Infrared Spectroscopic Investigation of the Heterogeneous Reaction of HNO<sub>3</sub> and NaCl(100)

Sporleder, David; Ewing, George E.

doi:10.1021/jp0034729

Cited by 25 publications

(34 citation statements)

References 32 publications

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“…A sample of condensed-phase nitric acid was prepared by applying a droplet of nitric acid to the Teflon filter. The observed vibration peaks between 860 and 900 cm −1 of nitric acid ( Figure 1b) were consistent with reported peak assignments (McGraw et al 1965;Maki and Wells 1992;Sporleder and Ewing 2001). These peaks differ significantly from the 849 cm −1 peak of ON groups and were not observed in SOA samples, suggesting that nitric acid, a terminal sink of NO x , was either not present in the particle phase or below DL of the FTIR analysis (the DL of HNO 3 is not quantified, but is estimated at 0.01 µg m −3 based on the DL of ON groups).…”

Section: Identification and Quantification Of On Groupssupporting

confidence: 90%

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Liu

Shilling

Song

et al. 2012

Aerosol Science and Technology

183

204

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Organonitrate (ON) groups are thought to be important substituents in secondary organic aerosols (SOAs). Model simulations and laboratory studies indicate a large fraction of ON groups in aerosol particles, but much lower quantities are observed in the atmosphere. Hydrolysis of ON groups in aerosol particles has been proposed recently to account for this discrepancy. To test this hypothesis, we simulated formation of ON molecules in a reaction chamber under a wide range of relative humidity (RH) (0 to 90%). The mass fraction of ON groups (5 to 20% for high-NO x experiments) consistently decreased with increasing RH, which was best explained by hydrolysis of ON groups at a rate of 4 day −1 (lifetime of 6 h) for reactions under RH greater than 20%. In addition, we found that secondary nitrogen-containing molecules absorb light, with greater absorption under dry and high-NO x conditions. This work provides the first evidence for particle-phase hydrolysis of ON groups, a process that could substantially reduce ON group concentration in atmospheric SOAs.

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Section: Identification and Quantification Of On Groupssupporting

confidence: 90%

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Liu

Shilling

Song

et al. 2012

Aerosol Science and Technology

183

204

View full text Add to dashboard Cite

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“…83 Additional bands due to O-H stretches of HNO 3 Á(H 2 O) n (n = 1-3) complexes were also observed in the present study between 2400 and 3200 cm À1 (not shown), similar to what was observed previously. 22 The presence of nitrate and nitric acid-water complexes suggests that residual water remains on the surface of the IRE, despite efforts to remove it under vacuum.…”

Section: Atr-ftir Investigation Of Hno 3 -No X Surface Filmssupporting

confidence: 92%

Complexes of HNO3 and NO3− with NO2 and N2O4, and their potential role in atmospheric HONO formation

Kamboures

Raff

Miller

et al. 2008

Phys. Chem. Chem. Phys.

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Calculations were performed to determine the structures, energetics, and spectroscopy of the atmospherically relevant complexes (HNO 3 )Á(NO 2 ), (HNO 3 )Á(N 2 O 4 ), (NO 3 À )Á(NO 2 ), and (NO 3 À )Á(N 2 O 4 ). The binding energies indicate that three of the four complexes are quite stable, with the most stable (NO 3 À )Á(N 2 O 4 ) possessing binding energy of almost À14 kcal mol À1 . Vibrational frequencies were calculated for use in detecting the complexes by infrared and Raman spectroscopy. An ATR-FTIR experiment showed features at 1632 and 1602 cm À1 that are attributed to NO 2 complexed to NO 3 À and HNO 3 , respectively. The electronic states of (HNO 3 )Á (N 2 O 4 ) and (NO 3 À )Á(N 2 O 4 ) were investigated using an excited state method and it was determined that both complexes possess one low-lying excited state that is accessible through absorption of visible radiation. Evidence for the existence of (NO 3 À )Á(N 2 O 4 ) was obtained from UV/vis absorption spectra of N 2 O 4 in concentrated HNO 3 , which show a band at 320 nm that is blue shifted by 20 nm relative to what is observed for N 2 O 4 dissolved in organic solvents. Finally, hydrogen transfer reactions within the (HNO 3 )Á(NO 2 ) and (HNO 3 )Á(N 2 O 4 ) complexes leading to the formation of HONO, were investigated. In both systems the calculated potential profiles rule out a thermal mechanism, but indicate the reaction could take place following the absorption of visible radiation. We propose that these complexes are potentially important in the thermal and photochemical production of HONO observed in previous laboratory and field studies.

