Pre-Excitation,Catalytic Oxidation of Analytes over Hopcalite in Flame/Furnace Infrared Emission (FIRE) Spectrometry

Abstract

Gas-phase infrared emission measurements made with the use of a new, specially designed, electrically heated furnace or a small hydrogen/air flame have shown that oxidation of a variety of carbon-based analytes to CO₂ over the catalyst hopcalite prior to vibrational excitation in the furnace or flame markedly improves the response of the FIRE radiometer. Calibration curves obtained with the use of the furnace alone were generally nonlinear, while those obtained with the flame alone had slopes that were compound dependent. By the use of hopcalite in conjunction with the furnace, conversion to CO₂ was significantly improved, and the FIRE response to pure acetone, benzene, dichloromethane, 1-chloro-2-methylpropane, heptane, methanol, and toluene became directly proportional to the number of moles of carbon introduced. In the case of the flame, as little as 0.1 g of hopcalite was sufficient to give a single, linear calibration curve (based on moles of carbon) for injection volumes of 0.2–1.0 μL of a test mixture composed of equal volumes of acetone, benzene, hexane, propanol, and tetrahydrofuran. With the use of hopcalite at its experimentally determined, optimum operating temperature of 380°C, an air flow rate of 45 mL min⁻¹, and a furnace temperature of 600°C, the detection limit for hexane was found to be 518 ng C s⁻¹. The use of hopcalite in conjunction with the flame (900°C) improved this detection limit by two orders of magnitude, due to the combined effects of an increase in excitation temperature and a decrease in source background noise. Injection of chlorinated compounds was found to temporarily poison the hopcalite, resulting in soot formation and loss of catalytic activity for periods of approximately ten minutes.