Kinetics and mechanism of X + ClNO yields XCl + NO (X = Cl, F, Br, OH, O, N) from 220 to 450 K. Correlation of reactivity and activation energy with electron affinity of X

Abbatt, J P.D.; Toohey, D W; Fenter, F F; Stevens, P S; Brune, W H; Anderson, J G

doi:10.1021/j100340a004

Title: Kinetics and mechanism of X + ClNO yields XCl + NO (X = Cl, F, Br, OH, O, N) from 220 to 450 K. Correlation of reactivity and activation energy with electron affinity of X

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Abstract

The rate constants for a series of radical reactions with ClNO, X + ClNO {yields} products where X = Cl, F, Br, OH, O, N, have been measured as a function of temperature in discharge flow systems at pressures between 1 and 2 Torr of helium buffer gas. Radicals were detected by resonance fluorescence (X = Cl, Br, OH, O), laser magnetic resonance (X = OH), and chemical conversion/resonance fluorescence (X = F, N). The rate constants, with units of cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} and to 95% confidence level, are for Cl + ClNO {yields} Cl{sub 2} + NO, ((6.6 {plus minus} 1.2) {times} 10{sup {minus}11}) e{sup (128{plus minus}46)/T}; for F + ClNO {yields} FCl + NO, ((1.4 {plus minus} 0.4) {times} 10{sup {minus}10}) e{sup ({minus}28{plus minus}84)/T}; for Br + ClNO {yields} BrCl + NO, ((1.5 {plus minus} 0.2) {times} 10{sup {minus}11}) e{sup ({minus}52{plus minus}43)/T}; for OH + ClNO {yields} ClOH + NO, ((9.0 {plus minus} 4.5) {times} 10{sup {minus}12}) e{sup ({minus}1130{plus minus}170)/T}; for OH + ClNO {yields} HONO + Cl, ((9.2 {plus minus} 6.5) {times} 10{sup {minus}14}) e{sup (240{plus minus}130)/T}; for O + ClNO {yields} ClO + NO, ((8.3 {plus minus} 0.9) {times} 10{sup {minus}12}) e{sup ({minus}1520{plusmore »« less

Authors:

Abbatt, J P.D.; Toohey, D W; Fenter, F F; Stevens, P S; Brune, W H; Anderson, J G ^[1]

Harvard Univ., Cambridge, MA (USA)

Publication Date:: Thu Feb 09 00:00:00 EST 1989

OSTI Identifier:: 5144232

Resource Type:: Journal Article

Journal Name:: Journal of Physical Chemistry; (USA)

Additional Journal Information:: Journal Volume: 93:3; Journal ID: ISSN 0022-3654

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 54 ENVIRONMENTAL SCIENCES; BROMINE; CHEMICAL REACTIONS; CHLORINE; FLUORINE; HYDROXY COMPOUNDS; NITROGEN; NITROGEN COMPOUNDS; OXYCHLORIDES; OXYGEN; ACTIVATION ENERGY; AFFINITY; EXPERIMENTAL DATA; HIGH TEMPERATURE; MEDIUM TEMPERATURE; CHLORINE COMPOUNDS; DATA; ELEMENTS; ENERGY; HALOGEN COMPOUNDS; HALOGENS; INFORMATION; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; OXYGEN COMPOUNDS; OXYHALIDES; 400201* - Chemical & Physicochemical Properties; 540110

Citation Formats


                    Abbatt, J P.D., Toohey, D W, Fenter, F F, Stevens, P S, Brune, W H, and Anderson, J G. Kinetics and mechanism of X + ClNO yields XCl + NO (X = Cl, F, Br, OH, O, N) from 220 to 450 K. Correlation of reactivity and activation energy with electron affinity of X.  United States: N. p., 1989. 
        Web.  doi:10.1021/j100340a004.

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                    Abbatt, J P.D., Toohey, D W, Fenter, F F, Stevens, P S, Brune, W H, & Anderson, J G. Kinetics and mechanism of X + ClNO yields XCl + NO (X = Cl, F, Br, OH, O, N) from 220 to 450 K. Correlation of reactivity and activation energy with electron affinity of X.  United States.  https://doi.org/10.1021/j100340a004

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                    Abbatt, J P.D., Toohey, D W, Fenter, F F, Stevens, P S, Brune, W H, and Anderson, J G. 1989.  
        "Kinetics and mechanism of X + ClNO yields XCl + NO (X = Cl, F, Br, OH, O, N) from 220 to 450 K. Correlation of reactivity and activation energy with electron affinity of X".  United States.  https://doi.org/10.1021/j100340a004.

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@article{osti_5144232,

  title        = {Kinetics and mechanism of X + ClNO yields XCl + NO (X = Cl, F, Br, OH, O, N) from 220 to 450 K. Correlation of reactivity and activation energy with electron affinity of X},

  author       = {Abbatt, J P.D. and Toohey, D W and Fenter, F F and Stevens, P S and Brune, W H and Anderson, J G},

  abstractNote = {The rate constants for a series of radical reactions with ClNO, X + ClNO {yields} products where X = Cl, F, Br, OH, O, N, have been measured as a function of temperature in discharge flow systems at pressures between 1 and 2 Torr of helium buffer gas. Radicals were detected by resonance fluorescence (X = Cl, Br, OH, O), laser magnetic resonance (X = OH), and chemical conversion/resonance fluorescence (X = F, N). The rate constants, with units of cm{sup 3} molecule{sup {minus}1} s{sup {minus}1} and to 95% confidence level, are for Cl + ClNO {yields} Cl{sub 2} + NO, ((6.6 {plus minus} 1.2) {times} 10{sup {minus}11}) e{sup (128{plus minus}46)/T}; for F + ClNO {yields} FCl + NO, ((1.4 {plus minus} 0.4) {times} 10{sup {minus}10}) e{sup ({minus}28{plus minus}84)/T}; for Br + ClNO {yields} BrCl + NO, ((1.5 {plus minus} 0.2) {times} 10{sup {minus}11}) e{sup ({minus}52{plus minus}43)/T}; for OH + ClNO {yields} ClOH + NO, ((9.0 {plus minus} 4.5) {times} 10{sup {minus}12}) e{sup ({minus}1130{plus minus}170)/T}; for OH + ClNO {yields} HONO + Cl, ((9.2 {plus minus} 6.5) {times} 10{sup {minus}14}) e{sup (240{plus minus}130)/T}; for O + ClNO {yields} ClO + NO, ((8.3 {plus minus} 0.9) {times} 10{sup {minus}12}) e{sup ({minus}1520{plus minus}35)/T}; and for N + ClNO {yields} NCl + NO, ((9.2 {plus minus} 2.2) {times} 10{sup {minus}12}) e{sup ({minus}2250{plus minus}90)/T}. Both the reaction activation energies and the logarithms of the room temperature rate constants are found to correlate strongly with the electron affinity of the radical in such a way that high electron affinity leads to enhanced reactivity. The reactivity trend is rationalized by a frontier orbital interaction dominated by the ease with which electron transfer from the ClNO molecule to the X radical can occur to stabilize a polar transition state, a mechanism shown to be widely prevalent in radical-molecule systems.},

  doi          = {10.1021/j100340a004},

  url          = {https://www.osti.gov/biblio/5144232},
  journal      = {Journal of Physical Chemistry; (USA)},

  issn         = {0022-3654},

  number       = ,

  volume       = 93:3,

  place        = {United States},

  year         = {Thu Feb 09 00:00:00 EST 1989},

  month        = {Thu Feb 09 00:00:00 EST 1989}

}

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