The HO<sub>4</sub>H → O<sub>3</sub> + H<sub>2</sub>O reaction catalysed by acidic, neutral and basic catalysts in the troposphere
Creators: name: Zhang, Tianlei
name: Bi, Xiujuan
name: Wen, Mingjie
name: Liu, Shuai
name: Chai, Guang
name: Zeng, Zhaopeng
name: Wang, Rui
name: Wang, Wenliang
name: Long, Bo
Publisher: name: Taylor & Francis
Year: 2019
Subjects: subject: Biophysics
subject: Biochemistry
subject: Microbiology
subject: FOS: Biological sciences
subject: Genetics
subject: Evolutionary Biology
subject: Chemical Sciences not elsewhere classified
subject: Biological Sciences not elsewhere classified

description: A detailed effects of catalyst <i>X</i> (<i>X =</i> H<sub>2</sub>O, (H<sub>2</sub>O)<sub>2</sub>, NH<sub>3</sub>, NH<sub>3</sub>···H<sub>2</sub>O, H<sub>2</sub>O···NH<sub>3</sub>, HCOOH and H<sub>2</sub>SO<sub>4</sub>) on the HO<sub>4</sub>H → O<sub>3</sub> + H<sub>2</sub>O reaction have been investigated by using quantum chemical calculations and canonical vibrational transition state theory with small curvature tunnelling. The calculated results show that (H<sub>2</sub>O)<sub>2</sub>-catalysed reactions much faster than H<sub>2</sub>O-catalysed one because of the former bimolecular rate constant larger by 2.6–25.9 times than that of the latter one. In addition, the basic H<sub>2</sub>O···NH<sub>3</sub> catalyst was found to be a better than the neutral catalyst of (H<sub>2</sub>O)<sub>2</sub>. However it is marginally less efficient than the acidic catalysts of HCOOH, and H<sub>2</sub>SO<sub>4</sub>. The effective rate constant (<i>k</i>'<sub>t</sub>) in the presence of catalyst <i>X</i> have been assessed. It was found from <i>k'<sub>t</sub></i> that H<sub>2</sub>O (at 100% RH) completely dominates over all other catalysts within the temperature range of 280–320 K at 0 km altitude. However, compared with the rate constant of HO<sub>4</sub>H → H<sub>2</sub>O + O<sub>3</sub> reaction, the <i>k</i><sub>eff</sub> values for H<sub>2</sub>O catalysed reaction are smaller by 1–2 orders of magnitude, indicating that the catalytic effect of H<sub>2</sub>O makes a negligible contribution to the gas phase reaction of HO<sub>4</sub>H → O<sub>3</sub> + H<sub>2</sub>O. <b>Highlights</b> A detailed effects of catalyst of H<sub>2</sub>O, (H<sub>2</sub>O)<sub>2</sub>, NH<sub>3</sub>, NH<sub>3</sub>···H<sub>2</sub>O, H<sub>2</sub>O···NH<sub>3</sub>, HCOOH and H<sub>2</sub>SO<sub>4</sub> on the HO<sub>4</sub>H → O<sub>3</sub> + H<sub>2</sub>O reaction has been performed.From energetic viewpoint, H<sub>2</sub>SO<sub>4</sub> exerts the strongest catalytic role in HO<sub>4</sub>H → O<sub>3</sub> + H<sub>2</sub>O reaction as compared with the other catalysts.At 0 km altitude H<sub>2</sub>O (at 100% RH) completely dominates over all other catalysts within the temperature range of 280–320 K.HO<sub>4</sub>H → H<sub>2</sub>O + O<sub>3</sub> reaction with H<sub>2</sub>O cannot be compete with the reaction without catalyst, due to the fact that the effective rate constants in the presence of H<sub>2</sub>O are smaller. A detailed effects of catalyst of H<sub>2</sub>O, (H<sub>2</sub>O)<sub>2</sub>, NH<sub>3</sub>, NH<sub>3</sub>···H<sub>2</sub>O, H<sub>2</sub>O···NH<sub>3</sub>, HCOOH and H<sub>2</sub>SO<sub>4</sub> on the HO<sub>4</sub>H → O<sub>3</sub> + H<sub>2</sub>O reaction has been performed. From energetic viewpoint, H<sub>2</sub>SO<sub>4</sub> exerts the strongest catalytic role in HO<sub>4</sub>H → O<sub>3</sub> + H<sub>2</sub>O reaction as compared with the other catalysts. At 0 km altitude H<sub>2</sub>O (at 100% RH) completely dominates over all other catalysts within the temperature range of 280–320 K. HO<sub>4</sub>H → H<sub>2</sub>O + O<sub>3</sub> reaction with H<sub>2</sub>O cannot be compete with the reaction without catalyst, due to the fact that the effective rate constants in the presence of H<sub>2</sub>O are smaller.