Characterization of Petroleum Sulfonates by a Nonaqueous Titration Method

Summary A new method is described for the determination of the equivalent weight for petroleum sulfonates. The method is based on the direct acidimetric titration of the sulfonate in acetic acid/acetic anhydride solvent using a titrant of perchloric acid in dioxane. From the titration, the moles of perchloric acid required to react with the sulfonate is measured. The equivalent weight is calculated from the grams of sample titrated and the moles of acid used. The potentiometric titration can be carried out in less than 10 minutes and can be done with 10 to 100 mg of sample. The accuracy and precision of the procedure were examined by the titration of sodium salts of p-toleuene sulfonate, 2-naphthalene sulfonate, and petroleum sulfonates. In general, values for the equivalent weight were within 2% of those values determined by the Epton titration, by wet ashing methods, or from the theoretical value. The relative standard deviation (RSD) for the procedure is estimated to be 0.5%. For p-toluene sulfonate, an RSD of 0.15% was calculated. The new method was used to determine the equivalent weights for three fractions of a petroleum sulfonate obtained by the preferential elution from silica gel with alcohol. A series of samples with varying equivalent weight was prepared by proportional combination of the three fractions. Analysis by high-performance liquid chromatography (HPLC) gave a set of data points of peak areas for the series. A plot of equivalent weight as a function of disulfonate to total peak area ratio resulted in a straight line. The slope of this line is descriptive of the molecular weight range for the petroleum sulfonate. Introduction Petroleum sulfonates are used to liberate a residual oil from a porous medium in a tertiary oil-recovery process. One mechanism for the release of oil is the reduction of the interfacial tension between water and oil to values on the order of 10−3 dyne/cm.1–5 The performance of a sulfonate as a surfactant depends on its molecular size and structure. For a pure single-species sulfonate, these properties can be correlated with the alteration of the interfacial tension between water and oil. The same cannot be done for a petroleum sulfonate because the sulfonate is a mixture of molecular species with unknown structures. Previous studies6,7 have shown that the overall composition of a petroleum sulfonate is altered by the preferential partitioning of the molecular species to the oil, water, and rock phases. This causes the composition of the sulfonate to change constantly as it flows through the porous media contacting water and oil. To correlate oil-recovery efficiency with a property of the sulfonate, analytical methods are needed to characterize the effluent from core floods. One parameter for characterizing petroleum sulfonates is the average equivalent weight, which is the weight in grams containing 1 mol of sulfonate functional groups. Sufficient sample is often not available for the equivalent weight analysis by the ASTM wet ashing procedure, and the oil in the sample may often interfere with the Epton titrate method. Therefore, a study was initiated to develop a method for the determination of equivalent weight of petroleum sulfonates in the 10- to 100-mg range. Of equal importance is a method to count sulfonate groups and to differentiate mono- and disulfonate molecules. The latter can be achieved by HPLC using an anion exchange column.8 However, quantification of the effluent from the HPLC column remains a problem. No detector is available that responds specifically to the sulfonate functional group -SO3−. Specific ion-electrodes of the liquid- or solid-membrane type show varying response to sulfonates depending on the molecular weight of the sulfonate.9,10