We perform reactive molecular dynamics simulations of monolayer formation by silanes on hydroxylated silica substrates. Solutions composed of alkylmethoxysilanes or alkylhydroxysilanes in hexane are placed in contact with a. hydroxylated silica surface and simulated using a reactive force field (ReaxFF). In particular, we have modeled the deposition of butyl-, octyl-, and dodecyltrimethoxysilane to observe the dependence of alkylsilyl chain length on monolayer formation. We additionally modeled silanization using dodecyltrihydroxysilane, which allows for the comparison of two grafting mechanisms of alkoxysilanes: (1) direct condensation of alkoxysilane with surface-bound silanols and (2) a two-step hydrolysis condensation mechanism. To emulate an infinite reservoir of reactive solution far away from the substrate, we have developed a method in which new precursor molecules are periodically added to a region of the simulation box located away from the surface. It is determined that the contact angle of alkyl tails bound to the surface is dependent on their grafting density. During the early stages of grafting alkoxy- and hydroxysilanes to the substrate, a preference is shown for silanes to condense with silanols further from the substrate surface and also close to neighboring surface-bound silanols. The kinetics of silica silanization by hydroxysilanes was observed to be much faster than for methoxysilanes. However, the as-deposited hydroxysilane monolayers show similar morphological characteristics to those formed by methoxysilanes.