- This article presents a method for numerical computation of the degree of coverage of chemisorbates and the resultant surface band bending as a function of the ambient gas pressure, temperature, and semiconductor doping level. This method enables quantitative evaluation of the effect of chemisorption on the electronic properties of semiconductor surfaces, such as the work function and surface conductivity, which is of great importance for many applications such as solid- state chemical sensors and electro-optical devices. The method is applied for simulating the chemisorption behavior of oxygen on n-type CdS, a process that has been investigated extensively due to its impact on the photoconductive properties of CdS photodetectors. The simulation demonstrates that the chemisorption of adions saturates when the Fermi level becomes aligned with the chemisorption-induced surface states, limiting their coverage to a small fraction of a monolayer. The degree of coverage of chemisorbed adions is proportional to the square root of the doping level, while neutral adsorbates are independent of the doping level. It is shown that the chemisorption of neutral adsorbates behaves according to the well-known Langmuir model, regardless of the existence of charged species on the surface, while charged adions do not obey Langmuir’s isotherm. In addition, it is found that in depletive chemisorption processes the resultant surface band bending increases by 2.3kT (where k is the Boltzmann constant and T is the temperature) when the gas pressure increases by one order of magnitude or when the doping level increases by two orders of magnitude. © 2002 American Institute of Physics.