Ab initio investigation of the nitrosation reactions of hydroxylamine in aqueous solutions

Kaiqiang Zhang, Stefan Thynell

Research output: Contribution to conferencePaper

Abstract

Ab initio calculations were performed to ascertain the details of the global reaction given by NH2OH+HONO=N2O+2H2O, which has been suggested as a major pathway in the rapid depletion of aqueous hydroxylammonium nitrate (HAN) under thermolysis conditions. The free energies of species and transition states were obtained using the Born-Haber thermodynamic cycle and the SMD solvation model. The performance of several potential nitrosating agents including HONO, N2O3, and H2ONO+ are compared. These nitrosating agents would react with NH3OH+ to form NH3ONO+, or react with NH2OH to produce NH2ONO, HONHNO, and ONNH2O. The decomposition of NH2ONO starts from -NO migration to form ONNH2O, then transforms to HONHNO via fast acid-base equilibrium. The rate-determining steps for the global reaction are predicted to be the formation reactions of the nitrosating agents and the nitrosation steps.

Original languageEnglish (US)
StatePublished - Jan 1 2017
Event10th U.S. National Combustion Meeting - College Park, United States
Duration: Apr 23 2017Apr 26 2017

Other

Other10th U.S. National Combustion Meeting
CountryUnited States
CityCollege Park
Period4/23/174/26/17

Fingerprint

Hydroxylamine
aqueous solutions
acid base equilibrium
thermodynamic cycles
Thermolysis
Surface mount technology
Solvation
Nitrates
Free energy
solvation
nitrates
depletion
free energy
Thermodynamics
Decomposition
decomposition
Nitrosation

All Science Journal Classification (ASJC) codes

  • Chemical Engineering(all)
  • Physical and Theoretical Chemistry
  • Mechanical Engineering

Cite this

Zhang, K., & Thynell, S. (2017). Ab initio investigation of the nitrosation reactions of hydroxylamine in aqueous solutions. Paper presented at 10th U.S. National Combustion Meeting, College Park, United States.
Zhang, Kaiqiang ; Thynell, Stefan. / Ab initio investigation of the nitrosation reactions of hydroxylamine in aqueous solutions. Paper presented at 10th U.S. National Combustion Meeting, College Park, United States.
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abstract = "Ab initio calculations were performed to ascertain the details of the global reaction given by NH2OH+HONO=N2O+2H2O, which has been suggested as a major pathway in the rapid depletion of aqueous hydroxylammonium nitrate (HAN) under thermolysis conditions. The free energies of species and transition states were obtained using the Born-Haber thermodynamic cycle and the SMD solvation model. The performance of several potential nitrosating agents including HONO, N2O3, and H2ONO+ are compared. These nitrosating agents would react with NH3OH+ to form NH3ONO+, or react with NH2OH to produce NH2ONO, HONHNO, and ONNH2O. The decomposition of NH2ONO starts from -NO migration to form ONNH2O, then transforms to HONHNO via fast acid-base equilibrium. The rate-determining steps for the global reaction are predicted to be the formation reactions of the nitrosating agents and the nitrosation steps.",
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Zhang, K & Thynell, S 2017, 'Ab initio investigation of the nitrosation reactions of hydroxylamine in aqueous solutions' Paper presented at 10th U.S. National Combustion Meeting, College Park, United States, 4/23/17 - 4/26/17, .

Ab initio investigation of the nitrosation reactions of hydroxylamine in aqueous solutions. / Zhang, Kaiqiang; Thynell, Stefan.

2017. Paper presented at 10th U.S. National Combustion Meeting, College Park, United States.

Research output: Contribution to conferencePaper

TY - CONF

T1 - Ab initio investigation of the nitrosation reactions of hydroxylamine in aqueous solutions

AU - Zhang, Kaiqiang

AU - Thynell, Stefan

PY - 2017/1/1

Y1 - 2017/1/1

N2 - Ab initio calculations were performed to ascertain the details of the global reaction given by NH2OH+HONO=N2O+2H2O, which has been suggested as a major pathway in the rapid depletion of aqueous hydroxylammonium nitrate (HAN) under thermolysis conditions. The free energies of species and transition states were obtained using the Born-Haber thermodynamic cycle and the SMD solvation model. The performance of several potential nitrosating agents including HONO, N2O3, and H2ONO+ are compared. These nitrosating agents would react with NH3OH+ to form NH3ONO+, or react with NH2OH to produce NH2ONO, HONHNO, and ONNH2O. The decomposition of NH2ONO starts from -NO migration to form ONNH2O, then transforms to HONHNO via fast acid-base equilibrium. The rate-determining steps for the global reaction are predicted to be the formation reactions of the nitrosating agents and the nitrosation steps.

AB - Ab initio calculations were performed to ascertain the details of the global reaction given by NH2OH+HONO=N2O+2H2O, which has been suggested as a major pathway in the rapid depletion of aqueous hydroxylammonium nitrate (HAN) under thermolysis conditions. The free energies of species and transition states were obtained using the Born-Haber thermodynamic cycle and the SMD solvation model. The performance of several potential nitrosating agents including HONO, N2O3, and H2ONO+ are compared. These nitrosating agents would react with NH3OH+ to form NH3ONO+, or react with NH2OH to produce NH2ONO, HONHNO, and ONNH2O. The decomposition of NH2ONO starts from -NO migration to form ONNH2O, then transforms to HONHNO via fast acid-base equilibrium. The rate-determining steps for the global reaction are predicted to be the formation reactions of the nitrosating agents and the nitrosation steps.

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Zhang K, Thynell S. Ab initio investigation of the nitrosation reactions of hydroxylamine in aqueous solutions. 2017. Paper presented at 10th U.S. National Combustion Meeting, College Park, United States.