The scanning tunneling microscope has been used to desorb hydrogen from hydrogen-terminated silicon (100) surfaces. As a result of control of the dose of incident electrons, a countable number of desorption sites can be created and the yield and cross section are thereby obtained. Two distinct desorption mechanisms are observed : (i) direct electronic excitation of the Si-H bond by field-emitted electrons and (ii) an atomic resolution mechanism that involves multiple-vibrational excitation by tunneling electrons at low applied voltages. This vibrational heating effect offers significant potential for controlling surface reactions involving adsorbed individual atoms and molecules.