Aldehyde as a potential source of aminol in troposphere: Influence of water and formic acid catalysis on ammonolysis of formaldehyde

Sarkar, Saptarshi; Monu,; Bandyopadhyay, Biman

doi:10.1016/j.atmosenv.2019.05.069

Cited by 24 publications

(15 citation statements)

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“…They undergo gas-phase reactions in the atmosphere with the hydroxyl radical OH, ozone O 3 , or nitrogen oxides NO x . , They lead to the formation of oxygenated products that are less volatile than the parent hydrocarbons and hence act as precursors of secondary organic aerosols (SOAs). − The first oxidation products are mostly aldehydes, ketones, and carboxylic acids. The amount of production of VOCs and SOAs depends on several parameters such as temperature, humidity, and luminosity. , The sequences of reactions conducting to highly oxidized products are far from being understood and could be influenced by hydration. − The present work aims at filling the gap between first and end products. It deals with the spectroscopic characterization of hydrates of S -(−)-perillaldehyde (C 10 H 14 O, 4-isopropenylcyclohex-1-ene-1-carbaldehyde).…”

Section: Introductionmentioning

confidence: 99%

Gas-Phase Hydration of Perillaldehyde Investigated by Microwave Spectroscopy Assisted by Computational Chemistry

2020

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The microsolvated complexes of two equatorial conformers of perillaldehyde were experimentally investigated in a supersonic molecular jet coupled to a cavity-based Fourier transform microwave spectrometer, in the 2.3–8 GHz frequency range. The structures of hydrates C10H14O·(H2O) n (n = 1,2,3) were first optimized at the MP2/6-311++G(d,p) and B3LYP-D3BJ/def2-TZVP levels of theory. The spectral signatures of four monohydrates and of two dihydrates could then be obtained. Additional rotational constants from the analysis of the spectra of their 18O isotopologues allowed the calculation of the substitution coordinates of the water oxygen atoms of each hydrate. They were found to be in good agreement with those of the optimized structures. SAPT2 calculations and noncovalent interaction analysis highlight the role of dispersion and quasi-hydrogen bonds in the stabilization of the structures.

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Section: Introductionmentioning

confidence: 99%

Gas-Phase Hydration of Perillaldehyde Investigated by Microwave Spectroscopy Assisted by Computational Chemistry

2020

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“…To get the suited basis set, single‐point energy calculations for the stationary points of CF 2 O + H 2 O were performed with CCSD(T) method with three different basis sets (6–311++G(3 df ,3 dp ), cc‐pVTZ and CBS), based on the optimized geometries at the M06‐2X/6–311++G(3 df ,3 pd ) level (see in Table 1). It is worth noting that the CCSD(T)/CBS to get high accurate energy calculation is well‐defined [37,43,48]. The obtained results show that the cc‐pVTZ basis set is reliable for the calculation of the hydrolysis reaction of CF 2 O.…”

Section: Resultsmentioning

confidence: 99%

“…1). It is worth noting that the CCSD(T)/CBS to get high accurate energy calculation is well-defined [37,43,48].…”

Section: Resultsmentioning

confidence: 99%

“…Thus, the overall rate expression was given including both rate coefficient and concentration terms. Relative rate is considered to be a very reliable method to compare the efficiency of various catalysts on the specific reaction [33,35,48,[51][52][53]. The relative rate expression for the X catalyzed hydrolysis process is given by the following equation…”

Section: Base Catalyzedmentioning

confidence: 99%

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The catalytic effects of H₂O, basic and acidic catalysts on the gas‐phase hydrolysis mechanism of carbonyl fluoride (CF₂O)

Zhang

Lily

et al. 2021

Int J of Quantum Chemistry

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The carbonyl fluoride (CF 2 O) is one of the significant atmospheric molecules, and its hydrolysis reaction has been considered the most potential removal process in the earth's troposphere. In this article, the hydrolysis reaction of CF 2 O assisted by H 2 O, basic (NH 3 and CH 3 NHCH 3 ), and acidic (H 2 SO 4 , HCOOH, and CF 3 COOH) catalysts have theoretically investigated using quantum chemical methods. These catalysts significantly decrease the hydrolysis reaction of barrier height by 20.4-28.8 kcal mol −1 .Here two H-transfer mechanisms have been identified in these catalyzed hydrolytic reactions as asynchronous collaborative caused by base molecules and the synchronous collaborative led by H 2 O and acid molecules. In addition, the rate coefficient and relative rate of all catalytic reactions have calculated using conventional transition state theory (TST) over a temperature range of 280-320 K. The results show that H 2 SO 4 has the best catalytic effect without considering the concentration of catalyst molecules in the atmosphere. On the contrary, a high concentration of HCOOH (10 ppbv) is dominant in the catalytic reaction when considered the concentrations of catalyst molecules. In this work, it was identified that the catalytic efficiencies of H 2 O, acid and base molecules upon addition reaction between CF 2 O and H 2 O is not only related to their catalytic mechanisms but also depending upon their concentrations in the atmosphere.

