Extraction of zinc(II) and copper(II) from HCl solutions with solutions of mono-and dialkynylsubstituted quaternary ammonium halides in chloroform and toluene is more efficient than the extraction with saturated quaternary ammonium salts and occurs by different mechanism. The dependences of the metal distribution factors on the HCl concentration have two maxima whose positions (absolute and relative) and relative intensities depend on the particular extractant, metal, and diluent.There are only a few papers on recovery and purification of metal ions with unsaturated compounds; nevertheless, their results allowed development of very efficient methods for extractive concentration of osmium with a-olefins [1] and extractive chromatography of actinides with allyltrialkylammonium nitrate [2]. The effect exerted on the extraction by a triple bond capable of complexation with soft Lewis acids was not examined previously.In [3] we described the extraction of Zn(II) from solutions of alkali metal halides in HCl with hept-2-ynyltrioctylammonium bromide and concluded that further studies in this direction would be promising.Here we continue a study of the effect exerted by the structure of quaternary ammonium salts containing a triple bond in the b-position relative to the nitrogen atom, and also by the diluent on extraction of copper and zinc from HCl solutions. We chose the following ammonium salts:17 ) 3 NCH 3 ] + I ! III R = C 8 H 17 , R`= H, X = Br (a); R = C 8 H 17 , R`= C 4 H 9 , X = Br (b); R = C 8 H 17 , R`= C 4 H 9 , X = I (c); R = C 10 H 21 , R`= C 4 H 9 , X = Br (d); R = C 10 H 21 , R`= C 6 H 13 , X = Br (e).The salts were prepared by quaternization of dioctylamine, trioctylamine, and tridecylamine with appropriate propargyl halides under very mild conditions following the previously developed procedure [4]. The reactions at room temperature are complete within 132 h in acetonitrile and 132 days in pentane; the yields of the quaternary ammonium salts are close to quantitative.A principal difference of the examined extractants Ia3Ie and II from those described in the literature [5,6] is the better steric accessibility of the nitrogen atom due to the linear structure of the CH 2 3C=C3CH 2 fragment. This is extremely important for the donor3 acceptor bonding R 4 NX:6MeX n [7] between the anion X of the quaternary ammonium salt and the metal cation Me in the extractable complex.First we studied how the distribution factors of Zn(II) and Cu(II) in extraction with quaternary ammonium salts (QASs) Ia, Ib, and III depend on the HCl concentration in the initial aqueous solution, varied from 0.75 to 9.0 M (Figs. 1, 2). These dependences appeared to be complex. In the extraction of the metals with solutions of Ia and Ib in chloroform and toluene, two local maxima are observed at HCl concentrations of 23 4 and 537 M. On the contrary, in extraction of Zn(II) with compound III containing no p bonds, the corresponding dependence is dome-shaped and has only one broad maximum at an HCl concentration of 335 M, in full agreement w...