Roles of HNOx and Carboxylic Acids in the Thermal Stability of Nitroplasticizer

Chen, Kitmin; Edgar, Alexander Steven; Li, Zheng-Hua; Marina, Oana C.; Yang, Dali

doi:10.1021/acsomega.3c00748

Roles of HNO_x and Carboxylic Acids in the Thermal Stability of Nitroplasticizer

Journal Article · Tue Apr 11 00:00:00 EDT 2023 · ACS Omega

DOI:https://doi.org/10.1021/acsomega.3c00748· OSTI ID:1969413

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Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

In the thermal aging of nitroplasticizer (NP), the produced nitrous acid (HONO) can decompose into reactive nitro-oxide species and nitric acid (HNO₃). 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, HNO₃, 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 HNO₃ 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, HNO₃, 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 HNO₃ 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 HNO₃ should be maintained below 1.35 mM and the temperature under 38 °C.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: 89233218CNA000001

OSTI ID:: 1969413

Alternate ID(s):: OSTI ID: 1974976

Report Number(s):: LA-UR-23-21042

Journal Information:: ACS Omega, Vol. 8, Issue 16; ISSN 2470-1343

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (27)

Reaction of nitrogen dioxide with linear polyurethane Jellinek, H. H. G.; Wang, T. J. Y. Journal of Polymer Science: Polymer Chemistry Edition, Vol. 11, Issue 12 https://doi.org/10.1002/pol.1973.170111216	journal	December 1973
A mechanism for the decomposition of dinitropropyl compounds Pauler, Denise K.; Henson, Neil J.; Kress, Joel D. Physical Chemistry Chemical Physics, Vol. 9, Issue 37 https://doi.org/10.1039/b707604e	journal	January 2007
Nitric/Nitrous Acid Equilibria in Supercritical Water Chlistunoff, Jerzy; Ziegler, Kirk J.; Lasdon, Leon The Journal of Physical Chemistry A, Vol. 103, Issue 11 https://doi.org/10.1021/jp983745o	journal	March 1999
Experimental Study of the Oxidative Degradation of PBX 9501 and its Components Salazar, Michael R.; Kress, Joel D.; Lightfoot, J. Michael Propellants, Explosives, Pyrotechnics, Vol. 33, Issue 3 https://doi.org/10.1002/prep.200700272	journal	June 2008
Understanding the Effect of Free Nitrous Acid on Biofilms Chislett, Mariella; Yu, Zhigang; Donose, Bogdan C. Environmental Science & Technology, Vol. 56, Issue 16 https://doi.org/10.1021/acs.est.2c01156	journal	August 2022
Thermal stability of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal: Part A. Degradation mechanisms in air and under nitrogen atmosphere Yang, Dali; Pacheco, Robin; Edwards, Stephanie Polymer Degradation and Stability, Vol. 129 https://doi.org/10.1016/j.polymdegradstab.2016.05.017	journal	July 2016
Structural changes in model compounds of sludge extracellular polymeric substances caused by exposure to free nitrous acid Chislett, Mariella; Guo, Jianhua; Bond, Philip L. Water Research, Vol. 188 https://doi.org/10.1016/j.watres.2020.116553	journal	January 2021
Towards Sustainable Oxalic Acid from CO ₂ and Biomass Schuler, Eric; Demetriou, Marilena; Shiju, N. Raveendran ChemSusChem, Vol. 14, Issue 18 https://doi.org/10.1002/cssc.202101272	journal	August 2021
Liquid Chromatography Quadrupole Time-of-Flight Mass Spectrometry: A Strategy for Optimization, Characterization, and Quantification of Antioxidant Nitro Derivatives Chen, Kitmin; Edgar, Alexander S.; Wong, Camille H. ACS Omega, Vol. 7, Issue 36 https://doi.org/10.1021/acsomega.2c04376	journal	September 2022
Thermal Stability of a Eutectic Mixture of Bis(2,2‐dinitropropyl) Acetal and Formal: Part C. Kinetic Compensation Effect Yang, Dali; Edgar, Alexander S.; Torres, Joseph A. Propellants, Explosives, Pyrotechnics, Vol. 46, Issue 1 https://doi.org/10.1002/prep.202000042	journal	October 2020
Enhanced Acidity of Acetic and Pyruvic Acids on the Surface of Water Eugene, Alexis J.; Pillar, Elizabeth A.; Colussi, Agustín J. Langmuir, Vol. 34, Issue 31 https://doi.org/10.1021/acs.langmuir.8b01606	journal	July 2018
