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

57320-U

Supelco

SPME Fiber Assembly Kit, Assortment #2, Fused Silica (1 cm), needle size 24 ga, Manual Holder, pk of 3

57325-U

Supelco

SPME Fiber Assembly Kit, Assortment #4, Fused Silica (1 cm), size 24 ga, Autosampler, pk of 3

57551-U

Supelco

SPME Fiber Assembly Kit, Assortment, StableFlex (1 cm), needle size 24 ga, Autosampler, pk of 4

57307

Supelco

SPME Fiber Assembly Kit, Assortment #1, Fused Silica (1 cm), needle size 24 ga, Autosampler, pk of 3

57306

Supelco

SPME Fiber Assembly Kit, Assortment #1, Fused Silica (1 cm), needle size 24 ga, Manual Holder, pk of 3

57321-U

Supelco

SPME Fiber Assembly Kit, Assortment #2, Fused Silica (1 cm), size 24 ga, Autosampler, pk of 3

57324-U

Supelco

SPME Fiber Assembly Kit, Assortment #4, Fused Silica (1 cm), size 24 ga, Manual Holder, pk of 3

57550-U

Supelco

SPME Fiber Assembly Kit, Assortment, StableFlex (1 cm), needle size 24 ga, Manual Holder, pk of 4

57287-U

Supelco

SPME Fiber Assembly Kit, Assortment #4, Fused Silica (1 cm), needle size 23 ga, Autosampler, pk of 3

57284-U

Supelco

SPME Fiber Assembly Kit, Assortment, StableFlex (1 cm), needle size 23 ga, Autosampler, pk of 4

57285-U

Supelco

SPME Fiber Assembly Kit, Assortment #1, Fused Silica (1 cm), needle size 23 ga, Autosampler, pk of 3

241997

Sigma-Aldrich

1-Pentene, 98%

295426

Sigma-Aldrich

Hydrogen chloride, ReagentPlus^®, ≥99%

76969

Supelco

1-Pentene, analytical standard

76971

Sigma-Aldrich

1-Pentene, ≥98.5% (GC)

57362-U

Supelco

SPME Fiber Assembly Kit, Assortment #5, Fused Silica (1 cm), needle size 23 ga, Autosampler, pk of 4

57286-U

Supelco

SPME Fiber Assembly Kit, Assortment #2, Fused Silica (1 cm), needle size 23 ga, Autosampler, pk of 3

705551

Sigma-Aldrich

Hydrogen chloride solution, 3 M in cyclopentyl methyl ether (CPME)

13-1790

Sigma-Aldrich

Hydrogen chloride – ethanol solution, 0.1 M in ethanol

13-1683

Sigma-Aldrich

Hydrochloric acid solution, 12 M

13-1740

Sigma-Aldrich

Hydrochloric acid solution, 0.05 M

13-1710

Sigma-Aldrich

Hydrochloric acid solution, 0.5 M

13-1686

Sigma-Aldrich

Hydrochloric acid solution, 6 M

11-0720

Sigma-Aldrich

Formaldehyde solution, JIS special grade, 36.0-38.0%, contains methanol as stabilizer

57928-U

Supelco

SPME Fiber Assembly, 100 μm PDMS, Metal Alloy (1 cm), needle size 23 ga, Autosampler, pk of 1, red hub

57293-U

Supelco

SPME Fiber Assembly, 65 μm PDMS/DVB, StableFlex (1 cm), needle size 23 ga, Autosampler, pk of 3, pink hub

57354-U

Supelco

SPME Fiber Assembly, 60 μm PEG, Metal Alloy (1 cm), needle size 23 ga, Autosampler, pk of 3, purple hub

11-0730

Sigma-Aldrich

Formaldehyde solution, SAJ first grade, ≥35.0%, contains methanol as stabilizer

13-1640

Sigma-Aldrich

Hydrochloric acid, JIS special grade, 35.0-37.0%

13-1720

Sigma-Aldrich

Hydrochloric acid solution, 0.2 M