Theoretical Kinetic Studies on Thermal Decomposition of Glycerol Trinitrate and Trimethylolethane Trinitrate in the Gas and Liquid Phases

Abstract

Glycerol trinitrate (NG) and trimethylolethane trinitrate (TMETN), as typical nitrate esters, are important energetic plasticizers in solid propellants. With the aid of high-precision quantum chemical calculations, the Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation theory and the transition state theory have been employed to investigate the decomposition kinetics of NG and TMETN in the gas phase (over the temperature range of 300–1000 K and pressure range of 0.01–100 atm) and liquid phase (using water as the solvent). The continuum solvation model based on solute electron density (SMD) was used to describe the solvent effect. The thermal decomposition mechanism is closely relevant to the combustion properties of energetic materials. The results show that the RO–NO2 dissociation channel overwhelmingly favors other reaction pathways, including HONO elimination for the decomposition of NG and TMETN in both the gas phase and liquid phase. At 500 K and 1 atm, the rate coefficient of gas phase decomposition of TMETN is 5 times higher than that of NG. Nevertheless, the liquid phase decomposition of TMETN is a factor of 5835 slower than that of NG at 500 K. The solvation effect caused by vapor pressure and solubility can be used to justify such contradictions. Our calculations provide detailed mechanistic evidence for the initial kinetics of nitrate ester decomposition in both the gas phase and liquid phase, which is particularly valuable for understanding the multiphase decomposition behavior and building detailed kinetic models for nitrate ester.

Combustion in a Sustainable World: From Molecules to Processes

“…Organic nitrate propellants , energetic compounds that can decompose by exothermic reactions without additional oxygen, are used, for example, for spacecraft to generate thrust or for underwater applications. , The pyrolysis kinetics of isopropyl nitrate as a nontoxic, noncorrosive compound with potentially superior properties compared to hydrazine and its derivatives has been studied both numerically and experimentally by Vin et al Such studies are also important for understanding the destruction behavior of explosives, for which isopropyl nitrate can serve as a surrogate . Niu et al used theoretical methods to analyze the destruction channels of several nitrate esters in both the gas and liquid phases to build a kinetic model for predicting the stability and decomposition behavior of such compounds . Another nitrogen-containing system that has been studied concerns urea , a compound widely used in the pharmaceutical, pesticide, and materials industry .…”

“…39 Niu et al used theoretical methods to analyze the destruction channels of several nitrate esters in both the gas and liquid phases to build a kinetic model for predicting the stability and decomposition behavior of such compounds. 40 Another nitrogen-containing system that has been studied concerns urea, a compound widely used in the pharmaceutical, pesticide, and materials industry. 41 Honorien et al conducted a theoretical study of the thermodynamics and decomposition behavior of 11 urea derivatives.…”

Kinetic Simulation of the Reaction between N,N-dimethylazidoethylamine (DMAZ) and Dinitrogen Tetroxide (NTO) based on Density Functional Theory

“…Since experiments can only measure the ignition delay period, there is little progress in the research on reducing the ignition delay period. Density functional theory can simulate molecular reactions, analyze the mechanism of the reaction and provide guidance for optimizing the reaction process [15][16][17] . It has developed rapidly and is widely used in the eld of molecular reaction mechanism.…”

Highly Scalable and Inherently Safer Preparation of Di, Tri and Tetra Nitrate Esters Using Continuous Flow Chemistry

“…The starting materials mono/di/tri ethylene glycols (EG, DEG, TEG) and 1,2‐propylene glycol (1,2‐PG) are commercially produced through hydrolysis of ethylene oxide [9] and propylene oxide, [10] respectively. Trimethylolethane trinitrate (TMETN) was developed as a potential alternative of NG due to its higher decomposition temperature and lower impact sensitivity [11] . It can be synthesized from trimethylolethane (TME) which can be produced commercially by aldol condensation of propionaldehyde with formaldehyde in presence of sodium hydroxide [12] .…”

“…Trimethylolethane trinitrate (TMETN) was developed as a potential alternative of NG due to its higher decomposition temperature and lower impact sensitivity. [11] It can be synthesized from trimethylolethane (TME) which can be produced commercially by aldol condensation of propionaldehyde with formaldehyde in presence of sodium hydroxide. [12] It is used as a plasticizer for lowsensitivity gun propellants.…”