A possible steady state kinetic model is presented for the atomization and excitation processes during inductively coupled plasma atomic emission spectrometry. The model takes into account the relative rates of (a) thermal dissociation of analyte salt, (b) recombination of counter atom and analyte atoms, (c) charge transfer between analyte and interferent species, (d) charge transfer between analyte and argon species, and (e) ion/electron collisional de-ionization. Number density ratio data, n(u)'/n(u), where n(u) denotes the excited state and the prime denotes the presence of an interferent element, are presented showing that the predictions of the model are consistent with the signal enhancement observed at low analyte concentrations when Ca is determined by ICP in the presence of excess Li.
The effects of excess Na and K on K and Mg atom line emission in the airacetylene flame and of excess Li and K on Ca, Mg, and Sr atom and ion lines in inductively coupled plasma spectroscopy were studied using emission signal ratios, I 0 /I as probes, where I 0 and I are the emission readings in the presence and absence of the interferent respectively. The I 0 /I plots as a function of analyte concentration in the test solution for the ICP experiments were similar to those obtained for the flame experiments in the analytical range 0 -10 mg/L. A simplified rate model based on analyte excitation via charge transfer between analyte ions and activated interferent atoms is proposed to account for the emission signal enhancement observed at low analyte concentrations (,1 mg/L) for both ICP-AES and flame atomic emission spectroscopy (AES). Data are presented showing good agreement between experimental E 0 calibration curves and theoretical E 0 calibration curves computed using the simplified rate model.
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