Elucidation of hydrolysis reaction mechanism of tungsten hexafluoride (WF6) using first-principles calculations

Hyunwook Jung, Jeemin Hwang, Hoje Chun, Byungchan Han

Research output: Contribution to journalArticle

Abstract

We identify hydrolysis reaction mechanism of water-reactive WF6 and its accompanying intermediates using first-principles calculations. For the purpose, we evaluate activation and free energy diagrams of elementary reaction steps. We find that WF6, WOF4, and WO2F2 form stable adducts, which quickly reacts with H2O by substituting the ligand F. Gaseous WOF4, WO2F2, WO3 are predicted as unstable in the increasing order, but polymerization reduces their instability, leading to solidification. In overall reaction, WOF4 hydrolysis is the bottleneck due to significantly higher activation barrier of trans isomeric complex than cis counterpart.

Original languageEnglish
JournalJournal of Industrial and Engineering Chemistry
DOIs
Publication statusAccepted/In press - 2018 Jan 1

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Tungsten
Hydrolysis
Free energy
Solidification
Activation energy
Chemical activation
Ligands
Polymerization
Water

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)

Cite this

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title = "Elucidation of hydrolysis reaction mechanism of tungsten hexafluoride (WF6) using first-principles calculations",
abstract = "We identify hydrolysis reaction mechanism of water-reactive WF6 and its accompanying intermediates using first-principles calculations. For the purpose, we evaluate activation and free energy diagrams of elementary reaction steps. We find that WF6, WOF4, and WO2F2 form stable adducts, which quickly reacts with H2O by substituting the ligand F. Gaseous WOF4, WO2F2, WO3 are predicted as unstable in the increasing order, but polymerization reduces their instability, leading to solidification. In overall reaction, WOF4 hydrolysis is the bottleneck due to significantly higher activation barrier of trans isomeric complex than cis counterpart.",
author = "Hyunwook Jung and Jeemin Hwang and Hoje Chun and Byungchan Han",
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AU - Jung, Hyunwook

AU - Hwang, Jeemin

AU - Chun, Hoje

AU - Han, Byungchan

PY - 2018/1/1

Y1 - 2018/1/1

N2 - We identify hydrolysis reaction mechanism of water-reactive WF6 and its accompanying intermediates using first-principles calculations. For the purpose, we evaluate activation and free energy diagrams of elementary reaction steps. We find that WF6, WOF4, and WO2F2 form stable adducts, which quickly reacts with H2O by substituting the ligand F. Gaseous WOF4, WO2F2, WO3 are predicted as unstable in the increasing order, but polymerization reduces their instability, leading to solidification. In overall reaction, WOF4 hydrolysis is the bottleneck due to significantly higher activation barrier of trans isomeric complex than cis counterpart.

AB - We identify hydrolysis reaction mechanism of water-reactive WF6 and its accompanying intermediates using first-principles calculations. For the purpose, we evaluate activation and free energy diagrams of elementary reaction steps. We find that WF6, WOF4, and WO2F2 form stable adducts, which quickly reacts with H2O by substituting the ligand F. Gaseous WOF4, WO2F2, WO3 are predicted as unstable in the increasing order, but polymerization reduces their instability, leading to solidification. In overall reaction, WOF4 hydrolysis is the bottleneck due to significantly higher activation barrier of trans isomeric complex than cis counterpart.

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