An introduction to surfactant and micellar systems is presented. The unique properties exhibited by micellar systems that are ideally suited and very useful in the field of analytical chemistry are outlined (ie. their solubilization power; their utilization as a novel reaction medium in which the rates, equilibrium position, products, and, in a few instances, stereochemistry can be affected; and their ability to greatly alter the microscopic properties and change the effective microenvironment about solubilized solutes). A summary of published work is presented in which micellar systems have been successfully utilized to either improve existing analytical methods or help overcome problems associated with the development of new analytical procedures. Specific examples of such practical and useful applications of micellar systems are given for spectral methods of analysis such as ultraviolet-visible absorption, fluorescence, and atomic absorption; for electroanalytical methods involving potentiometry and polarography; and for chemical separations including chromatographic and extraction techniques. In each case, the micellar chemistry and/or properties involved in the particular analytical application are elucidated. The advantages of these micellar-improved analytical methods are discussed. Several other miscellaneous applications as well as potential areas for future research involving micellar systems in analytical chemistry are pointed out in the overview.

Use of Surfactant and Micellar Systems in Analytical Chemistry

I. INTRODUCTION One of the most remarkable properties widely used in chemical analysis is the ability of a metal ion solution or a chemical substance to change its color under the effect of external factors, most often chemical reactions. Such reactions are known as color reactions. Color reactions of practical value have been found for almost all inorganic ions. It would hardly be an exaggeration to say that until recently almost half of all analyses, particularly in important branches of industry and in agriculture, were based on colorimetric and, later, photometric (or spectrophotometric) techniques.

Organic Reagents in Photometric Analysis

Study of the titanium-phenylfluorone complex formed in the presence of Triton X-305 and emulsifier OP.

A yttrium-TAC chelate anion reacts with a benzyldimethyltetradecylammonium chloride(Zephiramine) solution to form a ternary complex. The ternary complex has an absorption maximum at 610 nm in an aqueous solution of a pH range from 7.5 to 8.0. The ternary complex and ytrium-TAC chelate anion are stable for at least 5 hours and 20 minutes, respectively. Beer's law is obeyed up to the concentration of 1.2 μg ml−1 of yttrium. Molar absorptivity of the ternary complex is 3.7 × 104 l mol−1 cm−1 at 610 nm and sensitivity for yttrium is 2.4 × 10−3 μ cm−1 per 0.001 of absorbance. The composition of the ternary complex is estimated to be Y(tac)4(Zeph). A number of ions which interfere with the determination could be masked by the addition of various masking agents.

Spectrophotometric Study of the Yttrium-TAC-Zephiramine Ternary Complex

Firstly, the syntheses of various organic reagents {R} containing such xanthene derivatives as O-hydroxyhydro-quinonephthalein (QnPh), and 3,4,5,6-tetrahydroxyfluoran (gallein, Gall) were studied. Secondarily, the coexisting effects of surfactant (cationic-, anionic-, amphoteric- and nonionic-surfactants alone or combination) on the coloring or fluorescence reactions between various {R} such as xanthene derivatives, aromatic amines and various metal ions {M} such as bismuth (III), tin (IV), iron (III), molybdenum (VI), uranium (VI), cobalt (II), aluminum (III), etc. were systematically investigated. Thirdly, numerous simple and sensitive photometric analyses (spectrophotometry and fluorophotometry) for various {M} and organic compounds {Org} such as biological samples, and pharmaceutical preparations by formation reactions of {R-M} binary or {(R-M)-Org} ternary complexes were established in the coexistence of surfactant alone or combination.

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金属イオン {m}-有機試薬 {r} 反応を用いる光分析法

In the presence of excess cetylpyridinium chloride (CPC) in an acidic solution molybdenic acid(MoO42-) forms a water soluble complex with phenylfluorone, whose color was very stable. The color development of a water soluble reddish brown complex between phenylfluorone and Zr(IV) enhanced by the catalytic action of sodium fluoride, particluary in the coexistence of excess CPC which increased the absorbance of the complex. Their absorption maximum wavelength were at about 540 nm (MoO42-), 560 nm {Zr(IV)} against the reagent blank, and the coloration was stable over the pH range from 1.2 to 1.9 (pH was adjusted with NaCl glycocohol-HCl buffer solution) and pH range from 4.2 to 5.2 (pH was adjusted CH3COONa-CH3COOH buffer solution). A linear calibration curve was obtained for 460 μg MoO42-/10 ml and 07 μg Zr(IV)/10 ml. According to Sandell's expression the sensitivities were 0.01 μg/cm2 of MoO42- and 0.002 μg/cm2 of Zr(IV) for absorbance of 0.001. From the data, the recommended analytical procedures of MoO42-, and Zr(IV) are as follows.A sample containing 460 μg MoO42- is taken in a 10.0 ml measuring flask, and 1.0 ml of 1.0 × 10-2 M CPC solution, 2.0 ml of buffer solution(pH 1.5), and 2.0 ml of 1.0 × 10-3 M phenylfluorone methanolic solution are added. The solution is diluted to 10.0 ml with water, and allowed to stand at 45°C for 30 minutes, the absorbance of phenylfluorone-MoO42--CPC complex is measured at 540 nm against the reagent blank. To the solution of Zr(IV) is added each 1.5 ml of 1.0 × 10-2 M CPC solution, 0.8 ml of 1.0 × 10-2 M sodium fluoride solution, 1.0 ml of 2.0 × 10-3 M methanolic phenylfluorone solution, and 1.5 ml of buffer solution (pH 4.6). After making up to the volume to 10.0 ml and allowing it to stand for 10 minutes, the absorbance is measured at 560 nm against the reagent. The effects of diverse ions on the absorbance of the complex were examined and shown.

山本栄

Papers

フェニルフルオロンと塩化セチルピリジニウムを用いるモリブデン酸およびジルコニウム(iv)の吸光光度定量

山本 栄

Papers

フェニルフルオロンと塩化セチルピリジニウムを用いるモリブデン酸およびジルコニウム(iv)の吸光光度定量

山本栄