ChemInform Abstract: Proton Affinity of Methyl Nitrate: Less than Proton Affinity of Nitric Acid.

ChemInform ◽  
2010 ◽  
Vol 24 (5) ◽  
pp. no-no
Author(s):  
T. J. LEE ◽  
J. E. RICE
Keyword(s):  
Nitric Acid ◽  
Proton Affinity ◽  
Methyl Nitrate

Is the Proton Affinity of Nitric Acid Larger Than the Proton Affinity of Methyl Nitrate? A Direct Experimental Answer

1994 ◽  
Vol 116 (14) ◽  
pp. 6413-6417 ◽  
Author(s):  
Fulvio Cacace ◽  
Marina Attina ◽  
Giulia de Petris ◽  
Maurizio Speranza
Keyword(s):  
Nitric Acid ◽  
Proton Affinity ◽  
Methyl Nitrate

Proton affinity of methyl nitrate: less than proton affinity of nitric acid

1992 ◽  
Vol 114 (21) ◽  
pp. 8247-8256 ◽  
Author(s):  
Timothy J. Lee ◽  
Julia E. Rice
Keyword(s):  
Nitric Acid ◽  
Proton Affinity ◽  
Methyl Nitrate

Basicity and acidity promote hydrolysis of methyl nitrate in aqueous aerosols

2020 ◽  
Author(s):  
Fatemeh Keshavarz ◽  
Theo Kurtén ◽  
Hanna Vehkamäki
Keyword(s):  
Nitric Acid ◽  
Nitrous Acid ◽  
Rate Coefficients ◽  
Alkyl Nitrates ◽  
Hydronium Ions ◽  
Hydroxyl Ion ◽  
Solvent Model ◽  
Methyl Nitrate ◽  
Hydrolysis Of ◽  
Aqueous Aerosols

<p>The chemistry of organic nitrates (ONs), also known as alkyl nitrates (RONO<sub>2</sub>), controls the lifetime of nitrogen oxides in continental areas, which in turn affects air quality and varies ozone concentration throughout the troposphere. ONs can be emitted to the troposphere from marine sources. Also, they can be produced in the atmosphere through addition of NO to peroxy radicals or through the reaction of NO<sub>3</sub> radicals with volatile organic compounds. Atmospheric ONs may subsequently undergo oxidation or photolysis, in both gas and aerosol phases, or hydrolysis in aqueous aerosols. Though some recent studies have believed acid-catalysis promotes hydrolysis of ONs, earlier studies have claimed that acids have no effect on ON hydrolysis, and that it is the hydroxyl ion that can improve the hydrolysis process. The limited number of experimental studies performed so far have left this conflict with no appropriate answer, as mechanistic insight and full kinetics details have been partially or completely missing for the studied ONs. We report the detailed mechanism of methyl nitrate hydrolysis in acidic, neutral and basic conditions, in addition to analyzing the degradation of methyl nitrate into formaldehyde and nitrous acid in the presence of water and hydronium ions. According to the potential energy surfaces obtained at the CCSD(T)/cc-pVDZ//ωB97X-D/def2-TZVP level of theory (including the SMD solvent model) along with the rate coefficients estimated using asymmetric Eckart tunneling-corrected transition state theory (TST), mediation of water molecules and hydronium ions hinders degradation of methyl nitrate into formaldehyde and nitrous acid and, in general, this decomposition reaction is kinetically unfavorable. Furthermore, neutral hydrolysis of methyl nitrate is extremely slow with pseudo-first order rate coefficients (k; 298 K and 1 atm) falling below 10<sup>-27</sup> s<sup>-1</sup>. Similarly, hydrolysis of methyl nitrate by hydronium ions is observed to be extremely slow (k < 10<sup>-27</sup> s<sup>-1</sup>). However, under acidic conditions, protonation of methyl nitrate is quite feasible with the protonation Gibbs free energy of -429.1 kJ mol<sup>-1</sup>, at 298 K and 1 atm, and protonated methyl nitrate can hydrolyze into protonated methanol and nitric acid much faster relative to the hydronium ion-based and neutral hydrolysis (k = 3.83 s<sup>-1</sup>). On the other hand, the hydroxyl ions generated under basic conditions can hydrolyze methyl nitrate readily to give methanol and nitric acid (k = 6.63 × 10<sup>3</sup> s<sup>-1</sup>), or formaldehyde, nitrate and water (k = 9.40 × 10<sup>6</sup> s<sup>-1</sup>). In addition, regardless of the limitation on the rate of solvent-phase chemical reactions by the rate of diffusion, basic hydrolysis can produce methoxy ions and nitric acid quite fast (k = 8.95 × 10<sup>9</sup> s<sup>-1</sup>). In other words, methyl nitrate hydrolysis is faster in basic aerosols (i.e. some marine aerosols) and, to a less extent, in highly acidic aqueous aerosols (e.g. haze and urban aerosols).       </p>

