Reaction of chloride ions with chlorine nitrate and its implications for stratospheric chemistry

Journal Article · Thu Jul 07 00:00:00 EDT 1994 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100078a015· OSTI ID:7204009

Haas, B M; Crellin, K C; Kuwata, K T; Okumura, Mitchio ^[1]

---

1. California Inst. of Technology, Pasadena, CA (United States)

We present experimental and theoretical evidence for the rapid gas-phase reaction of Cl[sup [minus]] with ClONO[sub 2] to form Cl[sub 2] and NO[sub 3][sup [minus]]. The reaction was studied in a Fourier-transform ion-cyclotron-resonance mass spectrometer, and a reaction rate constant of k = (9.2 [+-] 3.0) x 10[sup [minus]10] cm[sup 3] s[sup [minus]1] molecule[sup [minus]1] at 298 K was determined. This value was [approx] 60% of the rate constant estimated from ion-dipole collision theory. We also performed ab initio calculations at the level of second-order Moller-Plesset perturbation theory using diffuse basis sets and at the singles-and-doubles coupled cluster level to examine portions of the potential energy surface for this reaction. We found no barrier for reaction for the approach of Cl[sup [minus]] toward the Cl atom on ClONO[sub 2], but we found a minimum along the reaction coordinate corresponding to an ion-molecule complex Cl[sub 2][center dot]NO[sub 3][sup [minus]]. The reaction enthalpy remains exothermic with the inclusion of ion hydration enthalpies, indicating that the reaction could proceed in condensed-phase water. These considerations suggest that chloride ions may react directly with ClONO[sub 2] on water ice films and type II polar stratospheric cloud particles. 51 refs., 4 figs., 1 tab.

• OSTI ID: 7204009
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 98:27; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

54 ENVIRONMENTAL SCIENCES
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CHEMICAL REACTIONS
REACTION KINETICS
CHLORIDES
CHLORINE NITRATES
ATMOSPHERIC CHEMISTRY
CLOUDS
ENTHALPY
HYDRATION
ICE
IONS
MASS SPECTROSCOPY
STRATOSPHERE
CHARGED PARTICLES
CHEMISTRY
CHLORINE COMPOUNDS
EARTH ATMOSPHERE
HALIDES
HALOGEN COMPOUNDS
KINETICS
NITRATES
NITROGEN COMPOUNDS
OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
SOLVATION
SPECTROSCOPY
THERMODYNAMIC PROPERTIES
540110*
540120 - Environment
Atmospheric- Chemicals Monitoring & Transport- (1990-)
400201 - Chemical & Physicochemical Properties
400102 - Chemical & Spectral Procedures