We present the analysis of 7.6-13.2 μm infrared (IR) spectrophotometry (R 250) of comet C/1995 O1 (Hale-Bopp), in conjunction with concurrent observations that extend the wavelength coverage of the spectral energy distribution from near- to far-infrared wavelengths. The observations include temporal epochs preperihelion (1996 October and 1997 February UT), near perihelion (1997 April UT), and postperihelion (1997 June UT). Through the modeling of the thermal emission from small, amorphous carbon grains and crystalline and amorphous silicate grains in Hale-Bopp's coma, we find that as the comet approached perihelion, the grain size distribution (the Hanner modified power law) steepened (from N = 3.4 preperihelion to N = 3.7 near and postperihelion), along with an increase in the fractal porosity of larger (greater than 1 μm) grains. The peak of the grain size distribution remained constant (ap = 0.2 μm) at each epoch. We attribute the emergence of the 9.3 μm peak near perihelion to crystalline orthopyroxene grains released during epochs of high jet activity. Crystalline silicates (olivine and orthopyroxene) make up about 30% (by mass) of the submicron-sized (≤1 μm) dust grains in Hale-Bopp's coma during each epoch.