Theoretical study of the gaseous hydrolysis of NO2 in the presence of NH3 as a source of atmospheric HONO

2016 ◽  
Vol 13 (4) ◽  
pp. 611 ◽  
Author(s):  
Xu Wang ◽  
Feng-Yang Bai ◽  
Yan-Qiu Sun ◽  
Rong-Shun Wang ◽  
Xiu-Mei Pan ◽  
...  
Keyword(s):  
Nitrogen Dioxide ◽  
Nitrous Acid ◽  
Energy Barrier ◽  
Theoretical Calculations ◽  
Hydrolysis Reaction ◽  
Phase Reaction ◽  
Chemical Mechanisms ◽  
Decomposition Processes ◽  
Additional Water ◽  
Hydrolysis Of

Environmental context Nitrous acid is an important atmospheric trace gas, but the sources and the chemical mechanisms of its production are not well understood. This study explores the effects of ammonia and water on the hydrolysis of nitrogen dioxide and nitrous acid production. The calculated results show that ammonia is more effective than water in promoting the hydrolysis reaction of nitrogen dioxide. Abstract The effects of ammonia and water molecules on the hydrolysis of nitrogen dioxide as well as product accumulation are investigated by theoretical calculations of three series of the molecular clusters 2NO2–mH2O (m=1–3), 2NO2–mH2O–NH3 (m=1, 2) and 2NO2–mH2O–2NH3 (m=1, 2). The gas-phase reaction 2NO2 + H2O → HONO + HNO3 is thermodynamically unfavourable. The additional water or ammonia in the clusters can not only stabilise the products by forming stable complexes, but also reduce the energy barrier for the reaction. There is a considerable energy barrier for the reaction at the reactant cluster 2NO2–H2O: 11.7kcalmol–1 (1kcalmol–1=4.18kJmol–1). With ammonia and an additional water in the cluster, 2NO2–H2O–NH3, the thermodynamically stable products t-HONO + NH4NO3–H2O can be formed without an energy barrier. With two ammonia molecules, as in the cluster 2NO2–mH2O–2NH3 (m=1, 2), the reaction is barrierless and the product complex NH4NO2–NH4NO3 is further stabilised. The present study, including natural bond orbital analysis on a series of species, shows that ammonia is more effective than water in promoting the hydrolysis reaction of NO2. The product cluster NH4NO2–NH4NO3 resembles an alternating layered structure containing the ion units NH4+NO2– and NH4+NO3–. The decomposition processes of NH4NO2–NH4NO3 and its monohydrate are all spontaneous and endothermic.

Hydrolysis Reaction and Amorphization of Ce–Ti Oxide Catalysts During Synthesis

2021 ◽  
Vol 21 (9) ◽  
pp. 4931-4935
Author(s):  
Joo-Yeon Ha ◽  
Min-Seo Kim ◽  
Tae-Woo Kim ◽  
Ji-Seung Ryu ◽  
Hyun-Gyoo Shin ◽  
...  
Keyword(s):  
Solvent Mixture ◽  
Hydrolysis Reaction ◽  
Anhydrous Ethanol ◽  
Phase Reaction ◽  
X Ray Diffraction ◽  
Atomic Concentration ◽  
Electron Microscopic ◽  
Transmission Electron ◽  
Hydrolysis Of ◽  
Water Contents

The change in the crystallinity of Ce–Ti oxide nanocatalysts with different water contents was investigated in terms of the local atomic structure and the surface atomic concentration. The crystallization of TiO2, which was induced by the hydrolysis of the Ti precursor, was observed in the catalyst synthesized via a liquid phase reaction employing a mixture of ethanol and distilled water as the solvent. The hydrolysis reaction of the Ti precursor was impeded in the solvent mixture of ethanol and anhydrous ethanol. CeO2 nanocrystallization occurred due to the suppression of the TiO2 crystal growth. Low crystallinity of the catalyst synthesized in a single anhydrous ethanol solvent was observed through the broadened X-ray diffraction (XRD) peak and the diffused ring pattern in transmission electron microscopic (TEM) images. In addition, the Ce–O and Ce–Ce bond lengths of the catalyst synthesized using the single solvent decreased beyond those of the catalysts synthesized in the mixed solvent, indicating the amorphization of the catalyst. It was also verified that the inhibition of the precursor crystallization during the synthesis led to the enhanced dispersion of the nanocatalyst, compared to the stoichiometry of the surface atomic concentration.

