Simulated kinetics of the atmospheric removal of aniline during daytime

Abdel-Rahman, Mohamed A.; Shibl, Mohamed F.; El‐Demerdash, Safinaz H.; El‐Nahas, Ahmed M.

doi:10.1016/j.chemosphere.2020.127031

Cited by 24 publications

(33 citation statements)

References 40 publications

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“…The present findings indicated that molecular modelling is an important tool for elucidating several parameters to fulfil the experimental findings. This is in good agreement with those obtained previously [24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40].…”

Section: Discussionsupporting

confidence: 93%

ICMMS-2: Metal−organic Frameworks for Hydrogen Storage: Theoretical Prospective

et al. 2021

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The adsorption of H2 in dehydrated and hydrated Materials of Institute Lavoisier (MIL-101) was investigated theoretically. The effect of terminal water molecules on adsorption as one of the more vital MIL-n trivalent chromium-based porous carboxylates in metal-organic frameworks application in the renewable energy field was also theoretically studied. The MIL-101 structures were optimized for geometry and energy minimization was performed. The calculations were carried out using density functional theory approach with B3LYP functional and mixed basis set of Lanl2DZ and 6-31G(d, p) for Cr and light atoms (C, H, O, F), respectively, as implemented in the Gaussian 09 program package. The spin and atomic charges distribution on the Cr metal atoms, adsorbate, and water molecules are calculated using natural bond orbital (NBO). The density of states (DOS) for the clusters was obtained using Gaussian smearing of Kohn-Sham orbital energies. The natural bond orbital (NBO) for molecular orbital analysis and atomic charge calculations were utilized. For the dehydrated MIL-101, more adsorbate molecules were found near the exposed Cr2 sites than the fluorine saturated Cr1 sites. Furthermore, terminal water molecules in the hydrated MIL-101 made more interaction sites and enhanced adsorption.

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Section: Discussionsupporting

confidence: 93%

ICMMS-2: Metal−organic Frameworks for Hydrogen Storage: Theoretical Prospective

et al. 2021

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Section: Introductionmentioning

confidence: 99%

“…In the atmosphere, the gas - phase OH-initiated reaction is of paramount importance for the primary fate of aniline since OH is one of the most reactive radicals relevant to the removal process of various volatile organic compounds from the tropospheric zone and is also commonly available in the atmosphere in abundance (i.e., [OH] ∼ 2 × 10 6 molecule/cm 3 ) . There are several laboratory − and theoretical studies on the atmospheric oxidation of aniline by OH radicals. The bimolecular rate constant for the removal of aniline using OH radicals was relatively fast, ∼1.2 × 10 –10 cm 3 /molecule/s under the ambient conditions measured by Rinke et al, Witte et al, and Atkinson et al Recently, Abdel-Rahman et al computationally investigated the oxidation mechanism of aniline initiated by OH radicals and the subsequent reactions in the presence of O 2 /NO, contributing substantially to the comprehensive insights into the mechanism of the title reaction.…”

Section: Introductionmentioning

confidence: 99%

“…There are several laboratory − and theoretical studies on the atmospheric oxidation of aniline by OH radicals. The bimolecular rate constant for the removal of aniline using OH radicals was relatively fast, ∼1.2 × 10 –10 cm 3 /molecule/s under the ambient conditions measured by Rinke et al, Witte et al, and Atkinson et al Recently, Abdel-Rahman et al computationally investigated the oxidation mechanism of aniline initiated by OH radicals and the subsequent reactions in the presence of O 2 /NO, contributing substantially to the comprehensive insights into the mechanism of the title reaction. Using the transition state theory (TST), canonical variational transition state theory, and RRKM-based master equation models based on the ROCBS-QB3 energies, the authors reported a global rate constant under atmospheric conditions for the reaction between aniline and OH radicals of 4.4 × 10 –10 cm 3 /molecule/s, ∼4 times higher than the experimental values. − Also, they pointed out that the OH-addition channel on the C atoms at ortho sites of the −NH 2 functional group is more kinetically favorable than the H-abstraction one from the −NH 2 group with branching ratios of 92.9 and 4.9%, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…For the reasons mentioned above, we reinvestigated the detailed kinetic mechanism of the oxidation of aniline by OH radicals to (i) resolve the disagreement between the recent theoretical and experimental − works and (ii) reveal its complex kinetic behaviors (e.g., the branching fractions of the formed intermediates/products) with the aim to comprehensively understand the risk concerns of the atmospheric degradation of aniline. To this end, the title reaction is studied using the density functional theory (DFT) calculations along with the meticulous stochastic statistical rate model within the RRKM-based master equation (RRKM-ME) scheme for a wide array of conditions ( T = 200–2000 K and P = 0.76–7600 Torr) relevant to various applications in atmospheric and even in combustion chemistry.…”

