Kinetics of extraction of Ti(IV) from SO₄^2– medium by Cyanex 301 dissolved in kerosene containing 5% heptan-1-ol

ABSTRACT

The kinetics of Ti(IV) extraction by Cyanex 301 (HA) were investigated by measuring initial flux of Ti(IV) transfer (F, kmol/m²s), using a Lewis cell, operated at 3 Hz. The empirical flux equation at 298 K is found to be as follows: F (kmol/m²s) = 10^–4.288 [Ti(IV)] (1 + 447 [H⁺])^–1 [HA]_(o) (1 + 1.18[SO₄^2–])^–1. The activation energy, E_a, has been measured to be within 37–60 kJ/mol, depending on experimental parameters and temperature region. The ΔS^± value is always highly negative. Analysis of the flux equation has been done, given various parametric conditions, to elucidate the mechanism of extraction. The rate-determining chemical reaction step, in most parametric conditions, appears to be as follows: TiO²⁺ + A^– → TiOA⁺; and this step occurs via an S_N2 mechanism as suggested by high negative ΔS^± values. However, in certain cases, the extraction process appears as intermediate controlled as supported by E_a value of less than ~48 kJ/mol.

KEYWORDS:

• Cyanex 301
• extraction
• Ti(IV)
• kinetics
• Lewis cell

Acknowledgements

Authors are grateful to Cytec Canada Inc. for supplying Cyanex 301 as gift.