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Solubility and reactivity of HNCO in water: insights into HNCO's fate in the atmosphere

机译:HNCO在水中的溶解度和反应性:在大气中洞察HNCO的命运

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A growing number of ambient measurements of isocyanic acid (HNCO) are being made, yet little is known about its fate in the atmosphere. To better understand HNCO's loss processes and particularly its atmospheric partitioning behaviour, we measure its effective Henry's Law coefficient KHeff with a bubbler experiment using chemical ionization mass spectrometry as the gas phase analytical technique. By conducting experiments at different pH values and temperature, a Henry's Law coefficient KH of 26?±?2?M?atm1 is obtained, with an enthalpy of dissolution of 34?±?2?kJ?mol1, which translates to a KHeff of 31?M?atm1 at 298?K and at pH 3. Our approach also allows for the determination of HNCO's acid dissociation constant, which we determine to be Ka?=?2.1?±?0.2??×??104?M at 298?K. Furthermore, by using ion chromatography to analyze aqueous solution composition, we revisit the hydrolysis kinetics of HNCO at different pH and temperature conditions. Three pH-dependent hydrolysis mechanisms are in play and we determine the Arrhenius expressions for each rate to be k1?=?(4.4?±?0.2)??×??107?exp(6000?±?240∕T)?M?s1, k2?=?(8.9?±?0.9)??×??106? exp(6770?±?450∕T)?s?1 and k3?=??(7.2?±?1.5)??×??108?exp(10?900?±?1400∕T)?s1, where k1 is for HNCO + H++ H2O ?→? NH4++ CO2, k2 is for HNCO + H2O ?→? NH3 + CO2 and k3 is for NCO+ 2 H2O ?→? NH3+ HCO3. HNCO's lifetime against hydrolysis is therefore estimated to be 10?days to 28?years at pH values, liquid water contents, and temperatures relevant to tropospheric clouds, years in oceans and months in human blood. In all, a better parameterized Henry's Law coefficient and hydrolysis rates of HNCO allow for more accurate predictions of its concentration in the atmosphere and consequently help define exposure of this toxic molecule.
机译:正在制造越来越多的异氰酸(HNCO)的环境测量,但大概是在大气中的命运知之甚少。为了更好地理解HNCO的损失过程,特别是其大气分区行为,我们使用化学电离质谱作为气相分析技术来测量其有效的亨利律系数Kheff。通过在不同的pH值和温度下进行实验,获得26?±2Ω·2Ω·2Ω·2Ω·2Ω·2Ω·2Ω··ΔMα的实验,具有34?±2?2?kj?mol1的溶解焓,这转化为kheff 31?m?atm1在298?k和pH 3。我们的方法还允许确定HNCO的酸解离常数,我们确定为Ka?= 2.1?±0.2 ??×104? 298?k。此外,通过使用离子色谱法分析水溶液组合物,我们在不同的pH和温度条件下重新拟接HNCO的水解动力学。三种pH依赖性水解机制在游戏中,我们确定每个速率的Arrhenius表达式为K1?=?(4.4?±0.2)??×?? 107?exp(6000?±240 / t)?m ?S1,K2?=?(8.9?±0.9)??×?? 106? exp(6770?±450 / t)?1和k3?= ??(7.2?±?1.5)??×?? 108?exp(10?900?±1400 / t)?s1,在哪里K1适用于HNCO + H ++ H2O?→? NH4 ++ CO2,K2用于HNCO + H2O?→? NH3 + CO2和K3用于NCO + 2 H2O?→? NH3 + HCO3。因此,HNCO的寿命估计在pH值,液体水含量和与对流层云相关的温度,人类血液中的多年期间,估计为10?天至28岁。总而言之,HNCO的更好的参数化亨利法律系数和水解率允许更准确地预测其在大气中的浓度,因此有助于定义该有毒分子的暴露。

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