Transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by permanganate

Chanat Chokejaroenrat, Steven Comfort, Clifford E. Harris, Daniel D Snow, David Cassada, Chainarong Sakulthaew, Tunlawit Satapanajaru

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The chemical oxidant permanganate (MnO4-) has been shown to effectively transform hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) at both the laboratory and field scales. We treated RDX with MnO4 - with the objective of quantifying the effects of pH and temperature on destruction kinetics and determining reaction rates. A nitrogen mass balance and the distribution of reaction products were used to provide insight into reaction mechanisms. Kinetic experiments (at pH ∼ 7, 25 °C) verified that RDX-MnO4- reaction was first-order with respect to MnO4- and initial RDX concentration (second-order rate: 4.2 × 10-5 M-1 s-1). Batch experiments showed that choice of quenching agents (MnSO4, MnCO3, and H2O2) influenced sample pH and product distribution. When MnCO3 was used as a quenching agent, the pH of the RDX-MnO 4- solution was relatively unchanged and N2O and NO3- constituted 94% of the N-containing products after 80% of the RDX was transformed. On the basis of the preponderance of N2O produced under neutral pH (molar ratio N2O/NO 3 ∼ 5:1), no strong pH effect on RDX-MnO4- reaction rates, a lower activation energy than the hydrolysis pathway, and previous literature on MnO4- oxidation of amines, we propose that RDX-MnO4- reaction involves direct oxidation of the methylene group (hydride abstraction), followed by hydrolysis of the resulting imides, and decarboxylation of the resulting carboxylic acids to form N2O, CO2, and H2O.

Original languageEnglish (US)
Pages (from-to)3643-3649
Number of pages7
JournalEnvironmental Science and Technology
Volume45
Issue number8
DOIs
StatePublished - Apr 15 2011

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triazine
reaction rate
hydrolysis
oxidation
decarboxylation
kinetics
carboxylic acid
oxidant
activation energy
mass balance
transform
experiment
Reaction rates
Quenching
Hydrolysis
nitrogen
pH effects
Imides
product
permanganic acid

ASJC Scopus subject areas

  • Chemistry(all)
  • Environmental Chemistry

Cite this

Transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by permanganate. / Chokejaroenrat, Chanat; Comfort, Steven; Harris, Clifford E.; Snow, Daniel D; Cassada, David; Sakulthaew, Chainarong; Satapanajaru, Tunlawit.

In: Environmental Science and Technology, Vol. 45, No. 8, 15.04.2011, p. 3643-3649.

Research output: Contribution to journalArticle

Chokejaroenrat, C, Comfort, S, Harris, CE, Snow, DD, Cassada, D, Sakulthaew, C & Satapanajaru, T 2011, 'Transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by permanganate', Environmental Science and Technology, vol. 45, no. 8, pp. 3643-3649. https://doi.org/10.1021/es104057v
Chokejaroenrat, Chanat ; Comfort, Steven ; Harris, Clifford E. ; Snow, Daniel D ; Cassada, David ; Sakulthaew, Chainarong ; Satapanajaru, Tunlawit. / Transformation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) by permanganate. In: Environmental Science and Technology. 2011 ; Vol. 45, No. 8. pp. 3643-3649.
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AU - Harris, Clifford E.

AU - Snow, Daniel D

AU - Cassada, David

AU - Sakulthaew, Chainarong

AU - Satapanajaru, Tunlawit

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