Many, if not most, redox reactions are coupled to proton transfers. This includes most common sources of chemical potential energy, from the bioenergetic processes that power cells to the fossil fuel combustion that powers cars. These proton-coupled electron transfer or PCET processes may involve multiple electrons and multiple protons, as in the 4 e–, 4 H+ reduction of dioxygen (O2) to water (eq 1), or can involve one electron and one proton such as the formation of tyrosyl radicals from tyrosine residues (TyrOH) in enzymatic catalytic cycles (eq 2). In addition, many multi-electron, multi-proton processes proceed in one-electron and one-proton steps. Organic reactions that proceed in one-electron steps involve radical intermediates, which play critical roles in a wide range of chemical, biological, and industrial processes. This broad and diverse class of PCET reactions are central to a great many chemical and biochemical processes, from biological catalysis and energy transduction, to bulk industrial chemical processes, to new approaches to solar energy conversion. PCET is therefore of broad and increasing interest, as illustrated by this issue and a number of other recent reviews.

/pdf/thermochemistry-of-proton-coupled-electron-transfer-reagents-v04esq6den.pdf

Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications

https://backend.orbit.dtu.dk/ws/files/145750384/Nreview_revised.pdf

Modeling nitrogen chemistry in combustion

Recent progress in the development of diesel surrogate fuels

https://hal.archives-ouvertes.fr/hal-00288708/document

Detailed chemical kinetic models for the low-temperature combustion of hydrocarbons with application to gasoline and diesel fuel surrogates

The ignition, oxidation, and combustion of kerosene: A review of experimental and kinetic modeling

https://elib.dlr.de/84598/2/Dagaut_BraUn2014cf_manuscript.pdf

Experimental and detailed kinetic model for the oxidation of a Gas to Liquid (GtL) jet fuel

A detailed reaction mechanism for cyclohexane oxidation has been evaluated by comparison of computed and experimental species mole fraction profiles measured in a jet-stirred reactor at 0.5≤≤1.5 and 1, 2, and 10 atm. Major and minor species mole fractions were obtained by gas chromatography: O2, CO, CO2, H2, CH2O, CH3HCO, acrolein, CH4, C2H6, C2H4, C3H6, C2H2, allene, 1-C4H8, 2-C4H8 (trans and cis), 1.3-C4H6, cyclopentene, cyclohexadiene, 1-hexene, cyclohexene, and C6H6. The main objective of this work was to extend the validity of a previously proposed mechanism for cyclohexane oxidation at 10 atm to lower pressure and to refine it by taking into account some new species analyzed in this work: 1-C4H8, 2-C4H8 (trans and cis), and aC6H12. Good agreement was obtained for most molecular species, especially intermediate olefins, dienes, and oxygenated species (CH2O, acrolein). Computed benzene, cyclopentene, and cyclohexene concentrations are also in reasonable agreement with experimental data. The mechanism also was validated at higher temperature by modeling the laminar flame speeds of cyclohexane/air flames measured by Davis and Law in a wide range of equivalence ratios. The model correctly reproduces experimental values. Reaction path analyses were used to interpret the results.

Detailed kinetic reaction mechanism for cyclohexane oxidation at pressure up to ten atmospheres

The thermal decomposition of toluene molecules and of phenyl radicals have been investigated behind reflected shock waves by monitoring the formation of hydrogen atoms with ARAS. The temperatures ranged between 1300 and 1800 K at total pressures between 1.5 and 7.8 bar. Nitrosobenzene C 6 H 5 NO served as a thermal source for the phenyl radicals. The test gas mixtures consisted of argon with relative concentrations of 2 to 30 ppm toluene and of 1 to 100 ppm nitrosobenzene, respectively. Due to the low initial concentrations of toluene and nitrosobenzene it was possible to evaluate first order rate coefficients for the initiation reactions and for some fast follow-up reactions in the phenyl pyrolysis subsystem. From a least squares analysis of all measured points the following rate expressions are deduced: k 1 =3.6×10 15 exp(−(45000±1800)/T)s −1 for C 7 H 8 →C 7 H 7 +H, 1380≤T≤1700 K and π=1.1−6.8×10 −5 mol cm −3 k 4 =(4.5±1.2)×10 13 exp(−(36500±1325)/T)s −1 for the intramolecular rearrangement of phenyl to “linear” C 6 H 5 : C 6 H 5 → l −C 6 H 5 1450≤T≤1730 K and π=1.0−1.7×10 −5 molcm −3 , which is followed by very fast unimolecular decomposition of the “linear” intermediate to C 4 H 3 +C 2 H 2 and C 5 H 4 +H.

A shock tube study on the thermal decomposition of toluene and of the phenyl radical at high temperatures

Formation of small PAHs in laminar premixed low-pressure propene and cyclopentene flames: Experiment and modeling

https://elib.dlr.de/75431/1/Kick2012Energy_manuscript.pdf

Marina Braun-Unkhoff

Papers

Experimental and detailed kinetic model for the oxidation of a Gas to Liquid (GtL) jet fuel

Detailed kinetic reaction mechanism for cyclohexane oxidation at pressure up to ten atmospheres

A shock tube study on the thermal decomposition of toluene and of the phenyl radical at high temperatures

Formation of small PAHs in laminar premixed low-pressure propene and cyclopentene flames: Experiment and modeling

An Experimental and Modeling Study of Burning Velocities of Possible Future Synthetic Jet Fuels