Exploring the thermal behavior of phosphorus pentachloride (PCl5): A kinetic analysis using differential scanning calorimetry

Article

Authorship

RESENTERA BEIZA, ALEXANDER CRISTIAN JESÚS ; RODRIGUEZ, MARIO HUMBERTO ; COZZARIN, MELINA VANESA

Date

2025

Publishing House and Editing Place

ELSEVIER SCIENCE BV

Magazine

THERMOCHIMICA ACTA, vol. 747 (pp. 1-7) - ISSN 0040-6031
ELSEVIER SCIENCE BV

ISSN

0040-6031

Summary Information provided by the agent in SIGEVA

Phosphorus pentachloride (PCl5) plays an important role in the chemical industry of pharmaceuticals, agrochemicals, and, more recently, the manufacture of electrolytes for energy storage systems. In this study, its thermokinetic behavior was analyzed for the first time using differential scanning calorimetry (DSC) under a nitrogen atmosphere. Kinetic parameters were determined using complementary methods, such as Friedman isoconversional analysis, Kissinger method, combined kinetic analysis, an... Phosphorus pentachloride (PCl5) plays an important role in the chemical industry of pharmaceuticals, agrochemicals, and, more recently, the manufacture of electrolytes for energy storage systems. In this study, its thermokinetic behavior was analyzed for the first time using differential scanning calorimetry (DSC) under a nitrogen atmosphere. Kinetic parameters were determined using complementary methods, such as Friedman isoconversional analysis, Kissinger method, combined kinetic analysis, and nonlinear regression optimization. The findings suggest that PCl5 sublimates at significantly lower temperatures than previously reported, starting at room temperature with a single endothermic event. The apparent activation energy obtained was 70.65 ± 0.04 kJ/mol, with a pre-exponential factor of ln?(A/s^(-1)) = 17.65 ± 0.06. The process follows a surface geometric contraction (R2) kinetic model, which well correlated with a sublimation process. This sublimation process was indirectly corroborated by XRD characterization of the recondensed gas. This obtained kinetic model can aid in optimizing PCl5 storage, transportation, and handling, contributing to safer and more efficient industrial processes.