X-ray Studies of Interfacial Strontium-Extractant Complexes in a Model Solvent Extraction System

The interfacial behavior of a model solvent extraction liquidliquid system, consisting of solutions of dihexadecyl phosphate (DHDP) in dodecane and SrCl2 in water, was studied to determine the structure of the interfacial ionextractant complex and its variation with pH. Previous experiments on a similar extraction system with ErCl3 demonstrated that the kinetics of the extraction process could be greatly retarded by cooling through an adsorption transition, thus providing a method to immobilize ionextractant complexes at the interface and further characterize them with X-ray interface-sensitive techniques. Here, we use this same method to study the SrCl2 system. X-ray reflectivity and fluorescence near total reflection measured the molecular-scale interfacial structure above and below the adsorption transition for a range of pH. Below the transition, DHDP molecules form a homogeneous monolayer at the interface with Sr2+ coverage increasing from zero to saturation (one Sr2+ per two DHDP) within a narrow range of pH. Experimental values of Sr2+ interfacial density determined from fluorescence measurements are larger than those from reflectivity measurements. Although both techniques probe Sr2+ bound to DHDP, only the fluorescence provides adequate sensitivity to Sr2+ in the diffuse double layer. A Stern equation determines the Sr2+ binding constant from the reflectivity measurements and the additional Sr2+ measured in the diffuse double layer is accounted for by GouyChapman theory. Above the transition temperature, a dilute concentration of DHDPSr complexes resides at the interface, even for temperatures far above the transition. A comparison is made of the structure of the interfacial ionextractant complex for this divalent metal ion to recent results on trivalent Er3+ metal ions, which provides insight into the role of metal ion charge on the structure of interfacial ionextractant complexes, as well as implications for extraction of these two differently charged ions.