Interfacial Tension and Phase Behavior of Surfactant Systems
Authors: Wade W.H. , Morgan James C. , Schechter R.S. , Jacobson J.K. , Salager J.L. 
Published: December 2007

Abstract
The conditions necessary for optimum low tension and phase behavior at high surfactant concentrations are compared with those required at low surfactant concentrations, where solubilization effects are not usually visible. Major differences in tension behavior between the high and low concentration systems may be observed when the surfactant used contains a broad spectrum of molecular species, or if a higher molecular weight alcohol is present, but not otherwise in the systems studied.
We compared the effects of a number of aliphatic alcohols on tension with phase behavior. An explanation of these results, and also of other observed parameter dependences, is proposed in terms of changes in surfactant chemical potential. Surfactant partitioning data is presented that supports this concept.

Introduction
Taber and Melrose and Brandner established that tertiary oil recovery by an immiscible flooding process should be possible at low capillary process should be possible at low capillary numbers. In practice, the required capillary number, which is a measure of the ratio of viscous to capillary forces governing displacement of trapped oil, may be achieved by lowering the oil/water interfacial tension to about 10(-3) dyne/cm, or less. Subsequent research has identified a number of surfactants that give tensions of this order with crude oils and hydrocarbon equivalents.
Interfacial tension studies tended to fall into two groups. Work at low surfactant concentrations, typically 0.7 to 2 g/L, has established that a crude oil may be assigned an equivalent alkane carbon number. Using pure alkanes instead of crude oil has helped the study of system parameters affecting low tension behavior. Important parameters examined include surfactant molecular structure, and electrolyte concentration, surfactant concentration, surfactant molecular weight, and temperature.
At higher surfactant concentrations, interfacial tension has been linked to the phase behavior of equilibrated systems. When an aqueous phase containing surfactant (typically 30 g/L), electrolyte, and low molecular weight alcohol is equilibrated with a hydrocarbon, the surfactant may partition largely into the oil phase, into the aqueous phase, or it may be included in a third (middle) phase containing both water and hydrocarbon. Low interfacial tensions occur when the solubilization of the surfactant-free phase (or phases) into the surfactant-containing phase is maximized. Maximum solubilization and minimum tensions have been shown to be associated with the formation of a middle phase.
Both the high and low surfactant concentration studies have practical importance because even though a chemical flood starts at high concentration, degradation of the injected surfactant slug will move the system toward lower concentrations. This study investigates the relationship between tension minima found with low concentration systems, and low tensions found with equivalent systems at higher surfactants concentrations, particularly those in which third-phase formation occurs.
Many of the systems studied here contain a low molecular weight alcohol, as do most surfactant systems described in the literature or proposed for actual oil recovery. Alcohol originally was added to surfactant systems to help surfactant solubility, but can affect tensions obtained with alkanes, and with refined oil. Few systematic studies of the influence of alcohol on tension behavior exist. Puerto and Gale noted that increasing the alcohol Puerto and Gale noted that increasing the alcohol molecular weight decreases the optimum salinity for maximum solubilization and lowest tensions. The same conclusions were reached by Hsieh and Shah, who also noted that branched alcohols had higher optimum salinities than straight-chain alcohols of the same molecular weight. Jones and Dreher reported equivalent solubilization results with various straight- and branched-chain alcohols.
In this study, we fix the salinity of each system and instead vary the molecule; weight of the hydrocarbon phase.
SPEJ
P. 242