Cationic surfactants, determination

Actually, the successful use of cationic surfactants (cSurf), as flotation reagents, frothers, metal corrosion inhibitors, pharmaceutical products, cosmetic materials, stimulates considerable increase in their production and as a result increases their content in natural water. As cationic surfactants are toxic pollutants in natural water and their maximum contaminant level (MCL) of natural water is 0.15-4.0 mg/dm, it is necessary to use methods for which provide rapid and reliable determination with sensitivity equal to at least 0.1 of MCL. Practically most sensitive methods of cationic surfactant determination include the preconcentration by extraction or sorption. Analytical methods without using organic solvents are more preferable due to their ecological safety. 

The investigation leads to the elaboration of solid-phase spectrophotometric and test methods of different cationic surfactants determination in water. The detection limits of cationic surfactants with hydrocarbon radical length is 0.7 mg/dm, is 0.2 mg/dm, C is 0.009 mg/dm and is 0.003 mg/dm by using a 100 cm sample. Metrological performance of method was examined on the natural samples. Proposed method is highly sensitive, simple, rapid and guarantees ecological purity of analysis. 

Wang, L.K. Cationic Surfactant Determination Using Alternate Organic Solvent, PB86-194164/ AS US Department of Commerce, National Technical Information Service Springfield, VA, 1983 ... 

Volumetric methods are the traditional methods employed in routine controL specifically two-phase titration for anionic and cationic surfactant determination, and are characteristically highly sensitive. They are based on the reaction between an anionic surfactant and cationic surfactant (one of which is a sample surfactant and the other a titrant surfactant) in a two-phase system (chloroform-water). The endpoint is detected by a transfer-phase indicator, the most common of which is a mixture of dimidium bromide and disulfine blue although methylene blue (Epton method), which is the first indicator chronologically, is also applied. Two commonly used titrants are sodium lauryl sulfate for cationic surfactants and benzethonium chloride, currently named Hyamine 1622, for anionic surfactants. 

SOLID-PHASE SPECTROPHOTOMETRIC AND TEST DETERMINATION OF CATIONIC SURFACTANTS ON PAPER FILTERS AS ION ASSOCIATE WITH BROMPHENOL BLUE... 

In this work hybrid method is suggested to determine cationic surfactants in water. It is based on preconcentration of cationic surfactants in the some of ion associates with acidic dyes on the paper filter and measurement of color intensity by solid-phase specdophotomenic method or visual comparison. 

An obvious modification of the above procedure will permit the determination of long-chain amines or quaternary ammonium salts (cationic surfactants) ... 

The role of a cationic surfactant must be to provide a necessary hydrophobic and polarized environment for the molecule of luciferin for its luminescence reaction. In the case of a common luciferin-luciferase reaction, such an environment is provided by the enzyme luciferase. The chemical structures of PMs, as well as that of the natural luciferin, have not been determined yet (see the next section). 

Sodium dodecyl sulfate is the universal analytical standard for the determination of anionic and cationic active matter. It is used to determine the analytical concentration factor of the cationic surfactant in the titration of anionic active matter and as titrant to determine the cationic active matter. 

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... 

The amount of the ester sulfonates, besides the mono- and disalt of the a-sulfo fatty acid, can be calculated by two titrations, one in the acid and one in the basic range. In the basic range both sulfonates and carbocylate functionalities are negatively charged and titrated with the cationic surfactant hyamine. In acid medium the RCOOH group is protonated and no longer available for the titration. Since hyamine-methylene blue (acid conditions) titrates only sulfonate and hyamine-phenol red (basic conditions) determines both sulfonates and carbo-cylates, substraction of the titration value with phenol red from the double value of the titration with methylene blue yields only the a-sulfo fatty acid ester. This is the only species of the three which has merely the sulfonate function [106]. 

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. 

Among cations, potassium, acetylcholine, some cationic surfactants (where the ion-exchanger ion is the / -chlorotetraphenylborate or tetra-phenylborate), calcium (long-chain alkyl esters of phosphoric acid as ion-exchanger ions), among anions, nitrate, perchlorate and tetrafluoro-borate (long-chain tetraalkylammonium cations in the membrane), etc., are determined with this type of ion-selective electrodes. 

Harrison, C.R., Lucy, C.A. (2002). Determination of zwitterionic and cationic surfactants by high-performance liquid chromatography with chemiluminescent nitrogen detection. J. Chromatogr. A 956(1-2), 237-244. 

Crisp et al. [212] has described a method for the determination of non-ionic detergent concentrations between 0.05 and 2 mg/1 in fresh, estuarine, and seawater based on solvent extraction of the detergent-potassium tetrathiocyana-tozincate (II) complex followed by determination of extracted zinc by atomic AAS. A method is described for the determination of non-ionic surfactants in the concentration range 0.05-2 mg/1. Surfactant molecules are extracted into 1,2-dichlorobenzene as a neutral adduct with potassium tetrathiocyanatozin-cate (II), and the determination is completed by AAS. With a 150 ml water sample the limit of detection is 0.03 mg/1 (as Triton X-100). The method is relatively free from interference by anionic surfactants the presence of up to 5 mg/1 of anionic surfactant introduces an error of no more than 0.07 mg/1 (as Triton X-100) in the apparent non-ionic surfactant concentration. The performance of this method in the presence of anionic surfactants is of special importance, since most natural samples which contain non-ionic surfactants also contain anionic surfactants. Soaps, such as sodium stearate, do not interfere with the recovery of Triton X-100 (1 mg/1) when present at the same concentration (i.e., mg/1). Cationic surfactants, however, form extractable nonassociation compounds with the tetrathiocyanatozincate ion and interfere with the method. 

