Anionic surfactants, determination

Nomura Y, Ikebukuro K, Yokoyama K, Takeuchi T, Arikawa Y, Ohno S, Karube I (1994) A novel microbial sensor for anionic surfactant determination. Anal Lett 27 3095 - 3108... 

E. Rodenas-Torralba, B.F. Reis, A. Morales-Rubio, M. de la Guardia, An environmentally friendly multicommutated alternative to the reference method for anionic surfactant determination in water, Talanta 66 (2005) 591. 

Nomura, Y., K. Ikebukuro, K. Yokoyama, T. Takeuchi, Y. Arikawa, S. Ohno, I. Karube, Novel microbial sensor for anionic surfactant determination. Anal. Lett., 1994, 27, 3095-3108. 

Rubio-Barroso, S., L. M. Polo-Diez, V. Rodriguez-Gamonal, M. Gomez-Rodriguez, Comparative study of spectrofluorometric and spectrophotometric methods for anionic surfactants determination in wastewater. An. Qhim., Sen B, 1988,84, 361-365. 

The concentration of anionic surfactants at the sub-ppm level in natural waters and industrial waters are determined spectrophotometrically. The anionic surfactants are extracted into a nonaqueous solvent following the formation of an ion association complex with a suitable cation. 

A reexamination of so-called renewabdity has shown that advantages for oleochemicals are not sufftcientiy clear (115), especially because manufacture of surfactants ia the United States accounts for only 0.03% of aimual cmde oil consumption (62). On these bases, the primary determinants of surfactant choice will continue to be cost effectiveness and availability. The 1993 U.S. market has been estimated to be worth 3.7 x 10 (110). Approximately one-half was anionic surfactant ( 1.8 x 10 ) and one-third nonionic surfactant ( 1.2 x 10 ). The balance was made up by cationics ( 1.2 X 10 ) and amphoterics ( 600 x 10 ). The U.S. International Trade Commission (116) provides a minutely detailed breakdown of surfactant production. 

The system of anionic surfactants is another example of organic compounds mixtures. The procedure of their determination is proposed using coordinate pH in two-dimensional spectra of ionic associates anionic surfactants with rhodamine 6G. This procedure was tested on the analysis of surfactant waters and domestic detergents. 

SOLID-PHASE SPECTROPHOTOMETRIC METHOD FOR THE DETERMINATION OF ANIONIC SURFACTANTS WITHOUT LIQUID-LIQUID EXTRACTION... 

In this work hybrid method is suggested to determine anionic surfactants in waters. It is based on preconcentration of anionic surfactants as their ion associates with cationic dyes on the membrane filter and measurement of colour intensity by solid-phase spectrophotometry method. Effect of different basic dyes, nature and hydrophobicity of anionic surfactants, size of membrane filter pores, filtration rate on sensitivity of their determination was studied. Various cationic dyes, such as Methylene Blue, Crystal Violet, Malachite Green, Rhodamine 6G, Safranin T, Acridine Yellow were used as counter ions. The difference in reflection between the blank and the sample was significant when Crystal Violet or Rhodamine 6G or Acridine Yellow were used. 

The aqueous micellai solutions of some surfactants exhibit the cloud point, or turbidity, phenomenon when the solution is heated or cooled above or below a certain temperature. Then the phase sepai ation into two isotropic liquid phases occurs a concentrated phase containing most of the surfactant and an aqueous phase containing a surfactant concentration close to the critical micellar concentration. The anionic surfactant solutions show this phenomenon in acid media without any temperature modifications. The aim of the present work is to explore the analytical possibilities of acid-induced cloud point extraction in the extraction and preconcentration of polycyclic ai omatic hydrocai bons (PAHs) from water solutions. The combination of extraction, preconcentration and luminescence detection of PAHs in one step under their trace determination in objects mentioned allows to exclude the use of lai ge volumes of expensive, high-purity and toxic organic solvents and replace the known time and solvent consuming procedures by more simple and convenient methods. 

Sodium dodecylsulphate was selected as an anionic surfactant Factors affecting acid-induced cloud point extraction including surfactant, hydrochloric acid, PAHs, and electrolyte concentration, centrifugation have been examined. Finally, we applied the optimized acid-induced CPE system for combination of the extraction and preconcentration steps with fluorimetric determination of some representatives of PAHs. Suggested means was used for PAHs determination in tap water. 

