研究报告
张启磊,张永灏,俞辉,林晓晓,盖艳波,张为俊.O3与异戊酸叶醇酯和己酸叶醇酯反应速率常数的测定[J].环境科学学报,2018,38(7):2796-2802
O3与异戊酸叶醇酯和己酸叶醇酯反应速率常数的测定
- Rate constants for reactions of O3 with cis-3-hexenyl isovalerate and cis-3-hexenyl hexanoate
- 基金项目：国家自然科学基金（No.41575125，91544228，41605102）
- 作者
- 单位
- 张启磊
- 1. 中国科学院安徽光学精密机械研究所, 合肥 230031;2. 中国科学技术大学, 合肥 230026
- 张永灏
- 1. 中国科学院安徽光学精密机械研究所, 合肥 230031;2. 中国科学技术大学环境科学与光电技术学院, 合肥 230031
- 俞辉
- 1. 中国科学院安徽光学精密机械研究所, 合肥 230031;2. 中国科学技术大学, 合肥 230026
- 林晓晓
- 中国科学院安徽光学精密机械研究所, 合肥 230031
- 盖艳波
- 中国科学院安徽光学精密机械研究所, 合肥 230031
- 张为俊
- 1. 中国科学院安徽光学精密机械研究所, 合肥 230031;2. 中国科学技术大学环境科学与光电技术学院, 合肥 230031
- 摘要：利用搭建的流动反应系统研究了两种生物源排放的挥发性有机物异戊酸叶醇酯和己酸叶醇酯与O3的反应动力学.实验采用绝对速率法，以保证异戊酸叶醇酯和己酸叶醇酯浓度远远高于臭氧浓度，在准一级实验条件下获得反应的速率常数信息.首先，利用该装置测得了臭氧与异戊二烯和α-蒎烯的反应速率常数，发现其与文献报道值在误差范围内非常吻合，验证了实验装置和实验方法的可靠性.进而实验测定了298 K和1.01×105 Pa条件下异戊酸叶醇酯和己酸叶醇酯与O3的气相反应速率常数，分别为（1.78±0.24）×10-16和（1.54±0.18）×10-16 cm3·molecule-1·s-1.利用测得的速率常数和大气中臭氧浓度，估算得到两种叶醇酯与臭氧反应的大气寿命约在2 h甚至更短，说明与臭氧的反应是它们在大气中的一种非常重要的消除途径，尤其是在污染严重地区.
- Abstract：C6 hexenyl esters, one important group of biogenic volatile organic compounds (BVOCs), are widely emitted into the atmosphere by plants and vegetation. Understanding their atmospheric fate is pivotal to environmental assessment and model simulation. In this work, a flow reactor has been developed. Based on that, the rate constants of O3 reactions with α-pinene and isoprene were measured firstly, which shows good agreement with the literature values, indicating the reliability of our experiment setup and methods. Then, kinetics for reactions of O3 with cis-3-hexenyl isovalerate and cis-3-hexenyl hexanoate were studied for the first time. At 298 K and 1.01×105 Pa, the measured absolute rate constants are (1.78±0.24)×10-16 cm3·molecule-1·s-1 and (1.54±0.18)×10-16 cm3·molecule-1·s-1, respectively. Finally, atmospheric lifetimes of these two esters were estimated based on the measured rate constants. It is suggested from this work that reaction with O3 is a very important loss pathway for these two esters in the atmosphere, especially in some cities and polluted areas.
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