Institute of Structural Biology Helmholtz Zentrum München, Ingolstädter Landstr. 1, 85764, Neuherberg, Germany.
Chemphyschem. 2022 Nov 4;23(21):e202200395. doi: 10.1002/cphc.202200395. Epub 2022 Aug 16.
Despite decades of efforts, much is still unknown about the hydrolysis of nitrogen dioxide (NO ), a reaction associated with the formation of acid rain. From the experimental point of view, quantitative analyses are hard, and without pH control the products decompose to some reagents. We resort to high-level quantum chemistry to compute Gibbs energies for a network of reactions relevant to the hydrolysis of NO . With COSMO-RS solvation corrections we calculate temperature dependent thermodynamic data in liquid water. Using the computed reaction energies, we determine equilibrium concentrations for a gas-liquid system at controlled pH. For different temperatures and initial concentrations of the different species, we observe that nitrogen dioxide should be fully converted to nitric and nitrous acid. The thermodynamic data in this work can have a potential major impact for several industries with regards to the understanding of atmospheric chemistry and in the reduction of anthropomorphic pollution.
尽管已经进行了几十年的努力，但对于二氧化氮（NO2）的水解反应，人们仍然知之甚少，该反应与酸雨的形成有关。从实验的角度来看，定量分析很困难，并且如果没有 pH 值控制，产物会分解为一些试剂。我们求助于高级量子化学来计算与 NO2水解相关的反应网络的吉布斯自由能。我们使用 COSMO-RS 溶剂化校正来计算液态水中的温度相关热力学数据。利用计算出的反应能，我们确定了在控制 pH 值的气液系统中的平衡浓度。对于不同温度和不同物种的初始浓度，我们观察到二氧化氮应该完全转化为硝酸和亚硝酸。这项工作中的热力学数据可能会对几个行业产生重大影响，有助于人们理解大气化学和减少人为污染。
