The products of the heterogeneous reactions of chlorine atoms and chlorine oxide radicals with acid coated Pyrex walls have been directly determined for the first time. Contrary to the usual assumption that chlorine atoms recombine to form Clz, we find that the major product is HCl, with small amounts of perchlorate also formed. Similarly, C10 radicals form HC1 rather than Clz. The source of hydrogen for these reactions is probably the water always found in this type of vacuum system. These results may change the interpretation of flow tube experiments with chlorine atoms. Application to the H + HC1 reaction is discussed as an example.
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