Effect of (H2O)n (n = 1 and 2) on HOCl + Cl reaction

Literature Information

Publication Date 2023-02-24
DOI 10.1039/D2CP04044A
Impact Factor 3.676
Authors

Amit Kumar, Pradeep Kumar


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Abstract

In the present work, we investigate the effect of water molecules (H2O and (H2O)2) on HOCl + Cl˙ → ClO˙ + HCl (R1), and HOCl + Cl˙ → OH˙ + Cl2 (R2) reactions using quantum chemical and kinetics calculations. The present investigation suggests that a water molecule decreases the energy barrier of both reactions significantly, compared to uncatalyzed reaction. However, the effective rate constants for the water catalyzed path for both channels (R1 and R2) were found to be lower than the bimolecular rate constant of the uncatalyzed path. Further, it was found that the R2 reaction will dominate over the R1 reaction, with or without catalyst. Interestingly, the uncatalyzed title reaction was found to be two times faster than the HOCl + OH˙ reaction, but in the presence of water, HOCl + OH˙ becomes the dominant reaction compared to the HOCl + Cl˙ reaction in the atmosphere. In addition, the concentration of bimolecular complexes formed in the presence of a catalyst are found to be higher than the precursor molecule of the uncatalyzed reaction, which suggests that in the presence of catalyst, the HOCl + Cl˙ reaction would favor the catalyzed path rather than the uncatalyzed path.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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