Other cationic surfactants such as TTAB, DTAB, DODAB, STAC, CEDAB, and DDDAB have been used in CL reactions with less frequency. Thus, tetradecyltrimethylammonium bromide [TTAB] has been used to increase the sensitivity of the method to determine Fe(II) and total Fe based on the catalytic action of Fe(II) in the oxidation of luminol with hydrogen peroxide in an alkaline medium [47], While other surfactants such as HTAB, hexadecylpiridinium bromide (HPB), Brij-35, and SDS do not enhance the CL intensity, TTAB shows a maximum enhancement at a concentration of 2.7 X 10 2 M (Fig. 11). At the same time it was found that the catalytic effect of Fe(II) is extremely efficient in the presence of citric acid. With regard to the mechanism of the reaction, it is thought that Fe(II) forms an anionic complex with citric acid, being later concentrated on the surface of the TTAB cationic micelle. The complex reacts with the hydrogen peroxide to form hydroxy radical or superoxide ion on the... 

When the influence was studied of different surfactants on the CL intensity of the reaction of lucigenin with isoprenaline, it was found that while cationic surfactants such as HTAH and HTAB and anionic surfactants such as SDS decrease the CL signal, the presence of Brij-35 increases the signal by a factor of 2.1 compared to that obtained in an aqueous medium [61]. As a result, a quite sensitive analytical method has been established for determination of isoprenaline, using Brij-35 as a CL enhancer. Application of the method has been satisfactorily verified with the determination of isoprenaline in pharmaceutical preparations. 

Direct determination of surfactants in complex matrices can also be carried out using ion-selective electrodes. Depending on the membranes and additives used, the detergent electrodes are optimized for the detection of anionic surfactants [81], cationic surfactants [82], and even nonionic surfactants [83]. The devices are sensitive to the respective group of surfactants but normally do not exhibit sufficient stability and reproducibility for their use in household appliances. With further optimization of membrane materials, plasticizers and measurement technology, surfactant-selective electrodes offer high potential for future applications. 

In abroad sense, the model developed for the cobaloxime(II)-catalyzed reactions seems to be valid also for the autoxidation of the alkyl mercaptan to disulfides in the presence of cobalt(II) phthalocyanine tetra-sodium sulfonate in reverse micelles (142). It was assumed that the rate-determining electron transfer within the catalyst-substrate-dioxygen complex leads to the formation of the final products via the RS and O - radicals. The yield of the disulfide product was higher in water-oil microemulsions prepared from a cationic surfactant than in the presence of an anionic surfactant. This difference is probably due to the stabilization of the monomeric form of the catalyst in the former environment. 

Suppliers of visible spectrophotometers are reviewed in Table 1.1. Spectroscopic methods are applicable to the determination of phenols, chlorophenols, amines, mixtures of organics, boron, halogens, total nitrogen and total phosphorus in soils, cationic surfactants, carbohydrates, total nitrogen, phosphorus and sulphur in non-saline sediments, boron, total organic carbon, total sulphur and arsenic in saline sediments, cationic surfactants, adenosine triphosphate and total organic carbon in sludges. 

This technique has been applied to the determination of heteroaromatic compounds, anthropogenic hydrocarbons, polymers, haloaromatic compounds in soils, polyaromatic hydrocarbons, cationic surfactants and polychlorobiphenyls and mixtures of organic compounds in non-saline sediments and bacteria identification in sludges. 

DTDMAC was the first widely used cationic surfactant produced at the industrial scale since the 1960s. Its main application was as a fabric softening active agent. Due to its physico-chemical properties, largely determined by the positively charged head group and the long alkyl chains, it adsorbs onto fabrics and makes textiles feel soft. 

The determination of cationic surfactants in the environment by GC and GC-MS is very scarce, as described above, but this is not the case for several compounds related to cationic surfactants. Thus, long chain tertiary amines that are amenable to direct analysis by GC have been... 

Numerous applications have been shown to exist that overcome the general problems of lack of volatility and instability at higher temperatures that principally hamper direct analysis of surfactants by GC methods. Thus, a whole suite of derivatisation techniques are available for the gas chromatographist to successfully determine anionic, non-ionic and cationic surfactants in the environment. This enables the analyst to combine the high-resolution chromatography that capillary GC offers with sophisticated detection methods such as mass spectrometry. In particular, for the further elucidation of the complex mixtures, which is typical for the composition of many of the commercial surfactant formulations, the high resolving power of GC will be necessary. 

These observations obtained from the application of different API techniques are determinative for qualitative and quantitative FIA results in the analysis of non-ionic and ionic surfactants. Therefore, both ionic surfactant types, anionic and cationic surfactant blends, besides a non-ionic AE surfactant blend were examined, recording their FIA-MS and MS-MS spectra from the blends before the spectra were generated from the mixture of all blends. The results, which show considerable variation, will be presented and discussed as follows. 

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