{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T19:16:03Z","timestamp":1788290163452,"version":"build-2803163510"},"reference-count":25,"publisher":"American Chemical Society (ACS)","issue":"34","license":[{"start":{"date-parts":[[2026,8,14]],"date-time":"2026-08-14T00:00:00Z","timestamp":1786665600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,27]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The kinetics of the gas-phase reaction between hydroxyl radicals (OH) and trimethyl phosphite (TMPi, (CH3O)3P): (OH + TMPi \u2192 products (reaction 1) was investigated over the 295\u2013735 K temperature range at a total pressure of 1 bar using helium as the bath gas. Hydroxyl radicals were generated in situ via the rapid reaction of electronically excited oxygen atoms, O(1D), with water vapor, providing a clean source of OH radicals. The time-resolved OH concentration profiles were monitored by ultraviolet absorption near 308 nm using a DC-discharge H2O\/Ar low-pressure resonance lamp. The pseudo-first-order rate coefficients were obtained from exponential fits to the initial portions of the OH temporal profiles and converted to the bimolecular rate constants based on the TMPi concentrations. The reaction rate constant shows a pronounced negative temperature dependence across the studied temperature interval, with the reaction rate decreasing as the temperature increases. This behavior is consistent with that observed for related organophosphorus esters, including trimethyl phosphate and dimethyl methyl phosphonate, and supports a mechanistic interpretation involving a submerged transition state along the reaction coordinate. The measured rate constant is represented by the Arrhenius expression over the 295\u2013735 K range: k1 = 1.27 \u00d7 10\u201311exp(619 K\/T) cm3 molecule\u20131 s\u20131, corresponding to an apparent negative activation energy of \u22125.15 kJ mol\u20131 (\u22121.23 kcal mol\u20131). The magnitude and the negative temperature dependence of k1 suggest that attractive long-range interactions and barrierless or near-barrierless channels dominate the entrance dynamics. These results extend the kinetic database for OH reactions with reduced phosphorus compounds and provide constraints for detailed reaction mechanisms relevant to phosphorus-containing species in combustion and atmospheric oxidation environments.<\/jats:p>","DOI":"10.1021\/acs.jpca.6c02720","type":"journal-article","created":{"date-parts":[[2026,8,14]],"date-time":"2026-08-14T22:01:31Z","timestamp":1786744891000},"page":"6730-6736","source":"Crossref","is-referenced-by-count":0,"title":["Kinetics of the\nGas-Phase Reaction of Hydroxyl Radicals\nwith Trimethyl Phosphite (TMPi) over the 295\u2013735 K Temperature\nRange"],"prefix":"10.1021","volume":"130","author":[{"given":"Xiaokai","family":"Zhang","sequence":"first","affiliation":[{"name":"New Jersey Institute of Technology , , , ,","place":["Newark, New Jersey, United States, 07102"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pavel V.","family":"Koshlyakov","sequence":"additional","affiliation":[{"name":"Siberian Branch of Russian Academy of Sciences , , ,","place":["Novosibirsk, Russian Federation, 630090"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0388-4812","authenticated-orcid":true,"given":"Evgeni N.","family":"Chesnokov","sequence":"additional","affiliation":[{"name":"Siberian Branch of Russian Academy of Sciences , , ,","place":["Novosibirsk, Russian Federation, 630090"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3693-6092","authenticated-orcid":true,"given":"Lev N.","family":"Krasnoperov","sequence":"additional","affiliation":[{"name":"New Jersey Institute of Technology , , , ,","place":["Newark, New Jersey, United States, 07102"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,14]]},"reference":[{"key":"2026090114375113300_cit1","doi-asserted-by":"publisher","DOI":"10.1016\/j.porgcoat.2022.107027","article-title":"Recent developments in phosphorus based flame retardant coatings\nfor textiles: Synthesis, applications and performance","volume":"171","author":"O\u0308zer","year":"2022","journal-title":"Prog. Org. Coat."