Departamento de Química Física, Facultad de Ciencias y Tecnologías Químicas, Universidad de Castilla-La Mancha (UCLM) , Avenue de Camilo José Cela, s/n, 13071 Ciudad Real, Spain.
Research Institute on Combustion and Atmospheric Pollution (UCLM) , Camino de Moledores 13071 Ciudad Real, Spain.
Environ Sci Technol. 2016 Feb 2;50(3):1234-42. doi: 10.1021/acs.est.5b04379. Epub 2016 Jan 8.
The assessment of the atmospheric impact of the potential foam expansion agent, CF3(CF2)2CH═CH2 (HFC-1447fz), requires the knowledge of its degradation routes, oxidation products, and radiative properties. In this paper, the gas-phase reactivity of HFC-1447fz with OH radicals is presented as a function of temperature, obtaining kOH (T = 263-358 K) = (7.4 ± 0.4) × 10(-13)exp{(161 ± 16)/T} (cm(3)·molecule(-1)·s(-1)) (uncertainties: ±2σ). The formation of gaseous oxidation products and secondary organic aerosols (SOAs) from the OH + HFC-1447fz reaction was investigated in the presence of NOx at 298 K. CF3(CF2)2CHO was observed at low- and high-NOx conditions. Evidence of SOA formation (ultrafine particles in the range 10-100 nm) is reported with yields ranging from 0.12 to 1.79%. In addition, the absolute UV (190-368 nm) and IR (500-4000 cm(-1)) absorption cross-sections of HFC-1447fz were determined at room temperature. No appreciable absorption in the solar actinic region (λ > 290 nm) was observed, leaving the removal by OH radicals as the main atmospheric loss process for HFC-1447fz. The major contribution of the atmospheric loss of HFC-1447fz is due to OH reaction (84%), followed by ozone (10%) and chlorine atoms (6%). Correction of the instantaneous radiative efficiency (0.36 W m(-2)·ppbv(-1)) with the relatively short lifetime of HFC-1447fz (ca. 8 days) implies that its global warming potential at a time horizon of 100 year is negligible (0.19) compared to that of HCFC-141b (782) and to that of modern foam-expansion blowing agents (148, 882, and 804 for HFC-152a, HFC-245fa and HFC-365mfc, respectively).
评估潜在泡沫膨胀剂 CF3(CF2)2CH═CH2 (HFC-1447fz) 的大气影响需要了解其降解途径、氧化产物和辐射特性。本文介绍了 HFC-1447fz 与 OH 自由基在气相中的反应活性随温度的变化关系,得到 kOH (T = 263-358 K) = (7.4 ± 0.4) × 10(-13)exp{(161 ± 16)/T} (cm(3)·molecule(-1)·s(-1)) (不确定度:±2σ)。在 298 K 时,在存在 NOx 的情况下,研究了 OH + HFC-1447fz 反应生成气态氧化产物和二次有机气溶胶 (SOA) 的情况。在低和高 NOx 条件下均观察到 CF3(CF2)2CHO 的形成。报告了 SOA 形成的证据(10-100 nm 范围内的超细颗粒),产率范围为 0.12 至 1.79%。此外,还在室温下测定了 HFC-1447fz 的绝对紫外线 (190-368nm) 和红外线 (500-4000cm(-1)) 吸收截面。在太阳光化区 (λ > 290nm) 没有观察到明显的吸收,这使得 OH 自由基的去除成为 HFC-1447fz 的主要大气损失过程。HFC-1447fz 的大气损失的主要贡献归因于 OH 反应 (84%),其次是臭氧 (10%) 和氯原子 (6%)。用 HFC-1447fz 相对较短的寿命(约 8 天)修正瞬时辐射效率 (0.36 W m(-2)·ppbv(-1)),意味着其在 100 年时间范围内的全球变暖潜势可以忽略不计(0.19),与 HCFC-141b(782)相比,以及与现代泡沫膨胀发泡剂(HFC-152a、HFC-245fa 和 HFC-365mfc 的 148、882 和 804)相比。