Computational Study of the Thermochemistry of N₂O₅ and the Kinetics of the Reaction N₂O₅ + H₂O → 2 HNO₃

Abstract

The multistructural method for torsional anharmonicity (MS-T) is employed to compute anharmonic conformationally averaged partition functions which then serve as the basis for the calculation of thermochemical parameters for N 2 O 5 over the temperature range 0−3000 K, and thermal rate constants for the hydrolysis reaction N 2 O 5 + H 2 O → 2 HNO 3 over the temperature range 180−1800 K. The M06-2X hybrid meta-GGA density functional paired with the MG3S basis set is used to compute the properties of all stationary points and the energies, gradients, and Hessians of nonstationary points along the reaction path, with further energy refinement at stationary points obtained via single-point CCSD(T)-F12a/cc-pVTZ-F12 calculations including corrections for core−valence and scalar relativistic effects. The internal rotations in dinitrogen pentoxide are found to generate three structures (conformations) whose contributions are included in the partition function via the MS-T formalism, leading to a computed value for

1,2‐Dimethoxyethane Degradation Thermodynamics in Li−O2 Redox Environments

“…A strong mitigation of the reactivity of ethers may be obtained by reducing the mean acidity of the hydrogen atoms in the solvent molecule or by innovative molecular design inspired by our general reaction mechanism. References are cited in the Supporting Information.…”

“…The herein-reported analysis of the fundamental degradation thermodynamicso fD ME, besidesd rawing for the first time ag eneral rationale for the comprehension of the parasitic processes in aL i ÀO 2 cell, can also pave the way fort he development of improved electrolyte solvents. As trong mitigation of the reactivity of ethers may be obtained by reducing the mean acidity of the hydrogen atoms in the solventm olecule or by innovative molecular designi nspired by our general reaction mechanism.R eferences [68]- [74] are cited in the Supporting Information.…”

Decomposition Pathways for Aqueous Hydroxylammonium Nitrate Solutions: a DFT Study

“…The same type of reaction in the gas phase was theoretically investigated previously [29]. We examined this self-decomposition reaction and the subsequent processes and Figure 8 depicts the potential energy profile and optimized structures.…”

The Role of Clouds in the Tropospheric NOx Cycle: A New Modeling Approach for Cloud Chemistry and Its Global Implications

“…Our result of 27% falls in the middle of this range. Homogeneous hydrolysis of N 2 O 5 is neglected in many models, because its rate and importance remain unclear (Alecu & Marshall, 2014;Atkinson et al, 2015;Brown & Stutz, 2012;Brown et al, 2009;Crowley, Schuster, et al, 2010), but the reaction has a meaningful impact on tropospheric O 3 when it is included in box models (Emmerson & Evans, 2009). Contrary to the box model results, tests in our global model using the upper limit rate from IUPAC (Atkinson et al, 2015) find that homogeneous hydrolysis supplies less than 2% of global HNO 3 production (0.1 Tmol N/year) and changes mean tropospheric O 3 and OH by under 0.5% each.…”