Solvent extraction of zirconium(IV) from acidic chloride solutions has been carried out with the thiosubstituted organophosphorus acids Cyanex 301 and Cyanex 302. The extraction follows an ion exchange mechanism: MO(aq)2+ +2 HA((org)) <----> MOA(2(org)) +2 H-(aq)(+), where, M = Zr(IV); HA = Cyanex 301 or Cyanex 302. The plots of log D (distribution ratio) vs log [HA], are linear with slopes of 2, indicating the association of two moles of extractant with the extracted metal species. The plots of log D vs log [H+] gave straight lines with a negative slope of 1.7 for Cyanex 301 and 1.8 for Cyanex 302, indicating the exchange of two moles of hydrogen ions for every mole of Zr(IV). Addition of sodium salts enhanced the extraction of metal. The stripping behavior of metal from the loaded organic (LO) with HCl and H2SO4 was studied. Increase of temperature during the extraction and the stripping stage increases the metal transfer, showing the process is exothermic. Mixed extractants, the extraction behavior of associated elements such as Hf (IV), Ti (IV), Al (III), Fe (III) and the IR spectra of the metal complexes were studied. (C) 2004 Society of Chemical Industry.