},{"issue":"5","key":"2026090114375113300_cit2","doi-asserted-by":"publisher","first-page":"345","DOI":"10.1177\/0734904106068426","article-title":"A review of recent\nprogress in phosphorus-based flame\nretardants","volume":"24","author":"Levchik","year":"2006","journal-title":"J. Fire Sci."},{"key":"2026090114375113300_cit3","first-page":"163","article-title":"Free radicals\nin combustion chemistry","author":"Walker","year":"1990","journal-title":"Sci. Prog."},{"issue":"7","key":"2026090114375113300_cit4","doi-asserted-by":"publisher","first-page":"1615","DOI":"10.3390\/molecules30071615","article-title":"History of organophosphorus\ncompounds in the context of their use as chemical warfare agents","volume":"30","author":"Boczkowski","year":"2025","journal-title":"Molecules"},{"issue":"5","key":"2026090114375113300_cit5","doi-asserted-by":"publisher","first-page":"745","DOI":"10.1016\/S0045-6535(01)00239-9","article-title":"A perspective\non the potential health risks of PBDEs","volume":"46","author":"McDonald","year":"2002","journal-title":"Chemosphere"},{"issue":"12","key":"2026090114375113300_cit6","doi-asserted-by":"publisher","first-page":"6995","DOI":"10.1021\/es5007862","article-title":"Potential estrogenic effects of phosphorus-containing flame retardants","volume":"48","author":"Zhang","year":"2014","journal-title":"Environ. Sci. Technol."},{"issue":"11","key":"2026090114375113300_cit7","doi-asserted-by":"publisher","first-page":"6330","DOI":"10.1021\/acs.est.8b07032","article-title":"Global historical\nstocks and emissions of PBDEs","volume":"53","author":"Abbasi","year":"2019","journal-title":"Environ. Sci.\nTechnol."},{"issue":"11","key":"2026090114375113300_cit8","doi-asserted-by":"publisher","DOI":"10.1021\/acs.estlett.9b00582","article-title":"Organophosphate Ester Flame Retardants: Are They a\nRegrettable Substitution for Polybrominated Diphenyl Ethers?","volume":"6","author":"Blum","year":"2019","journal-title":"Environ. Sci. Technol. Lett."},{"issue":"5","key":"2026090114375113300_cit9","doi-asserted-by":"publisher","DOI":"10.1289\/ehp.116-a210","article-title":"New thinking\non flame retardants","volume":"116","author":"Betts","year":"2008","journal-title":"Environ. Health Perspect."},{"issue":"24","key":"2026090114375113300_cit10","doi-asserted-by":"publisher","first-page":"13051","DOI":"10.1021\/cr500310b","article-title":"Environmental implications\nof hydroxyl radicals (\u2022OH)","volume":"115","author":"Gligorovski","year":"2015","journal-title":"Chem. Rev."},{"issue":"7","key":"2026090114375113300_cit11","doi-asserted-by":"publisher","DOI":"10.3390\/molecules27072301","article-title":"Kinetics of the Gas-Phase Reaction\nof Hydroxyl Radicals with Dimethyl Methylphosphonate (DMMP) over an\nExtended Temperature Range (273\u2013837 K)","volume":"27","author":"Zhang","year":"2022","journal-title":"Molecules"},{"issue":"23","key":"2026090114375113300_cit12","doi-asserted-by":"publisher","first-page":"14121","DOI":"10.1039\/D1RA00911G","article-title":"Kinetics of\nthe gas-phase reaction\nof hydroxyl radicals with trimethyl phosphate over the 273\u2013837\nK temperature range","volume":"11","author":"Koshlyakov","year":"2021","journal-title":"RSC Adv."},{"issue":"9","key":"2026090114375113300_cit13","doi-asserted-by":"publisher","first-page":"3110","DOI":"10.1021\/jp054435q","article-title":"Modified transition state theory\nand negative apparent activation energies of simple metathesis reactions:\napplication to the reaction CH3+ HBr\u2192 CH4+ Br","volume":"110","author":"Krasnoperov","year":"2006","journal-title":"J. Phys. Chem. A"},{"issue":"8","key":"2026090114375113300_cit14","doi-asserted-by":"publisher","first-page":"1542","DOI":"10.1021\/jp012720d","article-title":"Atmospheric gas-phase\nreactions of selected phosphorus-containing compounds","volume":"106","author":"Martin","year":"2002","journal-title":"J. Phys. Chem. A"},{"issue":"20","key":"2026090114375113300_cit15","doi-asserted-by":"publisher","first-page":"3993","DOI":"10.1021\/acs.jpca.0c00624","article-title":"Disproportionation\nchannel of the self-reaction of hydroxyl radical, OH+ OH\u2192 H2O+\nO, revisited","volume":"124","author":"Zhang","year":"2020","journal-title":"J. Phys. Chem. A"},{"issue":"48","key":"2026090114375113300_cit16","doi-asserted-by":"publisher","first-page":"11817","DOI":"10.1021\/jp308885j","article-title":"Disproportionation