Theoretical insight into the role of urea in the hydrolysis reaction of NO2 as a source of HONO and aerosols

2018 ◽  
Vol 15 (6) ◽  
pp. 372 ◽  
Author(s):  
Shuang Lv ◽  
Feng-Yang Bai ◽  
Xiu-Mei Pan ◽  
Liang Zhao
Keyword(s):  
Nitric Acid ◽  
Energy Barrier ◽  
Computational Study ◽  
Theoretical Calculations ◽  
Nbo Analysis ◽  
Hydrolysis Reaction ◽  
Hydrogen Bond Interaction ◽  
Distribution Maps ◽  
Urea Nitrate

Environmental contextUrea is an important component of dissolved organic nitrogen in rainfall and aerosols, but the sources and the mechanisms of its production are not well understood. This computational study explores the effects of urea and water on the hydrolysis of NO2 and urea nitrate production. The results will aid our interpretation of the role of urea in the formation of atmospheric secondary nitrogen contaminants and aerosols. AbstractThe effects of urea on the hydrolysis reaction 2NO2 + mH2O (m = 1–3) have been investigated by theoretical calculations. The energy barrier (−2.67 kcal mol−1) of the urea-promoted reaction is lower than the naked reaction by 14.37 kcal mol−1. Urea also has a better catalytic effect on the reaction than methylamine and ammonia. Urea acts as a catalyst and proton transfer medium in this process, and the produced HONO may serve as a source of atmospheric nitrous acid. In addition, the subsequent reactions include clusters of nitrite, urea, and nitric acid. Then urea nitrate (UN), which is a typical HNO3 aerosol, can be formed in the subsequent reactions. The production of the acid-base complex (UN-2) is more favourable with an energy barrier of 0.10 kcal mol−1, which is 3.88 kcal mol−1 lower than that of the zwitterions NH2CONH3+NO3− (UN-1). The formation of zwitterions and the hydrolysis reaction are affected by humidity. The multi water-promoted hydrolysis reactions exhibit better thermodynamic stability when the humidity is increased. The extra water molecules act as solvent molecules to reduce the energy barrier. The natural bond orbital (NBO) analysis is employed to describe the donor-acceptor interactions of the complexes. The hydrogen bond interaction between the urea carbonyl and nitric acid of UN-2 is the strongest. The potential distribution maps of the urea nitrate and hydrate are examined, and the result shows that they tend to form zwitterions.

DFT study on the hydrolysis of metsulfuron-methyl: A sulfonylurea herbicide

2018 ◽  
Vol 17 (08) ◽  
pp. 1850050 ◽  
Author(s):  
Qiuhan Luo ◽  
Gang Li ◽  
Junping Xiao ◽  
Chunhui Yin ◽  
Yahui He ◽  
...  
Keyword(s):  
Free Energy ◽  
Water Molecule ◽  
Carbonyl Group ◽  
Energy Barrier ◽  
Density Functional ◽  
Free Energy Barrier ◽  
Functional Theory ◽  
Metsulfuron Methyl ◽  
Catalytic Role ◽  
Hydrolysis Of

Sulfonylureas are an important group of herbicides widely used for a range of weeds and grasses control particularly in cereals. However, some of them tend to persist for years in environments. Hydrolysis is the primary pathway for their degradation. To understand the hydrolysis behavior of sulfonylurea herbicides, the hydrolysis mechanism of metsulfuron-methyl, a typical sulfonylurea, was investigated using density functional theory (DFT) at the B3LYP/6-31[Formula: see text]G(d,p) level. The hydrolysis of metsulfuron-methyl resembles nucleophilic substitution by a water molecule attacking the carbonyl group from aryl side (pathway a) or from heterocycle side (pathway b). In the direct hydrolysis, the carbonyl group is directly attacked by one water molecule to form benzene sulfonamide or heterocyclic amine; the free energy barrier is about 52–58[Formula: see text]kcal[Formula: see text]mol[Formula: see text]. In the autocatalytic hydrolysis, with the second water molecule acting as a catalyst, the free energy barrier, which is about 43–45[Formula: see text]kcal[Formula: see text]mol[Formula: see text], is remarkably reduced by about 11[Formula: see text]kcal[Formula: see text]mol[Formula: see text]. It is obvious that water molecules play a significant catalytic role during the hydrolysis of sulfonylureas.

scholarly journals Insights on forming N,O-coordinated Cu single-atom catalysts for electrochemical reduction CO2 to methane

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yanming Cai ◽  
Jiaju Fu ◽  
Yang Zhou ◽  
Yu-Chung Chang ◽  
Qianhao Min ◽  
...  
Keyword(s):  
Energy Barrier ◽  
Active Sites ◽  
Theoretical Calculations ◽  
High Energy ◽  
Single Atom ◽  
Faradaic Efficiency ◽  
High Energy Barrier ◽  
Catalytic Sites ◽  
Electron Reduction ◽  
First Time

