Silicon surfaces functionalized both in-situ (in vacuum) and ex-situ (via chemomechanical methods) with 1-butanol, tert-butanol, and 1-chlorobutane were examined by thermal desorption spectroscopy, Auger electron spectroscopy, and computational modelling. The desorption and thermal decomposition was probed for these species by these complimentary methods. The results are compared with binding and decomposition on the preferred silicon cleavage plane surfaces Si(100) and Si(111).