Development of a dual sensitive N,N,N’,N’,N”,N”-hexa-n-octylnitrilotriacetamide (HONTA) based potentiometric sensor for direct thorium(IV) estimation

A dual sensitive, simple, and rapid membrane-based potentiometric sensor was developed to determine thorium (Th) in nuclear fuel samples which does not require any prior chemical separation of other matrix elements. Sensor was prepared by incorporating N,N,N’,N’,N”,N”-hexa-n-octylnitrilotriacetamide (HONTA) in a polyvinyl chloride (PVC) matrix in presence of 2-nitrophenyl octyl ether (NPOE) and sodium tetraphenyl borate (NaTPB). The optimum membrane composition was found to be 14.1% HONTA, 3.2% NaTPB, 54.9% NPOE, 27.8% PVC, which showed a dual sensitive linear region in the calibration plot with sub-Nernstian and super-Nernstian slopes of 12.1 ± 0.4mV/decade and 71.7 ± 3.5mV/decade, respectively, with the corresponding linear dynamic ranges of 2.0 × 10-5 to 5.3 × 10-4M and 3.8 ×10-3 to 1.4 × 10-2M, respectively. The super-Nernstian sensitivity exhibited by the sensor increases with Th(IV) as well as HONTA concentrations in the membrane and can be thought to be due to micelle-mediated selective adsorption (MMSA) sensing of the metal ion. Solution speciation of Th(IV) in acetate buffer was determined by laser desorption/ionization mass spectrometry (LDI-MS) and Medusa software. Pristine and used membranes were characterized by Fourier transform infrared (FTIR), scanning electron microscopy–energy dispersive x–rays (SEM-EDS) and small angle neutron scattering (SAXS). Thorium was measured in an actual (Th–U) mixed solution and in a synthetic advance heavy water reactor (AHWR) fuel sample. The present study describes a new approach for the detection of Th(IV) ion through MMSA in an ion selective electrode (ISE).