Investigation of the contact charge transfer absorption of organic solvents with oxygen for use in oxygen determination

The contact charge transfer (CCT) absorption spectra of dimethylsulphoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), ethanol, methanol, water, benzene (Bz), N,N'-diethylaniline (DEA), N,N'-dimethyl-p-toluidine (DMT) and N,N'-diethyl-p-toluidine with molecular oxygen have been investigated. These solvents form strong ultraviolet/visible CCT absorption spectra with intensities that are related to the partial pressure of the applied oxygen. DMSO, DMF, DMA, Bz, DEA and DMT are shown to form 1:1 molecular contact complexes with molecular oxygen. A simple oxygen sensing system is described using CCT absorption spectroscopy of DMT at a wavelength of 400 nm, with a gas flow rate of 60 cm(3) min(-1) through the solvent in a cuvette with a pathlength of 1 cm. Inexpensive plastic fibres are used to relay the light from a xenon lamp source to the cuvette and back to a photo-detector. The response of the sensing system to changes in oxygen concentration is reversible, non-linear and in good agreement with the Beer-Lambert law. The most sensitive response region is from 0 to 20% O(2) with a change in signal level of about 35%. The solvent used shows no deterioration in performance over a long period and can be used to determine gaseous oxygen concentrations from 0 to 100%. It does not respond to carbon dioxide.