A methodology is presented for determining the rate constants of elementary surface reactions that can take place in chemical vapor deposition (CVD) processes. The calculations consider well-defined surfaces that can have one or more dangling bonds at a given site and adsorbates that can take up one or more different bonding configurations. Rate constants for each reaction are obtained independently of any process data using statistical mechanics, transition state theory, and bond dissociation energies. Specifically, the reactions are divided into types to classify transition state structures and determine preexponential factors, and the requirement of thermodynamic consistency is used to estimate activation energies. The level of sophistication of the calculations is suitable for treating the large number of plausible steps that could take place in a practical CVD system. Incorporation of the calculated rate constants into a reactor model that includes the effects of fluid flow, transport phenomena, and reactions in the gas and at the growing surface enables dominant reaction pathways and rate-limiting steps to be identified. Moreover, the dependence of growth rate and species compositions on operating conditions can be predicted without fitting any parameters. The utility of the approach is illustrated by modeling low pressure deposition of tungsten from tungsten hexafluoride and silane. Tk;is model treats 35 reactions in the gas and 213 reactions at the growing surface. Results are compared with available experimental data and sensitivity studies are used to assess the limitations of the approach.