Daniel Lillian

Atmospheric formation of chloroform from trichloroethylene

Abstract Chloroform has been observed as a photochemical product in simulated ambient air containing trichloroethylene, paralleling a previous observation of carbon tetrachloride formation from perchloroethylene. Some portion of the atmospheric budget of these chloromethanes may perhaps be attributed to this process. Toxic products such as phosgene and chloro‐acetylchlorides are formed. This process may well provide another source of stratospheric ozone‐destroying chlorine atoms.

Gas chromatographic methods for ambient halocarbon measurements

Abstract Gas Chromatographic procedures for the measurement of SF6, COC12 and twelve atmospheric halocarbons, including vinyl chloride, have been developed. The identities of these relatively unstudied important atmospheric constituents were established conventionally by extensive empirical cross checking of retention data and then confirmed by the novel application of electron attachment kinetics in a dual electron capture detector system. Nine packings were found useful for the measurement of one or more of the compounds under study. In an ongoing study of the fates of halocarbons, phosgene synthesis has been demonstrated in a smog chamber experiment in which a mixture of 1 ppm C2Cl4 and 0.5 ppm NO2 in air (RH=50%) was irradiated with simulated sunlight. Phosgene identity was confirmed by its ionization efficiency and retention data on a didecyl phthalate column. Gas phase coulometry can only be used for non‐reactive electron absorbers and suffers significant error for reactive compounds such as phosgen...