Wataru Funasaka

Salting-out chromatographie separation of hydroxybenzoic acid isomers

Abstract The separation of hydroxybenzoic acid isomers by salting-out chromatography using Amberlite CG-50 (Na+ form) as stationary phase and acidic sodium chloride solution as mobile phase has been studied. The distribution coefficients of hydroxybenzoic acids increased with increase in the concentration of sodium chloride and with decrease in the pH of the solution. The best separation was achieved when a mixture of the o- and m-isomers or the o- and p-isomers was eluted at 40 ± 1° through a column of length 150 mm and I.D. 10 mm with 2 M sodium chloride solution of pH 1.8. The determination of the acids in the eluates by UV spectrophotometry proved that the recovery of the acids was almost quantitative.

Studies on ligand-exchange chromatography : III. Separation of nitrosonaphthol isomers

Abstract The separation of α-nitroso-β- and β-nitroso-α-naphthols by ligand-exchange chromatography was studied. The best results were obtained by use of a strong acid type resin in the Fe 3+ form as a stationary phase and a 50 % v/v ethanolic ammonia solution (pH 9.5 and 12.0) as the mobile phase for stepwise elution. In view of the slow adsorption rate of both isomers to the resin, the Fe(III)-nitrosonaphthol complex formed in the resin phase seems to be a low-spin 1:1 complex for which the oxygen of the hydroxyl group and the nitrogen of the nitroso group are both responsible.

Studies in ligand-exchange chromatography : Part IV. Separation of hydroxybenzoic and hydroxynaphthoic acid isomers

Abstract The separation of isomers of hydroxybenzoic and hydroxynaphthoic acids by ligand-exchange chromatography using the metallic form of a cation-exchange resin as the stationary phase and dilute aqueous ammonia or water as the mobile phase was studied. The distribution coefficients and the separation factors of hydroxybenzoic acid isomers were larger on the Fe(III) form than on the Ti(IV) form of the resin, but a faster rate of adsorption was observed on the Ti(IV) form rather than on the Fe(III) form of the resin. The separation of hydroxybenzoic acid isomers was best achieved by eluting a mixture of the o - and p -isomers or fo the m - and p -isomers with water through a column of 50 cm in length and 9 mm I.D., packed with the Fe(III) form of the resin which had been equilibrated at pH 4.7 with aqueous ammonia. The controlled surface resin, having sulphonic acid groups only on the surface of the resin beads, was also tested as a stationary phase for the resolution of hydroxynaphthoic acid isomers.

Indirect determination of lanthanum in a mixture of rare earth oxide

Lanthanum in a mixture of rare earth oxide, consisting of the elements of cerium and yttrium groups, was determined indirectly by using a combination of gravimetric, volumetric and colorimetric procedures. The two groups were separated from each other by the double sulfate method, and the rare earth elements of the cerium group were determined by weighing the oxide. In addition to lanthanum and cerium, the cerium group contained praseodymium, neodymium and samarium, which were determined colorimetrically by utilizing their sharp absorptions at 444.5 nm, 521.8 nm and 401.5 nm, respectively. Cerium was determined volumetrically by the method of JIS 8404 without group separation. The lanthanum content was calculated by the equationLa2O3(%) =Cerium group rare earth oxide (%)-CeO2(%)-Pr6O11(%)-Nd2O3(%)-Sm2O3(%).The results obtained showed good precision, and were in fairly good agreement with those by the X-ray fluorescence method. It suggests that at the stage of the group separation the lanthanum and cerium in the sample were completely precipitated as their double sulfates and all the yttrium group elements were removed from the precipitate.The method reported here is expected to be generally applicable to the determination of lanthanum in a mixture of rare earth oxide which consists mainly of cerium group elements.

Microdetermination of carbon and hydrogen in organic fluorine compounds by sodium fluoride method

フッ素除去剤としてフッ化ナトリウムを用いる有機フッ素化合物の炭水素分析法を検討した.触媒としては酸化銅を用い,空気により燃焼させる方法をとった.フッ化ナトリウム粒は,フッ化ナトリウム粉末を加圧成型機を用いて固め,破砕してつくったが,この粒は固くて容易に粉末化せず,しかも寿命はかなり長かった.水素がフッ素に対して当量以上の試料では,炭素,水素とも良好な結果が得られた.水素がフッ素より少ない試料では,水素については良好な結果が得られたが,炭素については計算値に比べ低い傾向が認められた.ただし,試料がある程度水素を含んでいる場合には,計算値との差は著しいものではない.しかし,水素をまったく含まない場合には,試料によってはその差が著しく大きいことがあり,分析結果は一般に信頼できないことがわかった.

