Kinetics and Mechanism of the Thermal Decomposition of Sodium Percarbonate: Role of the Surface Product Layer

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 117; no. 9; pp. 1880 - 1889
• Main Authors: Wada, Takeshi, Koga, Nobuyoshi
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 07.03.2013
• Subjects: Atmospherics; Crystals; Diffusion layers; Reaction kinetics; Reaction mechanisms; Sodium; Thermal decomposition; Water vapor
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp3123924

The reaction mechanism and overall kinetics of the thermal decomposition of sodium percarbonate crystals were investigated by thermoanalytical measurements and morphological observations. The reaction proceeds via a surface reaction and subsequent advancement of the as-produced reaction interface toward the center of the crystals, where the seemingly smooth mass-loss behavior can be described by the apparent activation energy E a of ca. 100 kJ mol–1. However, considering the rate behavior, as the reaction advances, it is expected that the secondary reaction step characterized by an autocatalytic rate behavior takes part in the overall reaction. The hindrance of the diffusional removal of the evolved gases by the surface product layer, Na2CO3, is the most probable reason for the change in the reaction mechanism. In the deceleration part of the first reaction step, the second reaction step is accelerated due to an increase in the water vapor pressure at the reaction interface inside the reacting particles. We also expect the self-generated reaction condition of the high water vapor pressure and the existence of liquid phase due to the formation of Na2CO3 whiskers as the solid product and the insensitive rate behavior of the second reaction step to a higher atmospheric water vapor pressure. A relevant reaction model for the thermal decomposition of SPC crystals are discussed by focusing on the role of the surface product layer.