Gas-Phase Proton Affinity of Nitric Acid and Its Esters. A Mass Spectrometric and ab Initio Study on the Existence and the Relative Stability of Two Isomers of Protonated Ethyl Nitrate

1996 ◽  
Vol 100 (41) ◽  
pp. 16522-16529 ◽  
Author(s):  
Massimiliano Aschi ◽  
Fulvio Cacace ◽  
Giulia de Petris ◽  
Federico Pepi
Keyword(s):  
Nitric Acid ◽  
Ab Initio ◽  
Gas Phase ◽  
Proton Affinity ◽  
Relative Stability ◽  
Mass Spectrometric ◽  
Ab Initio Study

Temperature-dependent absorption cross-sections of gaseous nitric acid and methyl nitrate

1992 ◽  
Vol 66 (3) ◽  
pp. 313-326 ◽  
Author(s):  
O. Rattigan ◽  
E. Lutman ◽  
R.L. Jones ◽  
R.A. Cox ◽  
K. Clemitshaw ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Cross Sections ◽  
Absorption Cross ◽  
Temperature Dependent ◽  
Dependent Absorption ◽  
Methyl Nitrate

scholarly journals Blast Wave Parameters of Liquid Esters of Nitric Acid: Propane-1,2,3-triyl trinitrate, Propane-1,2-diyl Dinitrate, Ethane-1,2-diyl Dinitrate and Methyl Nitrate

2017 ◽  
Vol 14 (2) ◽  
pp. 375-390 ◽  
Author(s):  
Jiri Pachman ◽  
Jakub Selesovsky ◽  
Martin Künzel ◽  
Robert Matyas ◽  
Karel Kubat ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Blast Wave ◽  
Wave Parameters ◽  
Methyl Nitrate

Concerning the proton affinity of hydrazoic acid and methyl nitrate

1993 ◽  
Vol 58 (14) ◽  
pp. 3639-3642 ◽  
Author(s):  
Fulvio Cacace ◽  
Marina Attina ◽  
Maurizio Speranza ◽  
Giulia de Petris ◽  
Felice Grandinetti
Keyword(s):  
Proton Affinity ◽  
Hydrazoic Acid ◽  
Methyl Nitrate

The proton affinity of methyl nitrate

1994 ◽  
Vol 29 (1) ◽  
pp. 55-56 ◽  
Author(s):  
Andreina Ricci
Keyword(s):  
Proton Affinity ◽  
Methyl Nitrate

Temperature-dependent absorption cross-sections of gaseous nitric acid and methyl nitrate

1992 ◽  
Vol 69 (1) ◽  
pp. 125-126 ◽  
Author(s):  
O. Rattigan ◽  
E. Lutman ◽  
R.L. Jones ◽  
R.A. Cox ◽  
K. Clemitshaw ◽  
...  
Keyword(s):  
Nitric Acid ◽  
Cross Sections ◽  
Absorption Cross ◽  
Temperature Dependent ◽  
Dependent Absorption ◽  
Methyl Nitrate
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