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“…Longitudinal-transverse ͑LO-TO͒ splitting was reported by Fox and Hexter, 23 according to which the crystal shape can lower the overall environmental symmetry and lift the degeneracies of infrared models. When a NaNO 3 crystal appears as a thin plate, a single feature from the bulk crystal may be split, 24 as observed by Devlin et al for a thin crystalline plate of NaNO 3 on substrate. 25 In this work, the solid samples were obtained by drying the NaNO 3 droplets on the ZnSe substrate, and therefore thin plates may form and give rise to the splitting of the 3 -NO 3 − band.…”

Section: Ftir-atr Spectra Features and Phase Transitions Of Nano 3 Pamentioning

confidence: 72%

Molecular events in deliquescence and efflorescence phase transitions of sodium nitrate particles studied by Fourier transform infrared attenuated total reflection spectroscopy

Wang

Zhao

et al. 2008

The Journal of Chemical Physics

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The NaNO(3) droplets with sizes of 1-5 microm generated from a nebulizer were deposited on a ZnSe substrate in a Fourier transform infrared attenuated total reflection (FTIR-ATR) chamber. After solidification of the droplets with dry N(2) gas passing through the chamber, the solid NaNO(3) particles were monitored by in situ FTIR-ATR spectra in cycles of deliquescence and efflorescence processes with varying relative humidities (RHs). With an increase in the RH, a dominant peak at approximately 3539 cm(-1), together with three relatively weak peaks at approximately 3400, approximately 3272, and approximately 3167 cm(-1), in the O-H stretching band of water was resolved by the high signal-to-noise ratio FTIR-ATR spectra. The dominant peak and the three relatively weak peaks were contributed by the water monomers and the aggregated water molecules adsorbed on the surfaces of solid NaNO(3) particles, respectively. When the RH approached approximately 72%, slightly lower than the deliquescence RH (74.5%), the band component at approximately 3400 cm(-1) became the main peak, indicating that the water monomers and the aggregated water molecules aggregated to form a thin water layer on the surfaces of solid NaNO(3) particles. A splitting of the nu(3)-NO(3)(-) band at 1363 and 1390 cm(-1) at the RH of approximately 72%, instead of the single nu(3)-NO(3)(-) band at 1357 cm(-1) for the initial solid NaNO(3), was observed. We suggested that this reflected a phase transition from the initial solid to a metastable solid phase of NaNO(3). The metastable solid phase deliquesced completely in the region from approximately 87% to approximately 96% RH according to the fact that the nu(3)-NO(3)(-) band showed two overlapping peaks at 1348 and 1405 cm(-1) similar to those of bulk NaNO(3) solutions. In the efflorescence process of the NaNO(3) droplets, the nu(1)-NO(3)(-) band presented a continuous blueshift from 1049 cm(-1) at approximately 77% RH to 1055 cm(-1) at approximately 36% RH, indicating the formation of contact ion pairs between Na(+) and NO(3)(-). Moreover, in the RH range from approximately 53% down to approximately 26%, two peaks at 836 and 829 cm(-1) were observed in the nu(2)-NO(3)(-) band region, demonstrating the coexistence of NaNO(3) solid particles and droplets.

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Infrared Spectroscopic Investigation of the Heterogeneous Reaction of HNO₃ and NaCl(100)

Cited by 25 publications

References 32 publications

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Complexes of HNO3 and NO3− with NO2 and N2O4, and their potential role in atmospheric HONO formation

Molecular events in deliquescence and efflorescence phase transitions of sodium nitrate particles studied by Fourier transform infrared attenuated total reflection spectroscopy

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Infrared Spectroscopic Investigation of the Heterogeneous Reaction of HNO3 and NaCl(100)

Cited by 25 publications

References 32 publications

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Hydrolysis of Organonitrate Functional Groups in Aerosol Particles

Complexes of HNO3 and NO3− with NO2 and N2O4, and their potential role in atmospheric HONO formation

Molecular events in deliquescence and efflorescence phase transitions of sodium nitrate particles studied by Fourier transform infrared attenuated total reflection spectroscopy

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Infrared Spectroscopic Investigation of the Heterogeneous Reaction of HNO₃ and NaCl(100)