Gas phase reactions of HNO3 with Cl−, Cl−H2O, and Cl−HCl, of Cl2 with Cl−H2O and Cl−HCl, and of HCl with Cl−H2O

Amelynck, Crist; Arijs, E.; Schoon, Niels; Bavel, A.-M. Van

doi:10.1016/s1387-3806(98)14163-5

Cited by 8 publications

(6 citation statements)

References 14 publications

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“…Rather HNO 3 and HCl can be detected via Cl − transfer reactions from SO 2 Cl − , similarly to HONO. The reaction of HNO 3 with SO 2 Cl − is expected to yield ClHNO 3 − , as observed in laboratory studies on the reactions of HNO 3 with several ions containing Cl − . The production of ClHCl − by the Cl − transfer reaction from SO 2 Cl − to HCl has also been confirmed from experimental studies .…”

Section: Resultssupporting

confidence: 52%

In Situ Measurements of Atmospheric Nitrous Acid by Chemical Ionization Mass Spectrometry Using Chloride Ion Transfer Reactions

2009

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Recently, chemical ionization mass spectrometry (CIMS) has been widely applied to the in situ measurements of atmospheric trace species. In this article, we propose a new chemical ionization scheme using a chloride ion transfer reaction from SO(2)Cl(-) as the reagent ion and discuss the applicability of this technique to the detection of nitrous acid (HONO) in the atmosphere. From laboratory investigations, the detection sensitivity was found to depend on the flow rate of SO(2) introduced into the ion source region and the pressure inside the chemical ionization region, which suggests that the chemical ionization reaction is reversible. The detection sensitivity was well described in terms of the forward and backward rates. The present limit of detection is estimated to be 60 parts per trillion by volume (pptv) for an integration time of 1 min. Improvement of the CIMS instrument would enable the measurements of the daytime level of HONO, which might be less than 50 pptv. In addition, the possibility of the interference is discussed from thermodynamic considerations based on ab initio calculations, and the effects of the sampling artifacts are experimentally quantified.

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Section: Resultssupporting

confidence: 52%

In Situ Measurements of Atmospheric Nitrous Acid by Chemical Ionization Mass Spectrometry Using Chloride Ion Transfer Reactions

2009

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“…The ligand exchange reactions which contribute to their formation, [ m , n ] + HCl → [ m + 1, n − 1] + H 2 O, are indeed calculated to be slightly exothermic, as summarized in Table . Such a ligand exchange reaction of [0,1] forming [1,0] was previously observed in a flow-tube reactor mass spectrometer 2 Energy (in kJ/mol), Including Zero-Point Corrected (ZPC) Energies, Thermal Enthalpies (Δ H ), and Thermal Free Energies (Δ G ) at Ambient Conditions, of Ligand Exchange a energy of ligand exchange (kJ/mol) Cl - (HCl) m (H 2 O) n + HCl → Cl - (HCl) m +1 (H 2 O) n - 1 + H 2 OCl - (HCl) m (H 2 O) n Δ E + Δ ZPC Δ H 298K,1atm Δ G 298K,1atm m n calcdcalcdexptcalcdexpt 0 1 −49.5 −50.5 −23.0 −43.7 −19.1 1 1 −16.1 −16.6 −19.5 −16.1 −12.4 2 1 −14.8 −15.1 −13.6 3 1 −11.3 −11.6 −6.1 0 2 −40.2 −14.4 −41.7 −12.8 a The energies are calculated based on the binding energies listed in Table .…”

Section: Resultsmentioning

confidence: 99%

“…Such a ligand exchange reaction of [0,1] forming [1,0] was previously observed in a flow-tube reactor mass spectrometer. 79 In order to gain more insight into the final stage of the fragmentation, calculations for various structures of the [4,6] cluster have been performed (Table 3 and Supporting Information). This particular cluster size was chosen because it is the largest cluster that is treatable with the computing resources available to us and gives an idea about the structural motifs operative in the larger, saturated species.…”

Section: Resultsmentioning

confidence: 99%

Reactions of Large Water Cluster Anions with Hydrogen Chloride: Formation of Atomic Hydrogen and Phase Separation in the Gas Phase

et al. 2007

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The reactions of water cluster anions (H2O)n-, n = 30-70, with hydrogen chloride have been studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The first HCl taken up by the clusters is presumably ionically dissolved. The solvated electron recombines with the proton, which is thereby reduced to atomic hydrogen and evaporates from the cluster. This process is accompanied by blackbody radiation and collision induced loss of water molecules. Subsequent collisions lead to uptake of HCl and loss of H2O, yielding mixed clusters Cl-(HCl)m(H2O)n until they are saturated with HCl. Those saturated clusters lose H2O and HCl in a characteristic sequence. The final stage of the reaction, involving clusters with m = 0-4 and n = 0-6, is studied in detail with density functional theory calculations. The Cl-(HCl)4(H2O)6 cluster represents an example for supramolecular self-organization in the gas phase: it consists of a tetrahedral Cl-(HCl)4, connected on one side of the tetrahedron to a compact water hexamer.

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“…Measurement of the product ion is then used to quantify the abundance of the trace gas in the atmosphere. Reactions of many reagent ions with HNO 3 , HCl, and ClONO 2 , as well as other atmospheric trace gases, have been studied in the laboratory for the expressed purpose of using the reactions for atmospheric CIMS measurements [2][3][4][19][20][21][22][23]. In addition, several of these reactions have been used to make measurements of these three species in the atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Using chemical ionization mass spectrometry for detection of HNO3, HCl, and ClONO2 in the atmosphere

Marcy

Gao

Northway

et al. 2005

International Journal of Mass Spectrometry

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Gas phase reactions of HNO3 with Cl−, Cl−H2O, and Cl−HCl, of Cl2 with Cl−H2O and Cl−HCl, and of HCl with Cl−H2O

Cited by 8 publications

References 14 publications

In Situ Measurements of Atmospheric Nitrous Acid by Chemical Ionization Mass Spectrometry Using Chloride Ion Transfer Reactions

In Situ Measurements of Atmospheric Nitrous Acid by Chemical Ionization Mass Spectrometry Using Chloride Ion Transfer Reactions

Reactions of Large Water Cluster Anions with Hydrogen Chloride: Formation of Atomic Hydrogen and Phase Separation in the Gas Phase

Using chemical ionization mass spectrometry for detection of HNO3, HCl, and ClONO2 in the atmosphere

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