Decomposition of supercritical ammonia and modeling of supercritical ammonia–nitrogen–hydrogen solutions with applicability toward ammonothermal conditions

Abstract

Ammonothermal growth of nitrides occurs at temperatures in excess of 800K and pressures greater than 150MPa. For this region, no experimentally verified equation of state (EOS) exists for ammonia, nor is there any accurate description available for the equilibrium constant of the ammonia decomposition reaction for pressures in excess of 100MPa. To fill this void, experimental P-v-T data was collected for pure ammonia at T>700K and compared to extrapolated data from the reference EOS for ammonia. For the extrapolated region, the reference EOS provided excellent agreement to within error of the collected experimental data. A simplified EOS based on the Beattie–Bridgeman (BB) EOS was derived and fit to calculated and, for ammonia, extrapolated reference EOS data for ammonia, hydrogen, and nitrogen (T<1000K, P<300MPa). By applying mixing rules with separated contributions for polar and non-polar interactions, an EOS was derived for NH3–N2–H2 mixtures. With these expressions, an accurate description for the equilibrium constant for the ammonia decomposition reaction as a function of pressure and temperature was derived and verified against experimental data determined for total system pressures of 92, 151 and 210MPa at T ∼810K. Coupling of the EOSs with the equilibrium constant permitted accurate modeling of a sealed autoclave filled with pure ammonia, after incorporating corrections for the expansion of the internal free volume due to thermal expansion and elastic strain response of the autoclave walls due to internal pressure buildup. Calculated total system pressure and equilibrium ammonia density at various temperatures and initial ammonia fill densities are in very good to excellent agreement with experimental data. This paper thus provides a simple EOS for ammonia, hydrogen, nitrogen and NH3–N2–H2 mixtures accurate to within approximately 1–2% in pressure for temperatures greater than 700K. The equilibrium constant for the ammonia decomposition reaction includes non-ideal mixing contributions from the second virial coefficient with a resulting accuracy in the equilibrium mole fraction of ammonia of approximately 2% for T<850K.