Interfacial Properties of a Hydrophobic Dye in the Tetrachloroethylene-Water-Glass Systems

Abstract

Interfacial effects play an important role in governing multiphase fluid behavior in porous media. Strongly hydrophobic organic dyes, used in many experimental studies to facilitate visual observation of the phase distributions, have generally been implicitly assumed to have no influence on the interfacial properties of the various phases in porous media. Sudan IV is the most commonly used dye for non-aqueous phase liquids (NAPLs) in laboratory experiments. It has also been used in at least one field experiment. The effects of this dye on the tetrachloroethylene (PCE)-water-glass system were investigated to test the assumption that the dye does not effect the interfacial properties and therefore PCE mobility. The results indicate that the dye does indeed change the interfacial relationships.The effect of the dye on the interfacial relationships is a complex function of the dye concentration, the solid phase composition, and the dynamic rate of new interface formation. The dye caused a slight (<10 percent) increase in interfacial tension at low concentrations (<0.1 g/L) and high rates of new interface formation. The dye reduced interfacial tension between PCE and water at low rates of new interface formation for all dye concentrations tested (0.00508 to 5.08 g/L). At the highest dye concentration, the PCE-water interfacial tension was significantly reduced regardless of the rate of new interface formation. The apparent interfacial tension increase at low dye concentrations is suspected to be an artifact of a low measured IFT value for the undyed PCE caused by leaching of rubber o-rings by the PCE prior to testing in the final drop-volume configuration.In addition to reducing interfacial tension, the dye was found to significantly alter the wetting relationship between PCE and water on a glass surface at and above the range of reported dye concentrations cited in the literature (1.1 to 1.7 g/L). The wetting relationship was rendered neutral from a water-wet initial condition at the highest dye concentration. The contact angle, measured through the aqueous phase, changed from 58 degrees for undyed PCE to 93 degrees at a dye concentration of 5.08 g/L. Complete reversal of the wettability is likely given the short equilibration time used in this study (approximately five minutes) together with literature indications that hundreds to thousands of hours may be required to reach equilibrium during contact angle measurements. Observations suggesting changing wetting relationships were also noted between PCE, water, and the platinum-iridium surface used in the standard du No/374y ring method for measuring interfacial tension.Observations of the dyed-PCE-water interface behavior during du No/374y ring interfacial tension measurements were similar to observations noted previously during measurements of the interfacial tension between the Savannah River Site (SRS) M-Area Settling Basin DNAPL (M-Area DNAPL) and water. This observation suggests that the M-Area DNAPL may contain surface active components. If this proves to be the case, it would have significant implications for how the M-Area DNAPL is distributed and moves in the SRS subsurface.