Determination of Zirconium in Minerals by X-Ray Fluorescence Method

鉱物中のジルコニウムを迅速に定量するためにケイ光X線法を試み,内部標準としてストロンチウムを用いる検量線法が適当であることを認めた。すなわち,試料100～500mgに炭酸ストロンチウム100mgを加え,融剤としてフッ化水素ナトリウム5gおよびリン酸水素二ナトリウム5gを用い,さらに硫酸カリウム5gを添加して融解し,融成物についてZrKα(SrKβを含む)およびSrKαの強度を測定し,標準酸化ジルコニウムを用いて同様な処理によって得た検量線を使って定量値を求めた。ZrKαに対するThLβの重なりは.IThβ/IThα=0.446を用いてThLαにより補正した。諸種の共存元素の影響はほとんどなく,模擬試料(3種)および実試料(2種)について満足すべき結果が得られた。

Reactions of a-Halo Calbonyl Compounds with Grignard Reagents. (Part 3).. Reactions of Chloro- and of Fluoroacetic Acid

モノクロル酢酸とグリニャール化合物(RMgX,R=フェニル,p-メトキシフェニル,-フルオルフェニル,o-メトキシフェニル,n-ブチル)とをモル比1:2で0℃付近で反応させると,30～60%の収率でクロルメチルケトンCH2ClCORが得られること,モノフルオル酢酸でも同様な反応はおこるが,ハロゲンを含まないカルボン酸RCH2COOHの副生量が増加するために,ケトンCH2FCORの収率は低下すること,モノフルオル酢酸と臭化フェニルマグネシウムとをモル比1:4で70℃付近で反応させると,1,1-ジフェニル-1,2-エタンジオールが得られることなどを明らかにし,あわせてこれらの反応の径路について考察した。

Chromatography of dinitrophenols

パラニトロフェノール,2,4-および2,6-ジニトロフェノール,2,4,6-トリニトロフェノールをペーパークロマトグラフ法およびロ紙電気泳動法によって分離することを試みた.ペーパークロマトグラフ法ではクエン酸緩衝液で緩衝化したロ紙を用い,同様の緩衝液を含むアミルアルコール-ベンゼンで展開するか,または酢酸ナトリウム水溶液で処理したロ紙を用い,アミルアルコール-ベンゼン-酢酸で展開すれば分離は良好である.ロ紙電気泳動法ではpH3.2～3.6の酢酸-酢酸ナトリウム緩衝液を用い,500Vで1.5時間泳動をおこなえば,分離が完全であることを確かめた.2,4-ジニトロフェノール中の2,6-ジニトロフェノール,2,4,6-トリニトロフェノールを定量する目的でカラム電気泳動法について検討を加え,0.25%の2,6-ジニトロフェノール,2,4,6-トリニトロフェノールの定量が可能であることを確かめた.

Rapid determination of SO3 in Cements by an Anion Exchange Resin

The sulphate content of cements was determined by an anion exchange resin method. The sulphate ion was converted to chloride ion using Amberlite IRA-400. The chloride ion was titrated by the potentiometry. The results agreed with the results of the barium sulphate method, and were obtained in 2 or 3 hours.

Comparative Studies ou the Micro-Determination of Fluorine

Colorimetric determination of a sample solution of NaF containing less than 10p.p.m. F- were made by use of a) ferric thiocyanate method, b) ferric salicylate method, c) thorium alizarin method, d) zirconium alizarin method, and e) aluminum hematoxylin method in the presence or absence of the disturbing ions. Within the range of showing linear transmittancy coefficient against the concentration, statistical interpretation of the result by Youden method was applied and found that the b) method was disturbed by CO--3, and that of the a) and c) methods by SO--4, The b) method was the most suitable for determination of less than 10p.p.m. F-, since this method required less time, reagents used are stable and the method has good accuracy and high sensitivity. Also, c) or d) method was suitable for determination of less than 5p.p.m. F-.