Molecular absorption spectra of the diatomic molecules AlI, GaI, InI, TlI, MgI, CaI, SrI and BaI, generated in a graphite furnace, were studied using a high-resolution echelle spectrometer with the aim of finding a simple, reliable and sensitive analytical method for the determination of iodine. Among them, the barium mono-iodide (BaI) was found to have the strongest absorption bands around 538 nm and 560 nm, each of them consisting of a series of well-resolved rotational lines with half-widths of about 40–50 pm. The strongest BaI line, the band head at 538.308 nm has been evaluated systematically for its analytical use for the determination of iodine. High concentrations of hydrochloric acid (or chloride), hydrofluoric acid (or fluoride), iron, potassium and sodium resulted in significant reduction of the BaI molecular absorption. Apart from this, no other serious spectral or non-spectral interference has been observed. Different chemical forms of iodine, such as iodide, iodate and organically bound iodine produced identical BaI absorption sensitivity. The detection limit for iodine was 600 pg, and the calibration curve was linear up to 250 ng iodine. Two real samples with different chemical forms of iodine were analyzed using the proposed method. One sample was an iodide pill with a specified iodide content of 200 mg, the other one was a thyroid hormone pill with a specified content of 63.5 mg. The results were in good or satisfactory agreement with those of independent methods, the potentiometric titration and the inductively coupled plasma time-of-flight mass spectrometry (ICP-ToF-MS); the deviations were 2% and 8% for the iodide and the thyroid hormone sample, respectively. The relative standard deviation of the analytical results ( n = 3) was below 2%.
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