N,N'-Tetrasubstituted Malonamide Derivatives and Hydrochloric Acid Solutions: An Interfacial Study

"In this work, the influence of the malonamide structure, acidity of the aqueous phase and diluent on the equilibrium interfacial tension (IT) of N,N'-dimethyl-N,N'-diphenylmalonamide (DMDPHMA) and N,N'-dimethyl-N,N'-dicyclohexylmalonamide (DMDCHMA) in 1,2- dichloroethane (1,2-DCE), and DMDCHMA in toluene, with aqueous HCl, were investigated. IT isotherms were determined using the Du N ouy ring method. Densities of the organic phases were determined, and used to screen solute-diluent interactions. Formation of third phases was never observed; furthermore, ITs increase with the phase separation period, constant values being obtained for separation periods larger than 1000 seconds. Each malonamide interfacial efficiency at the oil/water interface is interpreted in terms of malonamide basicity, diluent polarity and malonamide - hydrochloric acid- diluent interfacial interactions.IntroductionFor several years now, N,N'-tetrasubstituted malonamide derivatives have been extensively investigated as liquid-liquid extraction agents since they were first proposed as the organic components of the DIAMEX process, with the aim of advantageously replacing tributylphosphate in PUREX [1]. Therefore, a significant part of research studies with malonamides appearing in the literature deal with the extraction of major and minor actinides in real or simulated spent nuclear fuels in nitric acid solutions [2]. Under typical experimental process conditions, the tendency shown by some N,N'-tetrasubstituted malonamide derivatives to aggregate in the organic phase, leading in a few cases to the formation of undesirable third phases, has been remarked and consequently thoroughly investigated [3, 4]. The increasing use of chloride streams as hydrometallurgical aqueous feeds is becoming a reality, and this fact is obviously deeply founded on an extensive research carried out to recover value-adding metals from these media. Following this trend, a number of N,N'-tetrasubstituted malonamides have already been screened for the recovery of iron(III) [5, 6] and platinum-group metals [7] from hydrochloric acid solutions. The results obtained are quite promising either in terms of total metal ion recoveries or selectivity patterns achieved. The formation of a third phase when iron(III) was extracted by the tested N,N'-tetrasubstituted malonamide derivatives has never been observed under the adopted experimental conditions, and the extraction data collected would need to be reinterpreted accordingly if any aggregation phenomena involving the considered extraction systems were to take place."