Section: Introductionmentioning

confidence: 99%

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New Mechanistic Insights into Atmospheric Oxidation of Aniline Initiated by OH Radicals

V.‐T.

Nguyen

et al. 2021

Environ. Sci. Technol.

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This study theoretically reports the comprehensive kinetic mechanism of the aniline + OH reaction in the range of 200–2000 K and 0.76–7600 Torr. The temperature- and pressure-dependent behaviors, including time-resolved species profiles and rate coefficients, were studied within the stochastic RRKM-based master equation framework with the reaction energy profile, together with molecular properties of the species involved, characterized at the M06-2X/aug-cc-pVTZ level. Hindered internal rotation and Eckart tunneling treatments were included. The H-abstraction from the −NH2 moiety (to form C6H5NH (P1)) is found to prevail over the OH-addition on the C atom at the ortho site of aniline (to form 6-hydroxy-1-methylcyclohexa-2,4-dien-1-yl (I2)) with the atmospheric rate expressions (in cm3/molecule/s) as k abstraction(P1) = 3.41 × 101 × T –4.56 × exp (−255.2 K/T) for 200–2000 K and k addition(I2) = 3.68 × 109 × T –7.39 × exp (−1163.9 K/T) for 200–800 K. The U-shaped temperature-dependent characteristics and weakly positive pressure dependence at low temperatures (e.g., T ≤ 800 K and P = 760 Torr) of k total(T) are also observed. The disagreement in k total(T) between the previous calculations and experimental studies is also resolved, and atmospheric aniline is found to be primarily removed by OH radicals (τOH ∼ 1.1 h) in the daytime. Also, via TD-DFT simulations, it is recommended to include P1 and I2 in any atmospheric photolysis-related model.

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Pervaporation recovery of aniline using the degradable material poly(butylene adipate‐terephthalate): Experiment and molecular simulation

Wang,

Xu,

et al. 2024

Polymer Engineering & Sci

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Pervaporation has been considered a promising technique in the recovery of organic matter in low concentrations. Developing new and efficient pervaporation membrane materials remains the main challenge. In this study, the biodegradable poly (butylene adipate‐terephthalate) (PBAT) membrane was used to recover aniline by pervaporation for the first time. The PBAT membrane showed a good pervaporation performance due to its unique affinity with aniline by the surface adsorption energy calculations. When the aniline concentration in the feed solution was 0.4 wt%, the separation factor of the PBAT membrane exceeded 80. Besides, the results showed that the flux rose with the aniline concentration increasing, which was because of the incremental free volume of PBAT membrane. Moreover, the H‐bond length between aniline and PBAT (1.947 Å) was shorter than that between water and PBAT (2.091 Å) according to the density functional theory (DFT) calculations, which could account for the low diffusion coefficient of aniline from the result of molecular dynamics (MD) simulations. In addition, PBAT membranes displayed excellent stability in pervaporation experiments of more than 80 h. It is anticipated that the PBAT membrane may have great potential in pervaporation recovery of valuable chemicals from dilute aqueous solutions.Highlights Biodegradable PBAT membrane was first used to recover aniline by pervaporation. Low diffusion coefficient of aniline was further explained combining MD and DFT. The PBAT membranes exhibited excellent performance for aniline recovery.

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Simulated kinetics of the atmospheric removal of aniline during daytime

Cited by 24 publications

References 40 publications

ICMMS-2: Metal−organic Frameworks for Hydrogen Storage: Theoretical Prospective

ICMMS-2: Metal−organic Frameworks for Hydrogen Storage: Theoretical Prospective

New Mechanistic Insights into Atmospheric Oxidation of Aniline Initiated by OH Radicals

Pervaporation recovery of aniline using the degradable material poly(butylene adipate‐terephthalate): Experiment and molecular simulation

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