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Title: Kinetics and mechanisms of the oxidation of hydrazinium ion (N{sub 2}H{sub 5}{sup +}) by aqueous Br{sub 2}, Cl{sub 2}, and BrCl. Electrophilicity scale for halogens and interhalogens

Abstract

Very rapid oxidations of N{sub 2}H{sub 5}{sup +} by Br{sub 2}, Cl{sub 2}, and BrCl are measured by stopped-flow and pulsed-accelerated-flow methods in acidic solutions with excess N{sub 2}H{sub 5}{sup +}. Second-order rate constants (M{sup {minus}1} s{sup {minus}1}) at 25.0 C, {mu} = 1.0 M are 1.49 x 10{sup 7}, 1.01 x 10{sup 8}, and 5.6 x 10{sup 8} for the reactions with Br{sub 2}, Cl{sub 2}, and BrCl, respectively. The reactions are postulated to proceed by nucleophilic reaction of N{sub 2}H{sub 5}{sup +} with XY electrophiles (XY = Br{sub 2}, Cl{sub 2}, BrCl) to form XN{sub 2}H{sub 4}{sup +} with Y{sup {minus}} and H{sup +} rapidly to form N{sub 2}H{sub 3}{sup +} and diazine, N{sub 2}H{sub 2}, which is oxidized by a second Br{sub 2}, Cl{sub 2}, or BrCl to form N{sub 2} in fast steps. The stoichiometries are measured and confirmed to be 1:2 for the Cl{sub 2} and BrCl reactions. The relative reactivities for the oxidation of N{sub 2}H{sub 5}{sup +} by halogens and interhalogens (BrCl > Cl{sub 2} > Br{sub 2} > ICl << IBr << I{sub 2}) are used to establish an electrophilicity scale (E{sub XY}) for this type of reaction in aqueous solution.

Authors:
; ;
Publication Date:
Research Org.:
Purdue Univ., West Lafayette, IN (US)
OSTI Identifier:
20075881
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 9; Other Information: PBD: 1 May 2000; Journal ID: ISSN 0020-1669
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; CHEMICAL REACTION KINETICS; OXIDATION; HYDRAZINE; HALOGENS; BROMINE CHLORIDES; REDUCING AGENTS; EXPLOSIVES; FEEDWATER; WATER CHEMISTRY

Citation Formats

Jia, Z., Salaita, M.G., and Margerum, D.W. Kinetics and mechanisms of the oxidation of hydrazinium ion (N{sub 2}H{sub 5}{sup +}) by aqueous Br{sub 2}, Cl{sub 2}, and BrCl. Electrophilicity scale for halogens and interhalogens. United States: N. p., 2000. Web. doi:10.1021/ic991220k.
Jia, Z., Salaita, M.G., & Margerum, D.W. Kinetics and mechanisms of the oxidation of hydrazinium ion (N{sub 2}H{sub 5}{sup +}) by aqueous Br{sub 2}, Cl{sub 2}, and BrCl. Electrophilicity scale for halogens and interhalogens. United States. doi:10.1021/ic991220k.
Jia, Z., Salaita, M.G., and Margerum, D.W. Mon . "Kinetics and mechanisms of the oxidation of hydrazinium ion (N{sub 2}H{sub 5}{sup +}) by aqueous Br{sub 2}, Cl{sub 2}, and BrCl. Electrophilicity scale for halogens and interhalogens". United States. doi:10.1021/ic991220k.
@article{osti_20075881,
title = {Kinetics and mechanisms of the oxidation of hydrazinium ion (N{sub 2}H{sub 5}{sup +}) by aqueous Br{sub 2}, Cl{sub 2}, and BrCl. Electrophilicity scale for halogens and interhalogens},
author = {Jia, Z. and Salaita, M.G. and Margerum, D.W.},
abstractNote = {Very rapid oxidations of N{sub 2}H{sub 5}{sup +} by Br{sub 2}, Cl{sub 2}, and BrCl are measured by stopped-flow and pulsed-accelerated-flow methods in acidic solutions with excess N{sub 2}H{sub 5}{sup +}. Second-order rate constants (M{sup {minus}1} s{sup {minus}1}) at 25.0 C, {mu} = 1.0 M are 1.49 x 10{sup 7}, 1.01 x 10{sup 8}, and 5.6 x 10{sup 8} for the reactions with Br{sub 2}, Cl{sub 2}, and BrCl, respectively. The reactions are postulated to proceed by nucleophilic reaction of N{sub 2}H{sub 5}{sup +} with XY electrophiles (XY = Br{sub 2}, Cl{sub 2}, BrCl) to form XN{sub 2}H{sub 4}{sup +} with Y{sup {minus}} and H{sup +} rapidly to form N{sub 2}H{sub 3}{sup +} and diazine, N{sub 2}H{sub 2}, which is oxidized by a second Br{sub 2}, Cl{sub 2}, or BrCl to form N{sub 2} in fast steps. The stoichiometries are measured and confirmed to be 1:2 for the Cl{sub 2} and BrCl reactions. The relative reactivities for the oxidation of N{sub 2}H{sub 5}{sup +} by halogens and interhalogens (BrCl > Cl{sub 2} > Br{sub 2} > ICl << IBr << I{sub 2}) are used to establish an electrophilicity scale (E{sub XY}) for this type of reaction in aqueous solution.},
doi = {10.1021/ic991220k},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 9,
volume = 39,
place = {United States},
year = {2000},
month = {5}
}