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

295426

Sigma-Aldrich

Hydrogen chloride, ReagentPlus^®, ≥99%

76971

Sigma-Aldrich

1-Pentene, ≥98.5% (GC)

76969

Supelco

1-Pentene, analytical standard

57551-U

Supelco

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

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

57287-U

Supelco

SPME Fiber Assembly Kit, Assortment #4, 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

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

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

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

57320-U

Supelco

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

57362-U

Supelco

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

705551

Sigma-Aldrich

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

13-1686

Sigma-Aldrich

Hydrochloric acid solution, 6 M

13-1640

Sigma-Aldrich

Hydrochloric acid, JIS special grade, 35.0-37.0%

13-1650

Sigma-Aldrich

Hydrochloric acid, SAJ first grade, 35.0-37.0%

11-0730

Sigma-Aldrich

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

13-1690

Sigma-Aldrich

Hydrochloric acid solution, 2 M

13-1710

Sigma-Aldrich

Hydrochloric acid solution, 0.5 M

57928-U

Supelco

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

57902-U

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

57906-U

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

57914-U

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

57912-U

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57293-U

Supelco

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