Atmospheric chemistry of perfluorinated carboxylic acids: Reaction with OH radicals and atmospheric lifetimes
Atmospheric chemistry of perfluorinated carboxylic acids: Reaction with OH radicals and atmospheric lifetimes
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DOI：
10.1021/jp036343b
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发表时间：
2004-01-29
影响因子：
2.9
通讯作者：
Mabury, SA
中科院分区：
文献类型：
--
作者：
Hurley, MD;Andersen, MPS;Mabury, SA
采用相对速率技术研究了羟基自由基与同源系列全氟酸F(CF2)(n)COOH （n = 1,2,3,4）在700 Torr空气中296 +/- 2 K下的反应动力学。对于n >1， F(CF2)(n)基团的长度对分子的反应性没有明显的影响。对于n = 1, k(哦+ F (CF2) (n)羧基)=(9.35 + / - 2.08)* 10(-14)厘米(3)分子(1)(1)。为n = 2 - 4 k(哦+ F (CF2) (n)羧基)=(1.69 + / - 0.22)* 10(-13)厘米(3)分子(1)(1)。当n = 1,2,3时，2F(CF2)(n)COOH = (F(CF2)(n)COOH)(2)的二聚化常数分别为0.32 +/- 0.03 Torr（-1）、0.30 +/- 0.03 Torr（-1）、0.41 +/- 0.04 Torr（-1）和0.46 +/- 0.05 Torr（-1）。4,分别。F(CF2)(n)COOH与OH自由基反应的大气寿命估计在n = 1时约为230天，在n = 1时约为130天。与OH自由基的反应是F(CF2)(n)COOH在大气中的次要宿命。F(CF2)(n)COOH在大气中的主要去除机制是湿沉降和干沉降，可能发生在10天左右的时间尺度上。
Relative rate techniques were used to study the kinetics of the reactions of OH radicals with a homologous series of perfluorinated acids, F(CF2)(n)COOH (n = 1, 2, 3, 4), in 700 Torr of air at 296 +/- 2 K. For n > 1, the length of the F(CF2)(n) group had no discernible impact on the reactivity of the molecule. For n = 1, k(OH + F(CF2)(n)COOH) = (9.35 +/- 2.08) x 10(-14) cm(3) molecule(-1) s(-1). For n = 2-4, k(OH + F(CF2)(n)COOH) = (1.69 +/- 0.22) x 10(-13) cm(3) molecule(-1) s(-1). Dimerization constants for 2F(CF2)(n)COOH = (F(CF2)(n)COOH)(2) were determined to be 0.32 +/- 0.03 Torr(-1), 0.30 +/- 0.03 Torr(-1), 0.41 +/- 0.04 Torr(-1), and 0.46 +/- 0.05 Torr(-1) for n = 1, 2, 3. 4, respectively. Atmospheric lifetimes of F(CF2)(n)COOH with respect to reaction with OH radicals are estimated to be approximately 230 days for n = 1 and 130 days for n > 1. Reaction with OH radicals is a minor atmospheric fate of F(CF2)(n)COOH. The major atmospheric removal mechanism for F(CF2)(n)COOH is believed to be wet and dry deposition which probably occurs on a time scale of the order of 10 days.