The hydroxyl radical reaction rate constant and products of 3,5‐dimethyl‐1‐hexyn‐3‐ol

Abstract

A bimolecular rate constant, k DHO , of (29 ± 9) × 10 −12 cm 3 molecule −1 s −1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,5-dimethyl-1-hexyn-3-ol (DHO, HC CC(OH)(CH 3 )CH 2 CH(CH 3 ) 2 ) at (297 ± 3) K and 1 atm total pressure. To more clearly define DHO's indoor environment degradation mechanism, the products of the DHO + OH reaction were also investigated. The positively identified DHO/OH reaction products were acetone ((CH 3 ) 2 C O), 3-butyne-2-one (3B2O, HC CC( O)(CH 3 )), 2-methyl-propanal (2MP, H(O )CCH(CH 3 ) 2 ), 4-methyl-2-pentanone (MIBK, CH 3 C( O)CH 2 CH(CH 3 ) 2 ), ethanedial (GLY, HC( O)C( O)H), 2-oxopropanal (MGLY, CH 3 C( O)C( O)H), and 2,3-butanedione (23BD, CH 3 C( O)C( O)CH 3 ). The yields of 3B2O and MIBK from the DHO/OH reaction were (8.4 ± 0.3) and (26 ± 2)%, respectively. The use of derivatizing agents O- (2,3,4,5,6-pentalfluorobenzyl)hydroxylamine (PFBHA) and N,Obis(trimethylsilyl)trifluoroacetamide (BSTFA) clearly indicated that several other reaction products were formed. The elucidation of these other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible DHO/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms. C

Gas‐phase chemistry of dihydromyrcenol with ozone and OH radical: Rate constants and products

“…The reaction products observed from the initial dihydromyrcenol/OH hydrogen abstraction or OH addition to the carbon-carbon double bond are consistent with previously observed OH radical reaction mechanisms for oxygenated organic species [12][13][14][15][16][17][18][19]. Typically, the oxygenated organic parent compound reacts with OH to subsequently generate other oxygenated organic products.…”

“…Many other dihydromyrcenol/OH reaction products were observed utilizing the derivatization methods described above. Elucidation of these other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible dihydromyrcenol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms [10,[12][13][14][15][16][17][18][19]. These other reaction products are listed in Table I.…”

“…Acetone is also a product of the dihydromyrcenol/O 3 reaction, but its peak area increased by only a few percent. Aside from the positively identified reaction products (Table I) with the synthesis of the derivatized oxime compound, dihydromyrcenol/OH and dihydomyrcenol/O 3 reaction product identification was derived from mass spectra data and previously published VOC/OH and VOC/O 3 reaction mechanisms [12][13][14][15][16][17][18][19]25].…”

Rate constants for the gas-phase reactions of nitrate radicals with geraniol, citronellol, and dihydromyrcenol

“…To determine possible chromatographic interferences from reference/NO 3 • and reaction products, geraniol, citronellol and dihydromyrcenol, and the reference compounds were mixed and were allowed to react with NO 3 • radical in separate experiments and were analyzed as described previously [24]. No chromatographic interferences were observed.…”

Atmospheric reactivity of HCCCH2OH (2-propyn-1-ol) toward OH radicals: experimental determination and theoretical comparison with its alkyne analogue

“…6 The stability of the alkoxy radical formed depends on the chain length and the possibilities of stabilization of the electronically excited adduct, which could minimize decomposition to initial reactants. 13,14 A relative kinetic study of the reaction of OH + 3,5dimethyl-1-hexin-3-ol in 1 atm of air in the presence of NO x was reported in the literature, and there is also an absolute determination of the rate coefficient of the reaction OH + 2P1OL at low pressures (1.33 to 2.67 kPa) using pulsed laser photolysis coupled with laser induced uorescence technique (PLP-LIF). 13,14 A relative kinetic study of the reaction of OH + 3,5dimethyl-1-hexin-3-ol in 1 atm of air in the presence of NO x was reported in the literature, and there is also an absolute determination of the rate coefficient of the reaction OH + 2P1OL at low pressures (1.33 to 2.67 kPa) using pulsed laser photolysis coupled with laser induced uorescence technique (PLP-LIF).…”