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

57287-U

Supelco

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

57551-U

Supelco

SPME Fiber Assembly Kit, Assortment, StableFlex (1 cm), needle size 24 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

57284-U

Supelco

SPME Fiber Assembly Kit, Assortment, StableFlex (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

57325-U

Supelco

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

241997

Sigma-Aldrich

1-Pentene, 98%

57307

Supelco

SPME Fiber Assembly Kit, Assortment #1, Fused Silica (1 cm), needle 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

57306

Supelco

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

57320-U

Supelco

SPME Fiber Assembly Kit, Assortment #2, 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

57550-U

Supelco

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

57362-U

Supelco

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

295426

Sigma-Aldrich

Hydrogen chloride, ReagentPlus^®, ≥99%

76971

Sigma-Aldrich

1-Pentene, ≥98.5% (GC)

76969

Supelco

1-Pentene, analytical standard

705551

Sigma-Aldrich

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

138185

Sigma-Aldrich

Hydroxyacetone, contains ≤500 ppm sodium carbonate as stabilizer, technical grade, 90%

W221902

Sigma-Aldrich

Butyraldehyde, ≥96.0%

57291-U

Supelco

SPME Fiber Assembly, 7 μm PDMS, Fused Silica (1 cm), needle size 23 ga, Autosampler, pk of 3, green hub

606758

Sigma-Aldrich

Formaldehyde-¹²C solution, 20% in H₂O, 99.9 atom % ¹²C

57344-U

Supelco

SPME Fiber Assembly, 75 μm CAR/PDMS, Fused Silica (1 cm), needle size 23 ga, Manual Holder, pk of 3, black hub

57310-U

Supelco

SPME Fiber Assembly, 65 μm PDMS/DVB, Fused Silica (1 cm), needle size 24 ga, Manual Holder, pk of 3, blue hub

57311

Supelco

SPME Fiber Assembly, 65 μm PDMS/DVB, Fused Silica (1 cm), needle size 24 ga, Autosampler, pk of 3, blue hub

57326-U

Supelco

SPME Fiber Assembly, 65 μm PDMS/DVB, StableFlex (1 cm), needle size 24 ga, Manual Holder, pk of 3, pink hub

57302

Supelco

SPME Fiber Assembly, 7 μm PDMS, Fused Silica (1 cm), needle size 24 ga, Manual Holder, pk of 3, green hub

57308

Supelco

SPME Fiber Assembly, 30 μm PDMS, Fused Silica (1 cm), needle size 24 ga, Manual Holder, pk of 3, yellow hub

57304

Supelco

SPME Fiber Assembly, 85 μm Polyacrylate, Fused Silica (1 cm), needle size 24 ga, Manual Holder, pk of 3, white hub

57329-U

Supelco

SPME Fiber Assembly, 50/30µm DVB/CAR/PDMS, StableFlex (1 cm), needle size 24 ga, Autosampler, pk of 3, plain gray hub