Temporal and spatial temperature distributions in transversely heated graphite tube atomizers and their analytical characteristics for atomic absorption spectrometry

The important role which temperature plays in atomic absorption spectrometry (AAS) for the formation and detection of atoms in the absorption volume is discussed and the literature is reviewed. Non-homogeneous temperature distribution in the absorption volume is in contradiction to one of the prerequisites for the application of Beer's law used in AAS to convert absorbance into analyte concentration or mass, and is particularly troublesome for an ''absolute analysis'' envisaged for electrothermal atomic absorption spectrometry (ETAAS). Coherent anti-Stokes Raman scattering (CARS) is used to study the gas-phase temperature distribution in a state-of-the-art transversely heated graphite tube atomizer (THGA). The effect of the internal gas flow on the size of the heated atmosphere is studied by steady-state temperature measurements. Temporally and spatially resolved measurements make it possible to study the temperature field within the atomizer volume in all three dimensions during the rapid heating of the furnace to final temperatures in the range 2173-2673 K. The role of the integrated platform of the THGA on the temperature field is investigated by temperature measurements of the gas phase in the presence and absence of the platform. The platform is identified as the major source of temperature gradients inside the tube volume, which may be as high as 1000 K in the radial direction during rapid heating. These gradients are most pronounced for heating cycles starting at room temperature and gradually decrease with increasing starting temperature. Shortly after the tube wall reaches its final temperature, the gas-phase temperature equilibrates and approaches the wall temperature. Because of the unavoidable contact with the cold environment at the open ends of the tube, minor temperature gradients are observed in the gas phase also in longitudinal direction, which can be further reduced by restricting the openings with end caps. The results obtained for the THGA are compared with those obtained earlier for a longitudinally heated graphite tube atomizer (HGA), including some analytical applications of these two furnace types. Both the temperature characteristics and the resulting analytical characteristics substantiate the superiority of the THGA in comparison to the HGA as an atomizer for ETAAS.