Dimerization of nitrogen dioxide in solution: a comparison of solution thermodynamics with the gas phase

Redmond, Thomas F.; Wayland, Bradford B.

doi:10.1021/j100851a040

Cited by 59 publications

(18 citation statements)

References 2 publications

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“…and chloroform compares approximately with the values calculated by some previous authors [16][17][18]. The techniques usually applied were colorimetric and spectrophotometric ones.…”

Section: Carotenoids 70supporting

confidence: 77%

β‐Carotene and Free Radical Reactions with Nitrogen Oxides

Mendiara¹,

Perissinotti²

2017

Carotenoids

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The following presentation is based on experimental work we have already developed and published. We investigated the nitrogen oxides in different solvents and analyzed their reaction with β-carotene. The electron paramagnetic resonance spectroscopy (EPR) and ultraviolet and visible (UV-vis) spectroscopy were applied to investigate the reaction of β-carotene with nitrogen dioxide and nitric oxide in both pure dioxane and dioxane/ water solvent. Free radicals were detected and evaluated with the EPR technique, which is highly selective and sensitive. A reaction mechanism was proposed on the basis of the experimental kinetic and EPR results. The validity of the mechanism was checked by applying simulation set up conditions that reproduced the results achieved. The radical intermediates proposed in the reaction: the β-carotene neutral radicals and the cyclic nitroxide neutral radicals were theoretically studied. For that purpose, the density functional theory (DFT) level was applied, selecting the most suitable method, the unrestricted Becke-style 3-parameter with the Lee-Yang-Parr correlation functional (UB3LYP) and the 6-31G(d) basis sets (d orbital functions). We developed an appropriate discussion on the importance of carotenoids compounds and their reactions in biological media. Also, we evaluated the role and the possible reactions of nitroxide intermediates.

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“…and chloroform compares approximately with the values calculated by some previous authors [16][17][18]. The techniques usually applied were colorimetric and spectrophotometric ones.…”

Section: Carotenoids 70supporting

confidence: 77%

β‐Carotene and Free Radical Reactions with Nitrogen Oxides

Mendiara¹,

Perissinotti²

2017

Carotenoids

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“…Values of equilibrium constants in the gas phase as a function of temperature can be found in works of Verhoek and Daniels [9] or Chao et al [10]. James and Marshall [11] have determined equilibrium data for the liquid mixture and Redmond and Wayland [12] have been interested in equilibrium constant data for the nitrogen dioxide dissolved in organic solvents.…”

Section: Generalities On Cellulose Oxidation By Nitrogen Dioxidementioning

confidence: 99%

Oxidation of cellulose in pressurized carbon dioxide

Camy

Montanari²,

Rattaz

et al. 2009

The Journal of Supercritical Fluids

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“…92 The stability of the N 2 O 4 complexes with HNO 3 and NO 3 À predicted here suggests that the surface concentration of N 2 O 4 may also be larger than expected from the gas phase equilibrium. 21 The amount of the surface-bound dimer may be limited by the amount of available adsorbed HNO 3 and NO 3 À .…”

mentioning

confidence: 64%

Complexes of HNO3 and NO3− with NO2 and N2O4, and their potential role in atmospheric HONO formation

Kamboures

Raff

Miller

et al. 2008

Phys. Chem. Chem. Phys.

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Calculations were performed to determine the structures, energetics, and spectroscopy of the atmospherically relevant complexes (HNO 3 )Á(NO 2 ), (HNO 3 )Á(N 2 O 4 ), (NO 3 À )Á(NO 2 ), and (NO 3 À )Á(N 2 O 4 ). The binding energies indicate that three of the four complexes are quite stable, with the most stable (NO 3 À )Á(N 2 O 4 ) possessing binding energy of almost À14 kcal mol À1 . Vibrational frequencies were calculated for use in detecting the complexes by infrared and Raman spectroscopy. An ATR-FTIR experiment showed features at 1632 and 1602 cm À1 that are attributed to NO 2 complexed to NO 3 À and HNO 3 , respectively. The electronic states of (HNO 3 )Á (N 2 O 4 ) and (NO 3 À )Á(N 2 O 4 ) were investigated using an excited state method and it was determined that both complexes possess one low-lying excited state that is accessible through absorption of visible radiation. Evidence for the existence of (NO 3 À )Á(N 2 O 4 ) was obtained from UV/vis absorption spectra of N 2 O 4 in concentrated HNO 3 , which show a band at 320 nm that is blue shifted by 20 nm relative to what is observed for N 2 O 4 dissolved in organic solvents. Finally, hydrogen transfer reactions within the (HNO 3 )Á(NO 2 ) and (HNO 3 )Á(N 2 O 4 ) complexes leading to the formation of HONO, were investigated. In both systems the calculated potential profiles rule out a thermal mechanism, but indicate the reaction could take place following the absorption of visible radiation. We propose that these complexes are potentially important in the thermal and photochemical production of HONO observed in previous laboratory and field studies.

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Dimerization of nitrogen dioxide in solution: a comparison of solution thermodynamics with the gas phase

Cited by 59 publications

References 2 publications

β‐Carotene and Free Radical Reactions with Nitrogen Oxides

β‐Carotene and Free Radical Reactions with Nitrogen Oxides

Oxidation of cellulose in pressurized carbon dioxide

Complexes of HNO3 and NO3− with NO2 and N2O4, and their potential role in atmospheric HONO formation

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