Alkanesulfonates titration

A number of proven methods is available for the analysis of commercial alkanesulfonates. The total sulfonate content and the monosulfonate content can be determined quite accurately by extractive methods and different forms of two-phase titration. 

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. 

FIG. 11 Titration plot of alkanesulfonates. Sample 60 wt % of Hostapur SAS 60, monosulfonates fraction contents ca. 140 mg/100 ml (10% MeOH) solution to be titrated 10 ml, 5 ml buffer pH 3 (Merck), 5 ml MeOH, diluted to 100 ml with water titrant 0.004 mol/l TEGOtrant A 100 (l,3-didecyl-2-methyl-imidazolium chloride, Metrohm 6.2317.000) titrator Titrino 716 DMS with automatic titrator 727 and propellant stirrer titration mode dynamic end point titration (DET), high-sense electrode Metrohm 6.0504.15Q, reference electrode Ag/AgCl Metrohm 6.0733.100, EP = end point. 

Sodium hydroxyalkanesulfonates may be determined in the presence of an unsaturated hydrocarbon, including sodium alkenesulfonate. The sulfonates are converted to the free sulfonic acids using a slight excess of 2,4-dinitrobenzene-sulfonic acid. The hydroxyl group of the sulfonic acid liberated is acetylated in ethyl acetate solution by a known excess of acetic anhydride. The unconsumed anhydride is hydrolyzed by a pyridine-water mixture and the acids titrated potentiometrically with standard sodium hydroxide solution. The hydroxy-alkanesulfonate content is calculated after correction for any traces of acidity or alkalinity in the original sample. 

Active agent content of anionics is usually determined by titration with a cationic surfactant such as benzethonium chloride. Two-phase titration is suitable for assay of alkylaryl sulfonates alkyl sulfates and hydroxysulfates, alkanesulfonates, fatty alcohol ethoxysul-fates and alkyIphenolethoxysulfates and dialkyIsulfosuccinates (4,5). The results on ma-... 

ISO standard 893 covers analysis of alkanesulfonates, specifying assay by gravimetry, alkane monosulfonates by titration or extraction (Sections 2(a) and 2(c), below), neutral oil by petroleum ether extraction of an isopropanol/water solution, pH of a 5% aqueous solution, water by Karl Fischer titration or azeotropic distillation, sulfate by titration with lead nitrate, sulfite by iodometric titration, and chloride by potentiometric titration (99). The value for neutral oil can be checked for losses due to evaporation by confirming that the weight of the sulfonates and other salts in the 2-propanol/water phase plus the water content and weight of neutral oil is equal to 100%. 

While the two-phase titration will not determine alkanedisulfonates if monosulfonates are absent, the presence of disulfonate impurities in commercial alkanesulfonate products will cause a variable interference (37). The response of the two-phase titration to molecules containing more than one sulfate or sulfonate group must be determined for each individual case. Lew reports stoichiometric reaction with each functional group for a C22 surfactant with two anionic sulfate groups separated by four carbon atoms (38). Wick-bold suggests addition of 10 mL 20% sodium sulfate solution to eliminate interference from disulfonates, and this was adopted in the ISO procedure (39). Alternatively, modification of the organic solvent to a 93 7 chloroform/l-hexanol mixture will allow complete recovery of disulfonates, regardless of pH (40). 

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