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The NASA Ames HIFOGS spectrometer observed comet C/1995 O1 (Hale–Bopp)) at epochs including 96 Oct 7–14 UT (2.8 AU)), 97 Feb 14–15 UT (1.2 AU)), 97 Apr 11 UT (0.93 AU)), and 97 Jun 22, 25 UT (1.7 AU)). The HIFOGS 7.5–13.5 μm spectrophotometry (R = 360 - 180)) of the silicate feature at 2.8 AU is identical in shape to the ISO SWS spectra of comet Hale–Bopp (Crovisier et al., 1997)); the strong 11.2 μm peak in the structured silicate feature is identified as olivine. Upon close passage to the sun, the HIFOGS spectra at 1.2 AU and 0.93 AU reveals strong peaks at 9.3 μm and 10.0 μm. The post-perihelion 10 μm silicate feature at 1.7 AU is weaker but has nearly the same shape as the pre-perihelion spectra at 1.2 AU, reverting to its pre-perihelion shape: there is no change in the dust chemistry by close passage to the sun. The appearance of the strong peaks at 9.3 μm and 10.0 μm at rh≲ 1.7 AU is attributed to the rise in the contribution of pryoxenes (clino-pyroxene and orthopyroxene crystals)) to the shape of the feature, and leads to the hypothesis that the pyroxenes are significantly cooler than the olivines. The pyroxenes are radiating on the Wien side of the blackbody at 2.8 AU and transition to the Rayleigh–Jeans tail of the blackbody upon closer approach to the Sun. Composite fits to the observed 10 μm silicate features using IDPs and laboratory minerals shows that a good empirical fit to the spectra is obtained when the pryoxenes are about 150 K cooler than the olivines. The pyroxenes, because they are cooler and contribute signficantly at perihelion, are more abundant than the olivines. The perihelion temperature of the pyroxenes implies that the pyroxenes are more Mg-rich than the other minerals including the olivines, amorphous olivines, and amorphous pyroxenes. The PUMA-1 flyby measurements of comet P/Halley also indicated an overabundance of Mg-rich pryoxenes compared to olivines. Comet Hale–Bopp's pyroxenes are similar to pyroxere IDPs from the ’Spray‘ class, known for their D-richness and their unaltered morphologies: Hale–Bopp's Mg-rich pyroxenes may be pristine relic ISM grains.