Author ORCID Identifier
0000-0001-8336-2362
Document Type
Dissertation
Date of Award
12-31-2024
Degree Name
Doctor of Philosophy in Chemical Engineering - (Ph.D.)
Department
Chemical and Materials Engineering
First Advisor
Edward L. Dreyzin
Second Advisor
Mirko Schoenitz
Third Advisor
Gennady Gor
Fourth Advisor
Alexei Khalizov
Fifth Advisor
Jeffery Davis
Abstract
The safe and efficient destruction of chemical weapon agents (CWAs) stockpiles remains a critical global challenge. Understanding the thermophysical properties, decomposition mechanisms, and interactions of CWAs with their environment is crucial for developing effective strategies to mitigate their threats. Diisopropyl methylphosphonate (DIMP) and Dimethyl methylphosphonate are commonly used nerve agent surrogates. This dissertation focuses on DIMP and DMMP, investigates their properties and behavior under conditions relevant to prompt defeat scenarios.
The thermophysical properties of DIMP and DMMP were experimentally characterized, including vapor-liquid surface tension (3-60 °C) and viscosities of neat and aqueous solutions. Results revealed significant non-ideal behavior in aqueous solutions, emphasizing the importance of these properties in understanding aerosol formation, spread, and decontamination processes associated with CWAs. To assess the synergistic effects of combustion products of reactive materials on DIMP decomposition, a heat and mass transfer model was developed to predict thermal runaway in burning metal particles (aluminum, magnesium, and boron). The model showed that neglecting the transition regime for heat transport in particles smaller than 100 gm results in inaccuracies, providing critical insights into the combustion product formation of reactive materials. Additionally, the interaction between DIMP and powders of metal oxides: alumina and silica, was investigated. Results indicated that DIMP begins to decompose before reaching its boiling point when exposed to these oxides, highlighting the significant role of combustion products of reactive materials in CWA destruction. The thermal decomposition of vapor-phase DIMP was quantified in the 200-350 °C temperature range under nitrogen, air, and water vapor environments. In air, the decomposition follows a first-order reaction with a rate constant K (T)[s-1] = 107.4±2.5 • exp(- 21.4±6.6[kcal/mol]/RT) and occurs much faster than in nitrogen. Experiments demonstrated that the presence of water vapor (-1.5% by mole) further accelerates the decomposition, with significant effects observed at 300 °C, emphasizing the importance of environmental factors such as oxygen and water vapor in decomposition kinetics.
These findings advance the understanding of CWA destruction under various conditions, providing a comprehensive view of their thermophysical properties, decomposition mechanisms, and interactions with combustion products. This work fills critical gaps in the literature and offers valuable insights for the development of rapid and effective CWA mitigation strategies.
Recommended Citation
Senyurt, Elif Irem, "Decomposition of diisopropyl methylphosphonate (dimp) exposed to elevated temperatures and combustion products of reactive materials" (2024). Dissertations. 1809.
https://digitalcommons.njit.edu/dissertations/1809
