OH-initiated photooxidations of 1-pentene and 2-methyl-2-propen-1-ol: mechanism and yields of the primary carbonyl products.

OH-initiated photooxidations of 1-pentene and 2-methyl-2-propen-1-ol: mechanism and yields of the primary carbonyl products.

Chemphyschem : a European journal of chemical physics and physical chemistry (2014-09-05)

Silvina A Peirone, Pablo M Cometto, Silvia I Lane

ABSTRACT

The products of the gas-phase reactions of OH radicals with 1-pentene and 2-methyl-2-propen-1-ol (221MPO) at T=298±2 K and atmospheric pressure were investigated by using a 4500 L atmospheric simulation chamber that was built especially for this work. The molar yield of butyraldehyde was 0.74±0.12 mol for the reaction of 1-pentene. This work provides the first product molar yield determination of formaldehyde (0.82±0.12 mol), 1-hydroxypropan-2-one (0.84±0.13 mol), and methacrolein (0.078±0.012 mol) from the reaction of 221MPO with OH radicals. The mechanism of this reaction is discussed in relation to the experimental results. Additionally, taking into consideration the complex mechanism, the rate coefficients of the reactions of OH with formaldehyde, 1-hydroxypropan-2-one, and methacrolein were derived at atmospheric pressure and T=298±2 K.; the obtained values were (8.9±1.6)×10(-12) , (2.4±1.4)×10(-12) , and (22.9±2.3)×10(-12) cm(3) molecule(-1) s(-1) , respectively.

MATERIALS

Product Number

Brand

Product Description

241997

Sigma-Aldrich

1-Pentene, 98%

57325-U

Supelco

SPME fiber assortment kit 4, for use with autosampler, size 24 ga

57286-U

Supelco

SPME fiber assortment kit 2, for use with autosampler, needle size 23 ga

57551-U

Supelco

SPME StableFlex^™ fiber assortment kit, needle size 24 ga, for use with autosampler

57287-U

Supelco

SPME fiber assortment kit 4, for use with autosampler, needle size 23 ga

57285-U

Supelco

SPME fiber assortment kit 1, for use with autosampler, needle size 23 ga

57307

Supelco

SPME fiber assortment kit 1, for use with autosampler, needle size 24 ga

57321-U

Supelco

SPME fiber assortment kit 2, for use with autosampler, size 24 ga

57324-U

Supelco

SPME fiber assortment kit 4, for use with manual holder, size 24 ga

57306

Supelco

SPME fiber assortment kit 1, for use with manual holder, needle size 24 ga

57320-U

Supelco

SPME fiber assortment kit 2, for use with manual holder, needle size 24 ga

57550-U

Supelco

SPME StableFlex^™ fiber assortment kit, for use with manual holder

57311

Supelco

SPME Fiber Assembly Polydimethylsiloxane/Divinylbenzene (PDMS/DVB), d_f 65 μm(PDMS/DVB, needle size 24 ga, for use with autosampler

57902-U

Supelco

SPME Fiber Assembly Polydimethylsiloxane/Divinylbenzene (PDMS/DVB), d_f 65 μm(PDMS/DVB, for use with autosampler, needle size 23 ga, metal alloy fiber

57362-U

Supelco

SPME fiber assortment kit 5, needle size 23 ga, for use with autosampler

08657

Sigma-Aldrich

7-Amino-1,3-naphthalenedisulfonic acid monopotassium salt monohydrate, BioReagent, suitable for fluorescence, ≥98.0% (T)

76969

Supelco

1-Pentene, analytical standard

76971

Sigma-Aldrich

1-Pentene, ≥98.5% (GC)

57284-U

Supelco

SPME StableFlex^™ fiber assortment kit, needle size 23 ga, StableFlex fiber, for use with autosampler

57914-U

Supelco

SPME fiber assembly Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), for use with autosampler, needle size 23 ga, metal alloy fiber, fiber L 2 cm

57912-U

Supelco

SPME fiber assembly Divinylbenzene/Carboxen/Polydimethylsiloxane (DVB/CAR/PDMS), needle size 23 ga, metal alloy fiber, for use with autosampler, fiber L 1 cm, pkg of 1 × ea

84429

Sigma-Aldrich

Hydrochloric acid solution, ~6 M in H₂O, for amino acid analysis

17935

Supelco

Hydrogen chloride – methanol solution, ~1.25 m HCl (T), for GC derivatization, LiChropur^™

47608

Sigma-Aldrich

Formaldehyde solution, for molecular biology, BioReagent, ≥36.0% in H₂O (T)

17934

Supelco

Hydrogen chloride – ethanol solution, ~1.25 M HCl, for GC derivatization, LiChropur^™