The sodium D-line is often present in optical spectra of combustion due to its high prevalence and emissivity. Collision theory predicts the spectral peak to have a red-shift dependent on pressure, P, and temperature, T. Here we show that the conditions reached during deflagration of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) permit the red-shift of the sodium D-line to be calibrated to 1.5 GPa. Deflagration at these pressures is achieved using a split Hopkinson pressure bar apparatus, with temperatures of circa 2900 K from the greybody continuum away from spectral features. Lower deflagration pressures, of 0.5 to 0.9 GPa, are achieved in a fallhammer test, with temperatures of circa 4000 K. The red-shift exhibits the predicted PT-0.7 dependence with a constant of proportionality of (950 ± 30) GPa-1 · K0.7 · nm. Using the serendipitous presence of sodium, this optical technique allows for fast measurements of both pressure and temperature from the same light source in one measurement.