Spectral study of the oligomerization products of α-pinene on kaolinite

Cheshchevoi, V.N.; Palamarev, D.N.; Diner, V.A.; Polushkin, V.A.

doi:10.1016/0032-3950(89)90079-8

Cited by 2 publications

(2 citation statements)

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“…The heterogeneous reactions of terpenes with mineral oxides are also well documented in the catalysis literature. For instance, LIM and α-pinene undergo acetoxylation and hydration processes over zeolites and acid clays. , While liquid terpenes are predominantly used in these catalytic processes, there are also reports on the polymerization of gaseous isoprene and α-pinene on kaolinite. , Acid activation is frequently used to increase the catalytic activity of mineral oxides and clays, further suggesting that uptake of nitric acid on atmospheric mineral dust may enhance its interactions with BVOCs.…”

Section: Introductionmentioning

confidence: 99%

“…20,21 While liquid terpenes are predominantly used in these catalytic processes, there are also reports on the polymerization of gaseous isoprene and αpinene on kaolinite. 22,23 Acid activation is frequently used to increase the catalytic activity of mineral oxides and clays, 24 further suggesting that uptake of nitric acid on atmospheric mineral dust may enhance its interactions with BVOCs.…”

Section: ■ Introductionmentioning

confidence: 99%

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Heterogeneous Reactions of Limonene on Mineral Dust: Impacts of Adsorbed Water and Nitric Acid

et al. 2016

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Biogenic volatile organic compounds (BVOCs), including the monoterpene limonene, are a major source of secondary organic aerosol (SOA). While gas-phase oxidation initiates the dominant pathway for BVOC conversion to SOA, recent studies have demonstrated that biogenic hydrocarbons can also directly react with acidic droplets. To investigate whether mineral dust may facilitate similar reactive uptake of biogenic hydrocarbons, we studied the heterogeneous reaction of limonene with mineral substrates using condensed-phase infrared spectroscopy and identified the formation of irreversibly adsorbed organic products. For kaolinite, Arizona Test Dust, and silica at 30% relative humidity, GC-MS identified limonene-1,2-diol as the dominant product with total organic surface concentrations on the order of (3-5) × 10 molecules m. Experiments with O-labeled water support a mechanism initiated by oxidation of limonene by surface redox sites forming limonene oxide followed by water addition to the epoxide to form limonenediol. Limonene uptake on α-alumina, γ-alumina, and montmorillonite formed additional products in high yield, including carveol, carvone, limonene oxide, and α-terpineol. To model tropospheric processing of mineral aerosol, we also exposed each mineral substrate to gaseous nitric acid prior to limonene uptake and identified similar surface adsorbed products that were formed at rates 2 to 5 times faster than without nitrate coatings. The initial rate of reaction was linearly dependent on gaseous limonene concentration between 5 × 10 and 5 × 10 molecules cm (0.22-20.5 ppm) consistent with an Eley-Rideal-type mechanism in which gaseous limonene reacts directly with reactive surface sites. Increasing relative humidity decreased the amount of surface adsorbed products indicating competitive adsorption of surface adsorbed water. Using a laminar flow tube reactor we measured the uptake coefficient for limonene on kaolinite at 25% RH to range from γ = 5.1 × 10 to 9.7 × 10. After adjusting for reactive surface areas, we estimate uptake coefficients for limonene on HNO-processed mineral aerosol on the order of (1-6) × 10. Although this heterogeneous reaction will not impact the atmospheric lifetime of gaseous limonene, it does provide a new pathway for mineral aerosol to acquire secondary organic matter from biogenic hydrocarbons, which in turn will alter the physical properties of mineral dust.

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Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Heterogeneous Reactions of Limonene on Mineral Dust: Impacts of Adsorbed Water and Nitric Acid

et al. 2016

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Partially (resp. fully) reversible adsorption of monoterpenes (resp. alkanes and cycloalkanes) to fused silica

Liu

Chase

Geiger

2019

The Journal of Chemical Physics

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This work compares the extent of reversibility and the thermodynamics of adsorption (Kads, ΔG°ads) of room-temperature vapors of common environmentally relevant monoterpenes (α-pinene, β-pinene, limonene, and 3-carene) and industrially relevant cyclic and acyclic non-terpene hydrocarbons (cyclohexane, hexane, octane, and cyclooctane) to fused silica surfaces. Vibrational sum frequency generation spectroscopy carried out in the C–H stretching region shows negligible surface coverage-dependent changes in the molecular orientation of all species surveyed except for cyclohexane. The group of monoterpenes studied here distinctly exhibits partially reversible adsorption to fused silica surfaces compared to the group of non-terpene hydrocarbons, demonstrating a link between molecular structure and adsorption thermodynamics. The standard Gibbs free energy of adsorption is nonlinearly correlated with the equilibrium vapor pressure of the compounds surveyed.

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Spectral study of the oligomerization products of α-pinene on kaolinite

Cited by 2 publications

References 3 publications

Heterogeneous Reactions of Limonene on Mineral Dust: Impacts of Adsorbed Water and Nitric Acid

Heterogeneous Reactions of Limonene on Mineral Dust: Impacts of Adsorbed Water and Nitric Acid

Partially (resp. fully) reversible adsorption of monoterpenes (resp. alkanes and cycloalkanes) to fused silica

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