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

Kaiqiang Zhang; Stefan T. Thynell

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

Kaiqiang Zhang, Stefan T. Thynell

Research output: Contribution to conference › Paper › peer-review

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 language	English (US)
State	Published - 2017
Event	10th U.S. National Combustion Meeting - College Park, United States Duration: Apr 23 2017 → Apr 26 2017

Other

Other	10th U.S. National Combustion Meeting
Country/Territory	United States
City	College Park
Period	4/23/17 → 4/26/17

All Science Journal Classification (ASJC) codes

General Chemical Engineering
Physical and Theoretical Chemistry
Mechanical Engineering

Cite this

@conference{32c3babb3093483f84ce7c08458d41d2,

title = "Ab initio investigation of the nitrosation reactions of hydroxylamine in aqueous solutions",

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.",

author = "Kaiqiang Zhang and Thynell, {Stefan T.}",

note = "Funding Information: The authors acknowledge the support from the Air Force Office of Scientific Research under grant number FA9550-13-1-0004.; 10th U.S. National Combustion Meeting ; Conference date: 23-04-2017 Through 26-04-2017",

year = "2017",

language = "English (US)",

}

TY - CONF

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

AU - Zhang, Kaiqiang

AU - Thynell, Stefan T.

N1 - Funding Information: The authors acknowledge the support from the Air Force Office of Scientific Research under grant number FA9550-13-1-0004.

PY - 2017

Y1 - 2017

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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UR - http://www.scopus.com/inward/citedby.url?scp=85049005051&partnerID=8YFLogxK

M3 - Paper

AN - SCOPUS:85049005051

T2 - 10th U.S. National Combustion Meeting

Y2 - 23 April 2017 through 26 April 2017

ER -

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

Abstract

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All Science Journal Classification (ASJC) codes

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