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“…Recently, a number of studies suggested that along with hydrolysis the ammonolysis process also plays a crucial role in the atmospheric loss processes of atmospherically important molecules. ,− Moreover, recently, we have shown that, like the hydrolysis process, the ammonolysis of SO 3 also plays an important role in the atmospheric acid formation . The hydrolysis and ammonolysis of SO 3 produce H 2 SO 4 and HSO 3 NH 2 , respectively.…”

Section: Introductionmentioning

confidence: 95%

Reaction between N₂O₅ and NH₃ under Tropospheric Conditions: A Quantum Chemical and Chemical Kinetic Investigation

Sarkar

Bandyopadhyay

2020

J. Phys. Chem. A

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The gas-phase reaction of N 2 O 5 with NH 3 under tropospheric conditions has been carried out employing quantum chemical calculations at the CCSD(T)/CBS//MP2/aug-cc-pVTZ level of theory. The activation barrier of the reaction was found to be 13.5 kcal mol −1 with respect to isolated reactants. Chemical kinetic calculations were carried out under pre-equilibrium approximation using transition-state theory employing Eckart tunneling, and the rate coefficient was found to be 1.02 × 10 −24 cm 3 molecule −1 s −1 at 298 K. To check the reliability of the result, calculations have also been carried out using the canonical variational transition-state theory employing both zero-and small-curvature tunneling as well as the master equation. The results obtained from these methods were found to be consistent with those obtained from the transition-state theory. The rate coefficient was found to show positive temperature dependence, and its rate of change with temperature was found to be very similar for all three methods. Further, the pressure dependence of the rate coefficient has been checked and it was found that it shows negligible pressure dependence under tropospheric conditions. Besides, all of the electronic structure calculations have been carried out at the CCSD(T)-F12/cc-pVTZ// M06-2X/aug-cc-pVTZ level of theory and the rate coefficients using all of the above-mentioned kinetic models have been computed using these results. The results were found to match closely with the CCSD(T)//CBS//MP2/aug-cc-pVTZ results.

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Aldehyde as a potential source of aminol in troposphere: Influence of water and formic acid catalysis on ammonolysis of formaldehyde

Cited by 24 publications

References 52 publications

Gas-Phase Hydration of Perillaldehyde Investigated by Microwave Spectroscopy Assisted by Computational Chemistry

Gas-Phase Hydration of Perillaldehyde Investigated by Microwave Spectroscopy Assisted by Computational Chemistry

The catalytic effects of H₂O, basic and acidic catalysts on the gas‐phase hydrolysis mechanism of carbonyl fluoride (CF₂O)

Reaction between N₂O₅ and NH₃ under Tropospheric Conditions: A Quantum Chemical and Chemical Kinetic Investigation

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Aldehyde as a potential source of aminol in troposphere: Influence of water and formic acid catalysis on ammonolysis of formaldehyde

Cited by 24 publications

References 52 publications

Gas-Phase Hydration of Perillaldehyde Investigated by Microwave Spectroscopy Assisted by Computational Chemistry

Gas-Phase Hydration of Perillaldehyde Investigated by Microwave Spectroscopy Assisted by Computational Chemistry

The catalytic effects of H2O, basic and acidic catalysts on the gas‐phase hydrolysis mechanism of carbonyl fluoride (CF2O)

Reaction between N2O5 and NH3 under Tropospheric Conditions: A Quantum Chemical and Chemical Kinetic Investigation

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The catalytic effects of H₂O, basic and acidic catalysts on the gas‐phase hydrolysis mechanism of carbonyl fluoride (CF₂O)

Reaction between N₂O₅ and NH₃ under Tropospheric Conditions: A Quantum Chemical and Chemical Kinetic Investigation