Poloxamers are used primarily in aqueous solution and may be quantified in the aqueous phase by the use of compleximetric methods. However, a major limitation is that these techniques are essentially only capable of quantifying alkylene oxide groups and are by no means selective for poloxamers. The basis of these methods is the formation of a complex between a metal ion and the oxygen atoms that form the ether linkages. Reaction of this complex with an anion leads to the formation of a salt that, after precipitation or extraction, may be used for quantitation. A method reported to be rapid, simple, and consistently reproducible [18] involves a two-phase titration, which eliminates interferences from anionic surfactants. The poloxamer is complexed with potassium ions in an alkaline aqueous solution and extracted into dichloromethane as an ion pair with the titrant, tet-rakis (4-fluorophenyl) borate. The end point is defined by a color change resulting from the complexation of the indicator, Victoria Blue B, with excess titrant. The Wickbold [19] method, widely used to determine nonionic surfactants, has been applied to poloxamer type surfactants 120]. Essentially the method involves the formation in the presence of barium ions of a complex be-... 

The chemical properties of the alkylarylsulfonates are used in its analytical determination. As anions, LAS and other anionic surfactants react with large cations to salts, which are soluble in organic solvents (e.g., CHC13). By analysis it can be seen that cations such as Hyamine 1622 (25) and methylene blue, which rearrange with LAS to complex (26), are widely spread. These reactions are the basis for the so-called two-phase titration, an extensively used method... 

TABLE 17 Titration Methods for the Determination of Anionic Surfactants... 

Anionic surfactants like alkanesulfonates can also be determined by poten-tiometric titration with ion-selective electrodes. Recently, a special PVC electrode was offered as a high-sense surfactant electrode in combination with the new titrant l,3-didecyl-2-methylimidazolium chloride [20]. This one-phase... 

A ring test proved that surfactant-selective electrodes are suitable for quantitative determination of anionic surfactants including alkanesulfonates [21]. The precision of this method, however, does not yet correspond to the state-of-the-art of the two-phase titration. Therefore, further development is needed to enhance the reproducibility and competitiveness of surfactant-sensitive titration. 

A sensitive determination of alkanesulfonates combines RP-HPLC with an on-line derivatization procedure using fluorescent ion pairs followed by an online sandwich-type phase separation with chloroform as the solvent. The ion pairs are detected by fluorescence. With l-cyano-[2-(2-trimethylammonio)-ethyl]benz(/)isoindole as a fluorescent cationic dye a quantification limit for anionic surfactants including alkanesulfonates of less than 1 pg/L per compound for a 2.5-L water sample is established [30,31]. 

Physical methods for endpoint detection have been suggested. Hellsten [226] proposed an instrumental turbidimetric method to determine the endpoint, which does not need indicators. Since chloroform is emulsified by the anionic surfactant, changes in the optical density can be followed by a colorimeter thus detecting the endpoint when the emulsion breaks. Another turbidimetric method based on commercially available automatic titrators has also been proposed [227],... 

Other detection methods are based on optical transmittance [228-231], Alcohol sulfates have been determined by spectrophotometric titration with barium chloride in aqueous acetone at pH 3 and an indicator [232] or by titration with Septonex (carbethoxypentadecyltrimethylammonium bromide) and neutral red as indicator at pH 8.2-8.4 and 540 nm [233]. In a modified two-phase back-titration method, the anionic surfactant solution is treated with hyamine solution, methylene blue, and chloroform and then titrated with standard sodium dodecyl sulfate. The chloroform passing through a porous PTFE membrane is circulated through a spectrometer and the surfactant is analyzed by determining the absorbance at 655 nm [234]. The use of a stirred titration vessel combined with spectrophotometric measurement has also been suggested [235]. Alternative endpoint detections are based on physical methods, such as stalag-mometry [236] and nonfaradaic potentiometry [237]. 

Turbidimetric titration has also been applied to one-phase titration of alcohol sulfates and other anionic surfactants. The titration is carried out with hyamine 1622 in aqueous solution without the organic phase and indicator and the endpoint is taken as the point of maximum turbidity. The presence of nonionics and inorganic salts at high concentration interfere with the endpoint determination [243]. 

Electrochemical analytical techniques are a class of titration methods which in turn can be subdivided into potentiometric titrations using ion-selective electrodes and polarographic methods. Polarographic methods are based on the suppression of the overpotential associated with oxygen or other species in the polarographic cell caused by surfactants or on the effect of surfactants on the capacitance of the electrode. One example of this latter case is the method based on the interference of anionic surfactants with cationic surfactants, or vice versa, on the capacitance of a mercury drop electrode. This interference can be used in the one-phase titration of sulfates without indicator to determine the endpoint... 

Similarly to quantitative determination of high surfactant concentrations, many alternative methods have been proposed for the quantitative determination of low surfactant concentrations. Tsuji et al. [270] developed a potentio-metric method for the microdetermination of anionic surfactants that was applied to the analysis of 5-100 ppm of sodium dodecyl sulfate and 1-10 ppm of sodium dodecyl ether (2.9 EO) sulfate. This method is based on the inhibitory effect of anionic surfactants on the enzyme system cholinesterase-butyryl-thiocholine iodide. A constant current is applied across two platinum plate electrodes immersed in a solution containing butyrylthiocholine and surfactant. Since cholinesterase produces enzymatic hydrolysis of the substrate, the decrease in the initial velocity of the hydrolysis caused by the surfactant corresponds to its concentration. Amounts up to 60 pg of alcohol sulfate can be spectrometrically determined with acridine orange by extraction of the ion pair with a mixture 3 1 (v/v) of benzene/methyl isobutyl ketone [271]. 

