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

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%

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

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

57286-U

Supelco

SPME Fiber Assembly Kit, Assortment #2, Fused Silica (1 cm), needle size 23 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

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

57307

Supelco

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

76971

Sigma-Aldrich

1-Pentene, ≥98.5% (GC)

76969

Supelco

1-Pentene, analytical standard

57362-U

Supelco

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

57298-U

Supelco

SPME Fiber Assembly, 50/30µm DVB/CAR/PDMS, StableFlex (1 cm), needle size 23 ga, Autosampler, pk of 3, plain gray hub

57914-U

Supelco

SPME Fiber Assembly, 50/30µm DVB/CAR/PDMS, Metal Alloy (2cm), needle size 23 ga, Autosampler, pk of 1, plain gray hub

57902-U

Supelco

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

57906-U

Supelco

SPME Fiber Assembly, 85 μm CAR/PDMS, Metal Alloy (1 cm), needle size 23 ga, Autosampler, pk of 1, light blue hub

57295-U

Supelco

SPME Fiber Assembly, 85 μm CAR/PDMS, StableFlex (1 cm), needle size 23 ga, Autosampler, pk of 3, light blue hub

57293-U

Supelco

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

57294-U

Supelco

SPME Fiber Assembly, 85 μm Polyacrylate, Fused Silica (1 cm), needle size 23 ga, Autosampler, pk of 3, white hub

606758

Sigma-Aldrich

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

57348-U

Supelco

SPME Fiber Assembly, 50/30µm DVB/CAR/PDMS, StableFlex (2cm), needle size 24 ga, Autosampler, pk of 3, notched gray hub

57334-U

Supelco

SPME Fiber Assembly, 85 μm CAR/PDMS, StableFlex (1 cm), needle size 24 ga, Manual Holder, pk of 3, light blue hub

57308

Supelco

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

57333-U

Supelco

SPME Sampling Stand, for use with 4 mL vials

57341-U

Supelco

SPME Fiber Assembly, 100 μm PDMS, Fused Silica (1 cm), needle size 23 ga, Autosampler, pk of 3, red hub

57304

Supelco

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