The most energetic planetary collisions attain shock pressures that result in abundant melting and vaporization. Accurate predictions of the extent of melting and vaporization require knowledge of vast regions of the phase diagrams of the constituent materials. To reach the liquid-vapor phase boundary of silica, we conducted uniaxial shock-and-release experiments, where quartz was shocked to a state sufficient to initiate vaporization upon isentropic decompression (hundreds of GPa). The apparent temperature of the decompressing fluid was measured with a streaked optical pyrometer, and the bulk density was inferred by stagnation onto a standard window. To interpret the observed post-shock temperatures, we developed a model for the apparent temperature of a material isentropically decompressing through the liquid-vapor coexistence region. Using published thermodynamic data, we revised the liquid-vapor boundary for silica and calculated the entropy on the quartz Hugoniot. The silica post-shock temperature measurements, up to entropies beyond the critical point, are in excellent qualitative agreement with the predictions from the decompressing two-phase mixture model. Shock-and-release experiments provide an accurate measurement of the temperature on the phase boundary for entropies below the critical point, with increasing uncertainties near and above the critical point entropy. Our new criteria for shock-induced vaporization of quartz are much lower than previous estimates, primarily because of the revised entropy on the Hugoniot. As the thermodynamics of other silicates are expected to be similar to quartz, vaporization is a significant process during high-velocity planetary collisions.