Thermal stability of a eutectic mixture of bis(2,2-dinitropropyl) acetal and formal: Part B. Degradation mechanisms under water and high humidity environments Yang, Dali; Pacheco, Robin; Edwards, Stephanie Polymer Degradation and Stability, Vol. 130 https://doi.org/10.1016/j.polymdegradstab.2016.06.007	journal	August 2016
Identification of 2,2‐dinitropropanol, a Hydrolyzed Product of Aged Eutectic Bis(2,2‐dinitropropyl) Acetal – Bis(2,2‐dinitropropyl) Formal Mixture Edgar, Alexander S.; Wong, Camille H.; Chen, Kitmin Propellants, Explosives, Pyrotechnics https://doi.org/10.1002/prep.202100345	journal	August 2022
The Kinetics of the Thermal Decomposition of Nitric Acid in the Liquid Phase Robertson, Glenn D.; Mason, David M.; Corcoran, William H. The Journal of Physical Chemistry, Vol. 59, Issue 8 https://doi.org/10.1021/j150530a004	journal	August 1955
Fast Ion Chromatographic Method for the Determination of Formates in Alcoholic Drinks Balcerzak, Maria; Kapica, Dawid Food Analytical Methods, Vol. 10, Issue 7 https://doi.org/10.1007/s12161-017-0812-7	journal	January 2017
Role of water in degradation of nitroplasticizer Yang, Dali; Zhang, Duan Z. Polymer Degradation and Stability, Vol. 170 https://doi.org/10.1016/j.polymdegradstab.2019.109020	journal	December 2019
Liquid Chromatography Mass Spectrometry Study of a Eutectic Mixture of bis(2,2‐Dinitropropyl) Acetal/Formal Wong, Camille Hing; Edgar, Alexander Steven; Yang, Dali Propellants, Explosives, Pyrotechnics, Vol. 46, Issue 12 https://doi.org/10.1002/prep.202100189	journal	October 2021
Assessment of free nitrous acid pre-treatment on a mixture of primary sludge and waste activated sludge: Effect of exposure time and concentration Zahedi, S.; Icaran, P.; Yuan, Z. Bioresource Technology, Vol. 216 https://doi.org/10.1016/j.biortech.2016.06.038	journal	September 2016
Oxidation of Catechols at the Air–Water Interface by Nitrate Radicals Rana, Md Sohel; Guzman, Marcelo I. Environmental Science & Technology, Vol. 56, Issue 22 https://doi.org/10.1021/acs.est.2c05640	journal	November 2022
Investigation into the Decomposition Pathways of an Acetal-Based Plasticizer Freye, Chris E.; Snyder, Christopher J. ACS Omega, Vol. 7, Issue 34 https://doi.org/10.1021/acsomega.2c03494	journal	August 2022
Solubility and decomposition kinetics of nitrous acid in aqueous solution Park, Jong Yoon; Lee, Yin Nan The Journal of Physical Chemistry, Vol. 92, Issue 22 https://doi.org/10.1021/j100333a025	journal	November 1988
Mechanisms of Nitrogen Dioxide Reactions: Initiation of Lipid Peroxidation and the Production of Nitrous Acid Pryor, William A.; Lightsey, John W. Science, Vol. 214, Issue 4519 https://doi.org/10.1126/science.214.4519.435	journal	October 1981
Liquid Chromatography Quadrupole Time-of-Flight Mass Spectrometry Analysis of Eutectic Bis(2,2-dinitropropyl) Acetal/Formal Degradation Profile: Nontargeted Identification of Antioxidant Derivatives Chen, Kitmin; Edgar, Alexander S.; Jung, Julie ACS Omega, Vol. 7, Issue 39 https://doi.org/10.1021/acsomega.2c05011	journal	September 2022
Trace Determination of Strong Acids in NitroPlasticizers Désilets, Sylvain; Villeneuve, Sylvie The Analyst, Vol. 122, Issue 9 https://doi.org/10.1039/a701722g	journal	January 1997
Photo-production of lactate from glyoxylate: how minerals can facilitate energy storage in a prebiotic world Guzman, Marcelo I.; Martin, Scot T. Chemical Communications, Vol. 46, Issue 13 https://doi.org/10.1039/b924179e	journal	January 2010
Stabilizers for nitrate ester-based energetic materials and their mechanism of action: a state-of-the-art review Trache, Djalal; Tarchoun, Ahmed Fouzi Journal of Materials Science, Vol. 53, Issue 1 https://doi.org/10.1007/s10853-017-1474-y	journal	August 2017
The Equilibrium Between Nitric Acid, Nitrous acid and Nitric Oxide. Lewis, Gilbert N.; Edgar, Arthur Journal of the American Chemical Society, Vol. 33, Issue 3 https://doi.org/10.1021/ja02216a004	journal	March 1911

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