Hydrolysis of methylphosphonic anhydride solid to methylphosphonic acid probed by Raman and infrared reflectance spectroscopies

Myers, Tanya L.; Saunders, Danielle L.; Szecsody, James E.; Tonkyn, Russell G.; Mo, Kai-For; Cappello, Benjamin F.; Banach, Catherine A.; Fraga, Carlos G.; Johnson, Timothy J.

doi:10.1039/d1ay00610j

Hydrolysis of methylphosphonic anhydride solid to methylphosphonic acid probed by Raman and infrared reflectance spectroscopies

Journal Article · Tue Sep 21 00:00:00 EDT 2021 · Analytical Methods

DOI:https://doi.org/10.1039/d1ay00610j· OSTI ID:1827357

Myers, Tanya L. ^[1]; Saunders, Danielle L. ^[1]; Szecsody, James E. ^[1]; Tonkyn, Russell G. ^[1]; Mo, Kai-For ^[1]; Cappello, Benjamin F. ^[1]; ^[1]; Fraga, Carlos G. ^[1]; Johnson, Timothy J. ^[1]

BATTELLE (PACIFIC NW LAB)

Much is still unknown about the mechanisms and rates of environmental degradation of organophosphorous pesticides and agents. In this study we focus on the degradation of one organophosphorous compound, namely solid methyl phosphonic acid anhydride [CH3P(O)OHOP(O)OHCH3, MPAN] and its rate of conversion to methyl phosphonic acid (MPA) via heterogeneous hydrolysis. Pure MPAN was synthesized and loaded in open sample cups placed inside exposure chambers containing saturated salt solutions to control the relative humidity (RH). The reaction was monitored in the sample cup at various times using both infrared hemispherical reflectance (HRF) spectroscopy and Raman spectroscopy. Calibrated HRF and Raman spectra of both pure reagents as well as gravimetrically prepared mixtures were used to quantify the concentrations of MPAN and MPA throughout the reaction. Results show that both HRF and Raman spectroscopies are convenient non-invasive methods for detection of solid chemicals. The MPAN degradation rate displayed a very strong dependence on relative humidity: At room temperature the reaction showed 50% conversion of the MPAN in 761 ± 54 hours at 33% RH, 33 ± 4 hours at 43% RH, 17 ± 2 hours at 54% RH and just 7 ± 1 hours at 75% RH. Although MPAN hydrolysis is a second-order reaction, the 33 and 43% RH data, at early reaction times, could be fit with a zeroth order reaction, indicating water vapor and MPAN concentrations were not initially rate controlling. The 54 and 75% RH experiments showed significant deliquescence and decay data could only be fit assuming multiple reactions, implying chemical and/or physical processes partially controlled the hydrolysis rate, in contrast to a single process at low relative humidity.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1827357

Report Number(s):: PNNL-SA-160396

Journal Information:: Analytical Methods, Journal Name: Analytical Methods Journal Issue: 35 Vol. 13

Country of Publication:: United States

Language:: English

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methyl phosphonic acid
methyl phosphonic anhydride
hydrolysis
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Hydrolysis of methylphosphonic anhydride solid to methylphosphonic acid probed by Raman and infrared reflectance spectroscopies

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