AbstractSingle-atom catalysts (SACs) are promising candidates to catalyze electrochemical CO2 reduction (ECR) due to maximized atomic utilization. However, products are usually limited to CO instead of hydrocarbons or oxygenates due to unfavorable high energy barrier for further electron transfer on synthesized single atom catalytic sites. Here we report a novel partial-carbonization strategy to modify the electronic structures of center atoms on SACs for lowering the overall endothermic energy of key intermediates. A carbon-dots-based SAC margined with unique CuN2O2 sites was synthesized for the first time. The introduction of oxygen ligands brings remarkably high Faradaic efficiency (78%) and selectivity (99% of ECR products) for electrochemical converting CO2 to CH4 with current density of 40 mA·cm-2 in aqueous electrolytes, surpassing most reported SACs which stop at two-electron reduction. Theoretical calculations further revealed that the high selectivity and activity on CuN2O2 active sites are due to the proper elevated CH4 and H2 energy barrier and fine-tuned electronic structure of Cu active sites.

scholarly journals Improvements in the profiles and distributions of nitric acid and nitrogen dioxide with the LIMS version 6 dataset

2010 ◽  
Vol 10 (10) ◽  
pp. 4741-4756 ◽  
Author(s):  
E. Remsberg ◽  
M. Natarajan ◽  
B. T. Marshall ◽  
L. L. Gordley ◽  
R. E. Thompson ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Nitrogen Dioxide ◽  
Theoretical Calculations ◽  
Spin Splitting ◽  
Oxides Of Nitrogen ◽  
Polar Night ◽  
Chemical Effects ◽  
Satellite Sensors ◽  
Precision And Accuracy

Abstract. The quality of the Nimbus 7 Limb Infrared Monitor of the Stratosphere (LIMS) nitric acid (HNO3) and nitrogen dioxide (NO2) profiles and distributions of 1978/1979 are described after their processing with an updated, Version 6 (V6) algorithm and subsequent archival in 2002. Estimates of the precision and accuracy of both of those species are developed and provided herein. The character of the V6 HNO3 profiles is relatively unchanged from that of the earlier LIMS Version 5 (V5) profiles, except in the upper stratosphere where the interfering effects of CO2 are accounted for better with V6. The accuracy of the retrieved V6 NO2 is also significantly better in the middle and upper stratosphere, due to improvements in its spectral line parameters and in the reduced biases for the accompanying V6 temperature and water vapor profiles. As a result of these important updates, there is better agreement with theoretical calculations for profiles of the HNO3/NO2 ratio, day-to-night NO2 ratio, and with estimates of the production of NO2 in the mesosphere and its descent to the upper stratosphere during polar night. In particular, the findings for middle and upper stratospheric NO2 should also be more compatible with those obtained from more recent satellite sensors because the effects of the spin-splitting of the NO2 lines are accounted for now with the LIMS V6 algorithm. The improved precisions and more frequent retrievals of the LIMS profiles along their orbit tracks provide for better continuity and detail in map analyses of these two species on pressure surfaces. It is judged that the chemical effects of the oxides of nitrogen on ozone can be studied quantitatively throughout the stratosphere with the LIMS V6 data.

Nitrous acid production and uptake by Zea mays plants in growth chambers in the presence of nitrogen dioxide

2021 ◽  
pp. 150696
Author(s):  
Aurélie Marion ◽  
Julien Morin ◽  
Elena Ormeno ◽  
Sylvie Dupouyet ◽  
Barbara D'Anna ◽  
...  
Keyword(s):  
Zea Mays ◽  
Nitrogen Dioxide ◽  
Nitrous Acid ◽  
Acid Production ◽  
Growth Chambers

scholarly journals A broadband cavity enhanced absorption spectrometer for aircraft measurements of glyoxal, methylglyoxal, nitrous acid, nitrogen dioxide, and water vapor

2016 ◽  
Vol 9 (2) ◽  
pp. 423-440 ◽  
Author(s):  
K.-E. Min ◽  
R. A. Washenfelder ◽  
W. P. Dubé ◽  
A. O. Langford ◽  
P. M. Edwards ◽  
...  
Keyword(s):  
Nitrogen Dioxide ◽  
Cross Sections ◽  
Nitrous Acid ◽  
Aircraft Measurements ◽  
Charge Coupled Device ◽  
Light Emitting ◽  
Enhanced Absorption ◽  
Field Campaigns ◽  
A Charge ◽  
Absorption Spectrometer

Abstract. We describe a two-channel broadband cavity enhanced absorption spectrometer (BBCEAS) for aircraft measurements of glyoxal (CHOCHO), methylglyoxal (CH3COCHO), nitrous acid (HONO), nitrogen dioxide (NO2), and water (H2O). The instrument spans 361–389 and 438–468 nm, using two light-emitting diodes (LEDs) and a single grating spectrometer with a charge-coupled device (CCD) detector. Robust performance is achieved using a custom optical mounting system, high-power LEDs with electronic on/off modulation, high-reflectivity cavity mirrors, and materials that minimize analyte surface losses. We have successfully deployed this instrument during two aircraft and two ground-based field campaigns to date. The demonstrated precision (2σ) for retrievals of CHOCHO, HONO and NO2 are 34, 350, and 80 parts per trillion (pptv) in 5 s. The accuracy is 5.8, 9.0, and 5.0 %, limited mainly by the available absorption cross sections.

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