Roles of HNO(x) and Carboxylic Acids in the Thermal Stability of Nitroplasticizer

[Image: see text] In the thermal aging of nitroplasticizer (NP), the produced nitrous acid (HONO) can decompose into reactive nitro-oxide species and nitric acid (HNO(3)). These volatile species are prone to cause cascaded deterioration of NP and give rise to various acidic constituents. To gain insight on the early stage of NP degradation, an adequate method for measuring changes in the concentrations of HONO, HNO(3), and related acidic species is imperative. The typical assessment of acidity in nonaqueous solutions (i.e., acid number) cannot differentiate acidic species and thus presents difficulty in the measurement of HONO and HNO(3) at a micromolar concentration level. Using liquid–liquid extraction and ion chromatography (IC), we developed a fast and unambiguous analytical method to accurately determine the concentration of HONO, HNO(3), acetic/formic acids, and oxalic acid in aged NP samples. Given by the overlay analysis results of liquid chromatography coupled with quadrupole time-of-flight mass spectrometry and IC, the prominent increase of produced HONO after the depletion of antioxidants is the primary cause of HNO(3) formation in the late stage of NP degradation, which results in the acid-catalyzed hydrolysis of NP into 2,2-dinitropropanol and acetic/formic acids. Our study has demonstrated that the aging temperature plays a crucial role in accelerating the formation and decomposition of HONO, which consequently increases the acidity of aged NP samples and hence accelerates the hydrolyzation of NP. Therefore, to prevent NP from undergoing rapid degradation, we suggest that the concentration of HNO(3) should be maintained below 1.35 mM and the temperature under 38 °C.