of pyridine to this solution.
The remaining dithizone-benzene extract containing Cu, Ni and Co was heated to almost dryness to expel the majority of benzene, concentrated perchloric acid was added, and the whole was heated to dryness. Stand to cool, 0.3N perchloric acid was added and Cu was determined by A. C. polarography. Ni and Co were also polarographically determined after an addition of pyridine to this solution.

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A new method of detecting cobalt ion has been presented, in which cobalt gives an intense blue coloration with the white emulsion produced by ammonium thiocyanate and benzalkonium chloride.
The procedure is as follows : benzalkonium. chloride solution is added to the test solution and agitated and ammonium thiocyanate solution is added drop by drop. When cobalt ion is present, a blue emulsion appears.
The method can be applied also in the spot test on the paper, as follows. A colorless oily product obtained by mixing benzalkonium chloride solution with ammonium thiocyanate solution is diluted with 56 times as much ethyl alcohol. A filter paper is impreganted with the alcoholic solution thus obtained, and dried.
A blue fleck by spotting the test paper indicates the presence of cobalt.
About 0.7γof cobalt in one drop of sample solution can be detected by this method.

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From the investigation of the determination of boron by 1, 1'-dianthrimide method, the following procedure has been established.
Aluminum sample is dissolved in hydrochloric, nitric, and sulfuric acids. After adjusting the acidity of the solution by adding distilled water, most of aluminum is removed by adsorption on cation exchanger Dowex 50. The effluent is evaporated to fumes of sulfuric acid, and after cooling, heated with 1, 1'-dianthrimide at 90°C for 90 min. Then, the absorbance is measured photometrically at 630 mμ.
Reaction ratio of this reagent and boron is found to be 1 : 1, but it is necessary to add a definite excess of the reagent, for the decomposition of the reagent proceeds at the same time with the complex formation.
It is unnecessary to hinder boron scattering by adding calcium oxide to the sample solution.
Calibration curve up to B 4 γ /10 ml is linear. Interfering elements are not found, except the precipitation of sulfates. Co-existence of aluminum less than 10 mg is not objectionable.

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Determination of K⁺ in urine by use of sodium dipicrylaminate has been investigated, and a simple colorimetric method was presented. Addition of an aqueous solution of sodium dipicrylaminate to the urine resulted in quantitative precipitation of K salt, and the method was based on the fact that the light absorbancy of the filtrate at 420 mμ (Fig. 1) was inversely related to the concentration of K⁺.
Although the presence of a large amount of NH₄⁺ in the urine interfered with the reaction, the influence was removed by boiling off ammonia with NaOH. Good reproducibilities were obtained for the concentrations of 50200 mg% of K⁺ (Table III), and the recovery of K⁺ added into the urine was 96.7% (Table IV).

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[in Japanese]

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