Solvent Pressure Effects in Free Radical Reactions. 2. Reconciliation of the Gas and Condensed Phase Chlorination of Cyclopropane

1994 ◽  
Vol 116 (12) ◽  
pp. 5162-5166 ◽  
Author(s):  
James M. Tanko ◽  
N. Kamrudin Suleman
Keyword(s):  
Free Radical ◽  
Condensed Phase ◽  
Pressure Effects ◽  
Radical Reactions ◽  
Free Radical Reactions

Anisole nitration during gamma-irradiation of aqueous nitrite and nitrate solutions: free radical versus ionic mechanisms

2010 ◽  
Vol 7 (2) ◽  
pp. 183 ◽  
Author(s):  
Gracy Elias ◽  
Bruce J. Mincher ◽  
Stephen P. Mezyk ◽  
Thomas D. Cullen ◽  
Leigh R. Martin
Keyword(s):  
Free Radical ◽  
Water Treatment ◽  
Condensed Phase ◽  
Aromatic Compounds ◽  
Nitrous Acid ◽  
Radical Reactions ◽  
Electrophilic Aromatic Substitution ◽  
Aromatic Substitution ◽  
Beam Irradiation ◽  
Free Radical Reactions

Environmental context. The nitration of aromatic compounds is an important source of toxic, carcinogenic, and mutagenic species in the atmosphere. Gas phase nitration typically occurs by free radical reactions. Condensed-phase free radical reactions may also be relevant in fog and cloud water in polluted areas, in urban aerosols with low pH, in water treatment using advanced oxidation processes such as e-beam irradiation, and in nuclear waste treatment applications. This paper discusses research towards an improved understanding of nitration of aromatic compounds in the condensed phase under conditions conducive to free radical formation. Abstract. In the irradiated, acidic condensed phase, radiation-enhanced nitrous acid-catalysed, nitrosonium ion, electrophilic aromatic substitution followed by oxidation reactions dominated over radical addition reactions for anisole. This ionic mechanism would predominate in urban atmospheric aerosols and nuclear fuel dissolutions. Irradiated neutral nitrate anisole solutions were dominated by mixed nitrosonium/nitronium ion electrophilic aromatic substitution reactions, but with lower product yields. Solutions such as these might be encountered in water treatment by e-beam irradiation. Irradiation of neutral nitrite anisole solutions resulted in a statistical substitution pattern for nitroanisole products, suggesting non-electrophilic free radical reactions involving the •NO2 radical. Although often proposed as an atmospheric nitrating agent, NO2 radical is unlikely to have an important effect in the acidic condensed phase in the presence of more reactive, competing species such as nitrous acid.

Solvent pressure effects in free-radical reactions. A selectivity inversion in free-radical brominations induced by solvent

1993 ◽  
Vol 115 (11) ◽  
pp. 4520-4526 ◽  
Author(s):  
James M. Tanko ◽  
N. Kamrudin Suleman ◽  
Glenn A. Hulvey ◽  
Anna Park ◽  
Jennifer E. Powers
Keyword(s):  
Free Radical ◽  
Pressure Effects ◽  
Radical Reactions ◽  
Free Radical Reactions

ChemInform Abstract: Solvent Pressure Effects in Free Radical Reactions. A Selectivity Inversion in Free Radical Brominations Induced by Solvent

ChemInform ◽  
2010 ◽  
Vol 24 (41) ◽  
pp. no-no
Author(s):  
J. M. TANKO ◽  
N. K. SULEMAN ◽  
G. A. HULVEY ◽  
A. PARK ◽  
J. E. POWERS
Keyword(s):  
Free Radical ◽  
Pressure Effects ◽  
Radical Reactions ◽  
Free Radical Reactions

The initial reaction mechanism and thermal sensitivity of a fluoropolymer-containing energetic molecular system: the coupling effect of interfacial interactions and free radical reactions

CrystEngComm ◽  
2021 ◽  
Vol 23 (16) ◽  
pp. 3006-3014
Author(s):  
Wen Qian
Keyword(s):  
Free Radical ◽  
Coupling Effect ◽  
Molecular System ◽  
Thermal Sensitivity ◽  
Radical Reactions ◽  
Initial Reaction ◽  
Interfacial Interactions ◽  
Free Radical Reactions ◽  
Molecular Systems ◽  
Reactive Molecular Dynamics

A strategy combining classic and reactive molecular dynamics is applied to find the coupling effect of interfacial interactions and free radical reactions during the initial thermal decomposition of fluoropolymer-containing molecular systems.

Further studies on free-radical pathology in the major central nervous system disorders: effect of very high doses of methylprednisolone on the functional outcome, morphology, and chemistry of experimental spinal cord impact injury

1982 ◽  
Vol 60 (11) ◽  
pp. 1415-1424 ◽  
Author(s):  
H. B. Demopoulos ◽  
E. S. Flamm ◽  
M. L. Seligman ◽  
D. D. Pietronigro ◽  
J. Tomasula ◽  
...  
Keyword(s):  
Spinal Cord ◽  
Central Nervous System ◽  
Nervous System ◽  
Free Radical ◽  
Tissue Injury ◽  
Functional Restoration ◽  
Radical Reactions ◽  
Free Radical Reactions ◽  
Cord Injury

The hypothesis that pathologic free-radical reactions are initiated and catalyzed in the major central nervous system (CNS) disorders has been further supported by the current acute spinal cord injury work that has demonstrated the appearance of specific, cholesterol free-radical oxidation products. The significance of these products is suggested by the fact that: (i) they increase with time after injury; (ii) their production is curtailed with a steroidal antioxidant; (iii) high antioxidant doses of the steroidal antioxidant which curtail the development of free-radical product prevent tissue degeneration and permit functional restoration. The role of pathologic free-radical reactions is also inferred from the loss of ascorbic acid, a principal CNS antioxidant, and of extractable cholesterol. These losses are also prevented by the steroidal antioxidant. This model system is among others in the CNS which offer distinctive opportunities to study, in vivo, the onset and progression of membrane damaging free-radical reactions within well-defined parameters of time, extent of tissue injury, correlation with changes in membrane enzymes, and correlation with readily measurable in vivo functions.

Solvent Effects on the Oxidative Free Radical Reactions of 2-Amino-1,4-naphthoquinones.

ChemInform ◽  
2005 ◽  
Vol 36 (14) ◽  
Author(s):  
Chao-Ming Tseng ◽  
Yi-Lung Wu ◽  
Che-Ping Chuang
Keyword(s):  
Free Radical ◽  
Solvent Effects ◽  
Radical Reactions ◽  
Free Radical Reactions

Simulation of dioxygen free radical reactions

1993 ◽  
Vol 21 (3) ◽  
pp. 256S-256S ◽  
Author(s):  
PEDRO MONIZ-BARRETO ◽  
DAVID A. FELL
Keyword(s):  
Free Radical ◽  
Radical Reactions ◽  
Free Radical Reactions
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