Effects of potassium nitrate on the solid phase transitions of ammonium nitrate particles

Abstract

Ammonium nitrate (NH 4NO 3) is a common constituent of atmospheric particulate pollutants. It exists in five stable polymorphic forms, designated as phases V, IV, III, II and I, below its melting point of 170 °C. In atmospheric research, very little attention has been paid to the solid phase transitions of NH 4NO 3 because phase IV NH 4NO 3 particles are stable over a wide range of tropospheric temperatures. Potassium nitrate (KNO 3) is often found to co-exist with NH 4NO 3 in atmospheric aerosols, and it can change the phase transition behaviors of solid NH 4NO 3 particles. In this study, we investigated the effects of KNO 3 on the solid phase transitions of NH 4NO 3 particles using in situ microscopic Raman spectroscopy. Both the transition path and transition temperature of NH 4NO 3 single particles (40–700 μm) depend on the KNO 3 mass percentage and the particle size. With the addition of KNO 3, the IV→II transition, which appears at 52 °C for pure NH 4NO 3 particles, is replaced by the IV→III transition. The KNO 3 mass percentage required for this change in transition path increases with decreasing particle size and the transition temperature decreases with increasing KNO 3 mass percentage. At a relatively high mass percentage of KNO 3 (⩾7.4 wt%), the KNO 3/NH 4NO 3 mixed particles undergo the IV→III transition under ambient temperatures, or even crystallize directly in phase III from droplets with a further increase in the mass percentage of KNO 3. Submicron KNO 3/NH 4NO 3 particles crystallize to phase IV at low KNO 3 mass percentages (⩽5.7 wt%) but to phase III at higher KNO 3 mass percentages (⩾7.4 wt%). These results suggest that atmospheric solid NH 4NO 3 particles may exist in phase III and the phase transitions should not be ignored in atmospheric chemical models.