A highly sensitive method for the determination of anionic surfactants, particularly sodium dodecyl sulfate, has been described [275]. The method is based on the formation of fluorescent ionic complexes of the anionic surfactant with acridine red and acridine yellow. The complexes are extracted with dichloro-... 

ISO 7875-1 1984, Water quality. Determination of surfactants—Part 1 Determination of anionic surfactants by the methylene blue spectrometric method. 

Active matter (anionic surfactant) in AOS consists of alkene- and hydroxy-alkanemonosulfonates, as well as small amounts of disulfonates. Active matter (AM) content is usually expressed as milliequivalents per 100 grams, or as weight percent. Three methods are available for the determination of AM in AOS calculation by difference, the two-phase titration such as methylene blue-active substances (MBAS) and by potentiometric titration with cationic. The calculation method has a number of inherent error factors. The two-phase titration methods may not be completely quantitative and can yield values differing by several percent from those obtained from the total sulfur content. These methods employ trichloromethane, the effects from which the analyst must be protected. The best method for routine use is probably the potentiometric titration method but this requires the availability of more expensive equipment. 

The amount of residual sulfonate ester remaining after hydrolysis can be determined by a procedure proposed by Martinsson and Nilsson [129], similar to that used to determine total residual saponifiables in neutral oils. Neutrals, including alkanes, alkenes, secondary alcohols, and sultones, as well as the sulfonate esters in the AOS, are isolated by extraction from an aqueous alcoholic solution with petroleum ether. The sulfonate esters are separated from the sultones by chromatography on a silica gel column. Each eluent fraction is subjected to saponification and measured as active matter by MBAS determination measuring the extinction of the trichloromethane solution at 642 nra. (a) Sultones. Connor et al. [130] first reported, in 1975, a very small amount of skin sensitizer, l-unsaturated-l,3-sultone, and 2-chloroalkane-l,3-sultone in the anionic surfactant produced by the sulfation of ethoxylated fatty alcohol. These compounds can also be found in some AOS products consequently, methods of detection are essential. 

Analytical methods for qualitative and quantitative determination of all kinds of surfactants have long been established. There can be found either wet chemical methods—like titration—or methods of instrumental analytics. A classical method for anionic surfactants is the so-called two-phase-titration [63]. Using this method nearly every molecule bearing an anionic group is detected. The correct determination of sulfosuccinates is limited to the interferences of the other ingredients and byproducts present. With few exceptions all sulfosuccinates react with special indicators, e.g., hyamin 1622 (Rohm and Haas), to form an anionic-cationic complex and hence are to be analyzed by active content titration. 

CE has been used for the analysis of anionic surfactants [946,947] and can be considered as complementary to HPLC for the analysis of cationic surfactants with advantages of minimal solvent consumption, higher efficiency, easy cleaning and inexpensive replacement of columns and the ability of fast method development by changing the electrolyte composition. Also the separation of polystyrene sulfonates with polymeric additives by CE has been reported [948]. Moreover, CE has also been used for the analysis of polymeric water treatment additives, such as acrylic acid copolymer flocculants, phosphonates, low-MW acids and inorganic anions. The technique provides for analyst time-savings and has lower detection limits and improved quantification for determination of anionic polymers, compared to HPLC. 

Figure 7.17 shows the asymmetry ratios of a series of compounds (acids, bases, and neutrals) determined at iso-pH 7.4, under the influence of sink conditions created not by pH, but by anionic surfactant added to the acceptor wells (discuss later in the chapter). The membrane barrier was constructed from 20% soy lecithin in dodecane. All molecules show an upward dependence on lipophilicity, as estimated by octanol-water apparent partition coefficients, log KdaA). The bases are extensively cationic at pH 7.4, as well as being lipophilic, and so display the highest responses to the sink condition. They are driven to interact with the surfactant by both hydrophobic and electrostatic forces. The anionic acids are largely indifferent... 

In this physical methodology, hand-rinsing the volunteers immediately following the activity period removed some test substance from the hands if left on the hands, this substance would have had the opportunity to be absorbed and therefore would have increased the biomonitoring values. In addition, we do not currently know the efficiency of the hand rinse. It is generally thought that the efficiency of the hand rinse using anionic surfactants to remove chlorpyrifos is no better than 50%,5 a value to be determined in future research. 

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