channel of self-reaction of hydroxyl\nradical, OH+ OH\u2192 H2O+ O, studied by time-resolved oxygen atom\ntrapping","volume":"116","author":"Sangwan","year":"2012","journal-title":"J. Phys. Chem. A"},{"issue":"24","key":"2026090114375113300_cit17","doi-asserted-by":"publisher","first-page":"6282","DOI":"10.1021\/jp211805v","article-title":"Reaction OH+ OH studied over the\n298\u2013834 K temperature and 1\u2013100 bar pressure ranges","volume":"116","author":"Sangwan","year":"2012","journal-title":"J. Phys. Chem. A"},{"issue":"1","key":"2026090114375113300_cit18","doi-asserted-by":"publisher","first-page":"935","DOI":"10.1016\/j.proci.2004.08.223","article-title":"Elementary\nreactions of formyl (HCO) radical studied by laser photolysis\u2500transient\nabsorption spectroscopy","volume":"30","author":"Krasnoperov","year":"2005","journal-title":"Proc. Combust. Inst."},{"issue":"D2","key":"2026090114375113300_cit19","doi-asserted-by":"publisher","first-page":"3739","DOI":"10.1029\/93JD02659","article-title":"Branching ratios for the O (1 D)+\nN2O reaction","volume":"99","author":"Cantrell","year":"1994","journal-title":"J. Geophys. Res.: Atmos."},{"key":"2026090114375113300_cit20","doi-asserted-by":"publisher","DOI":"10.1016\/j.fuel.2025.137424","article-title":"An experimental\nand kinetic modeling study of the autoignition delay times of trimethyl\nphosphite","volume":"408","author":"Bruce","year":"2026","journal-title":"Fuel"},{"issue":"43","key":"2026090114375113300_cit21","doi-asserted-by":"publisher","first-page":"11699","DOI":"10.1021\/jp1043464","article-title":"Correlation between\nthe Rate Order\nand the Number of Molecules in the Reaction of Trimethyl Phosphite\nwith Water in Acetonitrile Solvent","volume":"114","author":"Yamabe","year":"2010","journal-title":"J. Phys.\nChem. A"},{"issue":"12","key":"2026090114375113300_cit22","doi-asserted-by":"publisher","first-page":"1022","DOI":"10.1002\/mrc.2094","article-title":"17O NMR investigation of phosphite hydrolysis mechanisms","volume":"45","author":"McIntyre","year":"2007","journal-title":"Magn. Reson. Chem."},{"issue":"11","key":"2026090114375113300_cit23","doi-asserted-by":"publisher","first-page":"2427","DOI":"10.1007\/BF00911859","article-title":"Kinetics of\nthe hydrolysis of tri-and diethyl phosphite","volume":"16","author":"Bel\u2019skii","year":"1967","journal-title":"Bull. Acad. Sci. USSR, Div. Chem. Sci."},{"key":"2026090114375113300_cit24","unstructured":"A Manion R. E. H.; Levin R. D.; Burgess D. R.; Orkin V. L.; Tsang W.; McGivern W. S.; Hudgens J. W.; Knyazev V. D.; Atkinson D. B.; Chai E.; Tereza A. M.; Lin C.-Y.; Allison T. C.; Mallard W. G.; Westley F.; Herron J. T.; Hampson R. F.; Frizzell D. H. NIST Standard Reference Database 17., Version 7.0, Release 1.6.8, Data version 2015.09., https:\/\/kinetics.nist.gov (accessed 04\/01\/2026)."},{"issue":"46","key":"2026090114375113300_cit25","doi-asserted-by":"publisher","first-page":"10673","DOI":"10.1021\/acs.jpca.5c06066","article-title":"The Gas Phase Thermochemistry\nand the Hydrogen Atom Abstraction Reactions of Trimethyl Phosphite","volume":"129","author":"Bruce","year":"2025","journal-title":"J. Phys. Chem. A"}],"container-title":["The Journal of Physical\nChemistry A"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpca.6c02720","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpcafh\/article-pdf\/130\/34\/6730\/66576220\/acs.jpca.6c02720.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpcafh\/article-pdf\/130\/34\/6730\/66576220\/acs.jpca.6c02720.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T18:38:01Z","timestamp":1788287881000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpcafh\/article\/130\/34\/6730\/5257375\/Kinetics-of-the-Gas-Phase-Reaction-of-Hydroxyl"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,14]]},"references-count":25,"journal-issue":{"issue":"34","published-online":{"date-parts":[[2026,8,14]]},"published-print":{"date-parts":[[2026,8,27]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpca.6c02720","relation":{},"ISSN":["1089-5639","1520-5215"],"issn-type":[{"value":"1089-5639","type":"print"},{"value":"1520-5215","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,14]]}}}