Surfactant‐mediated enhanced‐oil‐recovery (EOR) techniques, such as surfactant/polymer (SP) flooding, have received increased attention because of their ability to reduce capillary forces at the pore‐scale to ultralow values and mobilize trapped oil. Recently, there have been increased efforts in microemulsion‐phase‐behavior modeling capabilities by relying on the hydrophilic/lipophilic‐difference (HLD) measure for surfactant‐affinity quantification. One common assumption of most microemulsion‐phase‐behavior models is the assumption of pure excess phases, which states that the surfactant component is only present in the microemulsion phase. This assumption can lead to significant errors for some surfactant systems, especially when applied to chemical simulations in which discontinuities may arise.
The main novelty of this paper is to allow for surfactant partitioning into both the water and oil excess phases by use of a simple approach, and then relate relevant surfactant‐partitioning coefficients (i.e., K‐values) to HLD. Surfactant screening that is based on surfactant‐structure parameters is also considered based on estimated K‐values. Key dimensionless groups are identified as a function of activity coefficients, which allow for a simplified description of the surfactant‐partition coefficients. These surfactant‐partition coefficients are combined with the chemical-potentials (CP) equation‐of‐state (EoS) model to describe and predict the phase behavior when the excess phases are not pure. Further, the developed surfactant‐partitioning model can be used in other microemulsion‐phase‐behavior models to allow for impure excess phases.