An Exploration of the Gas Phase Reactions of Chlorine Dioxide and Malodorous Compounds of Putrefaction Using FT-IR Instrumentation

Anna M. Love, Ngee Sing Chong

Abstract


Chlorine dioxide has been used to replace traditional water treatments, deactivate Anthracis bacillus, and remediate various molds and bacteria. This study aims to analyze the products of the gas phase reaction between chlorine dioxide and malodorous compounds produced during putrefaction. The study focuses on the reactions between chlorine dioxide and three specific chemicals: cadaverine (amine), 2-hexanone (ketone), and cyclohexyl mercaptan (thiol). The analysis of the gas phase reaction products is carried out using a Varian 7000 Fourier Transform infrared spectrometer (FTIR) with a 2.4 m gas cell. The measurement of most reaction by-products requires spectral resolution of 0.5 cm-1 because the spectra of most gas phase standards are available for spectral resolutions of 0.5 cm-1 or 0.25 cm-1 only. The time-dependent release of chlorine dioxide gas from solid-phase reagents is studied so that an appropriate concentration of chlorine dioxide can be used for the degradation of odorous or toxic compounds. The reaction between cadaverine and chlorine dioxide resulted in the rapid formation of ammonia gas. The GC-MS analysis of the reaction between chlorine dioxide and cadaverine showed the presence of the following nitrogenous compounds: cyanogen chloride; chloromethane; dichloromethane; chloroform; dichloro-acetonitrile; and hexachloroacetone. The reaction by-products of cyclohexyl mercaptan were identified as sulfur dioxide, methanesulfonyl chloride, cyclohexene, 1-chlorocyclohexene, cyclohexanone, and 2-chlorocyclohexanone. GC-MS coupled with a pre-concentrator has the benefit of detecting reaction products at lower levels but the Tenax sorbent material can react with chlorine dioxide thereby complicating the identification of reaction products of the odorous compounds. Detected byproducts of the reaction between the Tenax sorbent material and chlorine dioxide include acetophenone; 2-chlorophenol; benzyl chloride; chlorobenzene, benzeneacetaldehyde; phenylethyne; and benzene. Increasing concentrations of carbon dioxide and other reaction products were mirrored by decreased concentrations of chlorine dioxide and the malodorous chemicals.

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