Mechanism of formation and spatial distribution of lead atoms in quartz tube atomizers

• Published in: Spectrochimica acta. Part B: Atomic spectroscopy 1997-05, Vol.52 (5), p.643-656
• Main Authors: Johansson, M., Baxter, D.C., Ohlsson, K.E.A., Frech, W.
• Format: Article
• Language: English
• Subjects: Alkyllead; Analytical chemistry; Atomization mechanism; Chemistry; Exact sciences and technology; Quartz tube atomizer; Spatially resolved atomic absorption spectrometric measurements; Spectrometric and optical methods
• ISSN: 0584-8547; 1873-3565
• DOI: 10.1016/S0584-8547(96)01619-9

The cross-sectional and longitudinal spatial distributions of lead atoms in a quartz tube (QT) atomizers coupled to a gas chromatograph have been investigated. A uniform analyte atom distribution over the cross-section was found in a QT having an inner diameter (i.d.) of 7 mm, whereas a 10 mm i.d. QT showed an inhomogeneous distribution. These results accentuate the importance of using QTs with i.d.s below 10 mm to fulfil the prerequirement of the Beer—Lambert law to avoid bent calibration curves. The influence of the make up gas on the formation of lead atoms from alkyllead compounds has been studied, and carbon monoxide was found equally efficient in promoting free atom formation as hydrogen. This suggests that hydrogen radicals are not essential for mediating the atomization of alkyllead in QT atomizers at ∼ 1200 K. Furthermore, thermodynamic equilibrium calculations describing the investigated system were performed supporting the experimental results. Based on the presented data, a mechanism for free lead atom formation in continuously heated QT atomizers is proposed; thermal atomization occurs under thermodynamic equilibrium conditions in a reducing gas. The longitudinal atom distribution has been further investigated applying other make up gases, N 2 and He. These results show the effect of the influx of atmospheric oxygen on the free lead atom formation. Calculations of the partial pressure of oxygen in the atomizer gas phase assuming thermodynamic equilibrium have been undertaken using a convective-diffusional model. © 1997 Elsevier Science B.V.