Rusu Vasilache Ana-Maria, Roman Claudiu, Bejan Iustinian G, Arsene Cecilia, Olariu Romeo I
Department of Chemistry, Faculty of Chemistry, "Alexandru Ioan Cuza" University of Iasi, 11 Carol I, 700506 Iasi, Romania.
Integrated Centre of Environmental Science Studies in the North Eastern Region (CERNESIM), "Alexandru Ioan Cuza" University of Iasi, 11 Carol I, 700506 Iasi, Romania.
J Phys Chem A. 2024 Aug 15;128(32):6745-6756. doi: 10.1021/acs.jpca.4c03653. Epub 2024 Aug 6.
Methyl-butenols are a category of oxygenated biogenic volatile organic compounds emitted by plants as part of their natural metabolic processes. This study examines the gas-phase reactions of ozone (O) with five methyl-butenols (2-methyl-3-buten-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 2-methyl-3-buten-1-ol, and 3-methyl-3-buten-2-ol) under atmospheric conditions at a temperature of (298 ± 2) K and pressure of (1000 ± 10) mbar. The experimental values for the gas-phase reaction rate coefficients obtained in this study, by using the relative rate method, are as follows (in cm molecule s): k(3-methyl-2-buten-1-ol + O) = (311 ± 20) × 10, (2-methyl-3-buten-2-ol + O) = (9.55 ± 1.04) × 10, (3-methyl-3-buten-1-ol + O) = (7.29 ± 0.46) × 10, (2-methyl-3-buten-1-ol + O) = (4.25 ± 0.29) × 10, and (3-methyl-3-buten-2-ol + O) = (62.9 ± 6.8) × 10. The results are discussed in detail, with particular emphasis on the degree and type of substitutions of the double bond. The determined rate coefficient values are also compared to the available literature data and with estimates of the structure-activity relationship. Additionally, the atmospheric implications toward the tropospheric lifetime and photochemical ozone generation potential for the investigated compounds are provided, which highlight the atmospheric impact of methyl-butenol decomposition into the lower atmosphere.
甲基丁烯醇是植物在自然代谢过程中排放的一类含氧生物源挥发性有机化合物。本研究考察了在温度为(298±2)K、压力为(1000±10)毫巴的大气条件下，臭氧(O)与五种甲基丁烯醇（2-甲基-3-丁烯-2-醇、3-甲基-2-丁烯-1-醇、3-甲基-3-丁烯-1-醇、2-甲基-3-丁烯-1-醇和3-甲基-3-丁烯-2-醇）的气相反应。本研究采用相对速率法获得的气相反应速率系数实验值如下（单位为cm³·分子⁻¹·s⁻¹）：k(3-甲基-2-丁烯-1-醇 + O) = (311±20)×10⁻¹²，k(2-甲基-3-丁烯-2-醇 + O) = (9.55±1.04)×10⁻¹²，k(3-甲基-3-丁烯-1-醇 + O) = (7.29±0.46)×10⁻¹²，k(2-甲基-3-丁烯-醇 + O) = (4.25±0.29)×10⁻¹²，k(3-甲基-3-丁烯-2-醇 + O) = (62.9±6.8)×10⁻¹²。对结果进行了详细讨论，特别强调了双键的取代程度和类型。还将测定的速率系数值与现有文献数据以及结构-活性关系估计值进行了比较。此外，还给出了所研究化合物对对流层寿命和光化学臭氧生成潜力的大气影响，突出了甲基丁烯醇分解进入低层大气的大气影响。
