Interfacial tension (IFT) is one of the major parameters which govern the fluid flow in oil production and recovery. This paper investigates the interfacial activity of different natural surfactants found in crude oil. The main objective was to better understand the competition between carboxylic acids and asphaltenes on toluene/water interfaces. Dynamic IFT was measured for water-in-oil pendant drops contrary to most studies using oil-in-water drops. Stearic acid (SA) was used as model compound for surface-active carboxylic acids in crude. The influence of concentration of these species on dynamic IFT between model oil and deionized water was examined. The acid concentrations were of realistic values (total acid number 0.1 to 2 mg KOH/g oil) while asphaltene concentrations were low and set between 10 and 100 ppm. In mixtures, the initial surface pressure was entirely determined by the SA content while asphaltenes showed a slow initial diffusion to the interface followed by increased adsorption at longer times. The final surface pressure was higher for asphaltenes compared to SA, but for binaries, the final surface pressure was always lower than the sum of the individuals. At high SA concentration, surface pressures of mixtures were dominated entirely by the SA, although, Langmuir isotherm analysis shows that asphaltenes bind to the interface 200-250 times stronger than SA. The surface area/molecule for both SA and asphaltenes were found to be larger than the values reported in recent literature. Various approaches to dynamic surface adsorption were tested, showing that apparent diffusivity of asphaltenes is very low, in agreement with other works. Hence, the adsorption is apparently under barrier control. A possible hypothesis is that at the initial phase of the experiment and at lower concentration of asphaltenes, the interface is occupied by stearic acid molecules forming a dense layer of hydrocarbon chains that may repel the asphaltenes.

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h i g h l i g h t s• Investigated the surface energy of a reservoir rock using IGC.• Examined the effect of moisture and temperature on their surface energetics.• The surface interaction forces at the rock-fluid interface were quantified.• Proposed a new approach for measuring the wettability index of a rock-fluid system.• Wettability index scales from −1 (strongly oil-wet) to +1 (strongly water-wet). g r a p h i c a l a b s t r a c t a b s t r a c tAn accurate description of the surface chemistry of the reservoir rock-fluid system is essential to understand the attractive forces between the various phases (crudes, brines and the rock surface). These physico-chemical interactions determine the fundamental nature of the reservoir wettability and the wetting behavior of fluids on the reservoir rock surface. Inverse gas chromatography (IGC) is used to characterize the surface chemistry of a Saudi Arabian reservoir rock (henceforth referred to as 'reservoir rock') at different moisture coverage and temperatures. This information combined with the surface tension of the interacting reservoir fluids is utilized to develop a new method for quantifying wettability in terms of a wettability index. This index is based on the relative magnitude of the work of adhesion between the rock surface and the competing oleic/aqueous phase.Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/3.0/).

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Fundamental understanding of the wettability of carbonate formations can potentially be applied to the development of oil recovery strategies in a complex carbonate reservoir. In the present study, surface energies of representative carbonate samples were evaluated by direct quantitative force measurements, using scanning force microscopy (SFM) at sub-micron scale, to develop a reliable method to predict reservoir wettability. Local adhesion force measurements were conducted on appropriate calcite and dolomite samples and performed in air as well as in the presence of polar and nonpolar fluids. This study demonstrated that, by comparing measurements of adhesion forces between samples of the same mineral in different fluids, it is feasible to determine the surface energy of a given mineral as well as its polar and nonpolar components. The derived values are in agreement with literature. A proof-of-principle protocol has been established to quantify surface energy using SFM-based adhesion measurements. This novel methodology complements the conventional contact angle measurement technique, where surface energy can only be examined at large length scale. The reported methodology has great potential for further optimization into a new standard method for fast and accurate surface energy determination, and hence provides a new tool for reservoir rock wettability characterization.