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Interactions of N2O5 and Related Nitrogen Oxides with Ice Surfaces: Desorption Kinetics and Collision Dynamics

Romero Lejonthun, Liza; Andersson, Patrik U; Hallquist, Mattias; Thomson, Erik S and Pettersson, Jan B. C. (2014) In The Journal of Physical Chemistry Part B 118(47). p.13427-13434
Abstract
The detailed interactions of nitrogen oxides with ice are of fundamental interest and relevance for chemistry in cold regions of the atmosphere. Here, the interactions of NO, NO2, N2O4, and N2O5 with ice surfaces at temperatures between 93 and 180 K are investigated with molecular beam techniques. Surface collisions are observed to result in efficient transfer of kinetic energy and trapping of molecules on the ice surfaces. NO and NO2 rapidly desorb from pure ice with upper bounds for the surface binding energies of 0.16 +/- 0.02 and 0.26 +/- 0.03 eV, respectively. Above 150 K, N2O4 desorption follows first-order kinetics and is well described by the Arrhenius parameters E-a = 0.39 +/- 0.04 eV and A = 10((15.41.2)) s(1), while a stable... (More)
The detailed interactions of nitrogen oxides with ice are of fundamental interest and relevance for chemistry in cold regions of the atmosphere. Here, the interactions of NO, NO2, N2O4, and N2O5 with ice surfaces at temperatures between 93 and 180 K are investigated with molecular beam techniques. Surface collisions are observed to result in efficient transfer of kinetic energy and trapping of molecules on the ice surfaces. NO and NO2 rapidly desorb from pure ice with upper bounds for the surface binding energies of 0.16 +/- 0.02 and 0.26 +/- 0.03 eV, respectively. Above 150 K, N2O4 desorption follows first-order kinetics and is well described by the Arrhenius parameters E-a = 0.39 +/- 0.04 eV and A = 10((15.41.2)) s(1), while a stable N2O4 adlayer is formed at lower temperatures. A fraction of incoming N2O5 reacts to form HNO3 on the ice surface. The N2O5 desorption rates are substantially lower on pure water ice (Arrhenius parameters: Ea = 0.36 +/- 0.02 eV; A = 10(15.3 +/- 0.7) s(-1)) than on HNO3-covered ice (Ea = 0.24 +/- 0.02 eV; A = 10(11.5 +/- 0.7) s(-1)). The N2O5 desorption kinetics also sensitively depend on the sub-monolayer coverage of HNO3, with a minimum in N2O5 desorption rate at a low but finite coverage of HNO3. The studies show that none of the systems with resolvable desorption kinetics undergo ordinary desorption from ice, and instead desorption likely involves two or more surface states, with additional complexity added by coadsorbed molecules. (Less)
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author
publishing date
type
Contribution to journal
publication status
published
subject
keywords
REACTIONS, VIBRATIONAL-EXCITATION, DINITROGEN TETROXIDE, OZONE, DEPLETION, ADSORPTION, TEMPERATURE, CRYSTALLINE, HETEROGENEOUS, MOLECULAR-BEAM, WATER-ICE, NITRIC-ACID TRIHYDRATE
in
The Journal of Physical Chemistry Part B
volume
118
issue
47
pages
13427 - 13434
publisher
The American Chemical Society
external identifiers
  • Scopus:84914163296
ISSN
1520-5207
DOI
10.1021/jp5053826
project
MERGE
language
English
LU publication?
no
id
fc3e519e-0364-48e6-b00f-e800e5423e49 (old id 7515532)
date added to LUP
2015-07-08 14:50:28
date last changed
2016-10-13 04:32:18
@misc{fc3e519e-0364-48e6-b00f-e800e5423e49,
  abstract     = {The detailed interactions of nitrogen oxides with ice are of fundamental interest and relevance for chemistry in cold regions of the atmosphere. Here, the interactions of NO, NO2, N2O4, and N2O5 with ice surfaces at temperatures between 93 and 180 K are investigated with molecular beam techniques. Surface collisions are observed to result in efficient transfer of kinetic energy and trapping of molecules on the ice surfaces. NO and NO2 rapidly desorb from pure ice with upper bounds for the surface binding energies of 0.16 +/- 0.02 and 0.26 +/- 0.03 eV, respectively. Above 150 K, N2O4 desorption follows first-order kinetics and is well described by the Arrhenius parameters E-a = 0.39 +/- 0.04 eV and A = 10((15.41.2)) s(1), while a stable N2O4 adlayer is formed at lower temperatures. A fraction of incoming N2O5 reacts to form HNO3 on the ice surface. The N2O5 desorption rates are substantially lower on pure water ice (Arrhenius parameters: Ea = 0.36 +/- 0.02 eV; A = 10(15.3 +/- 0.7) s(-1)) than on HNO3-covered ice (Ea = 0.24 +/- 0.02 eV; A = 10(11.5 +/- 0.7) s(-1)). The N2O5 desorption kinetics also sensitively depend on the sub-monolayer coverage of HNO3, with a minimum in N2O5 desorption rate at a low but finite coverage of HNO3. The studies show that none of the systems with resolvable desorption kinetics undergo ordinary desorption from ice, and instead desorption likely involves two or more surface states, with additional complexity added by coadsorbed molecules.},
  author       = {Romero Lejonthun, Liza and Andersson, Patrik U and Hallquist, Mattias and Thomson, Erik S and Pettersson, Jan B. C.},
  issn         = {1520-5207},
  keyword      = {REACTIONS,VIBRATIONAL-EXCITATION,DINITROGEN TETROXIDE,OZONE,DEPLETION,ADSORPTION,TEMPERATURE,CRYSTALLINE,HETEROGENEOUS,MOLECULAR-BEAM,WATER-ICE,NITRIC-ACID TRIHYDRATE},
  language     = {eng},
  number       = {47},
  pages        = {13427--13434},
  publisher    = {ARRAY(0xb9a9c88)},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Interactions of N2O5 and Related Nitrogen Oxides with Ice Surfaces: Desorption Kinetics and Collision Dynamics},
  url          = {http://dx.doi.org/10.1021/jp5053826},
  volume       = {118},
  year         = {2014},
}