Kinetic insights into the reaction of hydroxyl radicals with 1,4-pentadiene: A combined experimental and theoretical study

Giri, Binod Raj; V.‐T., Tam; Nguyen, Thi T.-D.; Szőri, Milán; Huynh, Lam K.; Farooq, Aamir

doi:10.1016/j.combustflame.2022.112153

Cited by 9 publications

(7 citation statements)

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“…Similar to our earlier work on NH 2 + CH 3 OH/C 2 H 5 OH reactions [14], we optimized the geometry of all the stationary points for the NH 2 + C 3 H 8 reaction at the M06-2X//augcc-pVTZ level of theory. Our choice of the M06-2X level of theory is based on several earlier studies that reported the best suitability of the M06-2X//aug-cc-pVTZ level of theory for geometry optimizations, frequency calculations, and accurate energetics of many chemical systems [14,[26][27][28][29][30][31][32]. We characterized the identity of each stationary point in the potential energy surface (PES) of the NH 2 + C 3 H 8 reaction through normal model analysis.…”

Section: Methodsmentioning

confidence: 99%

A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends’ Oxidation

et al. 2023

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The reaction of NH2 radicals with C3H8 is crucial for understanding the combustion behavior of NH3/C3H8 blends. In this study, we investigated the temperature dependence of the rate coefficients for the hydrogen abstraction reactions of C3H8 by NH2 radicals using high-level theoretical approaches. The potential energy surface was constructed at the CCSD(T)/cc-pV(T, Q)//M06-2X/aug-cc-pVTZ level of theory, and the rate coefficients were computed using conventional transition state theory, incorporating the corrections for quantum tunneling and hindered internal rotors (HIR). The computed rate coefficients showed a strong curvature in the Arrhenius behavior, capturing the experimental literature data well at low temperatures. However, at T > 1500 K, the theory severely overpredicted the experimental data. The available theoretical studies did not align with the experiment at high temperatures, and the possible reasons for this discrepancy are discussed. At 300 K, the reaction of NH2 with C3H8 predominantly occurs at the secondary C-H site, which accounts for approximately 95% of the total reaction flux. However, the hydrogen abstraction reaction at the primary C-H site becomes the dominant reaction above 1700 K. A composite kinetic model was built, which incorporated the computed rate coefficients for NH2 + C3H8 reactions. The importance of NH2 + C3H8 reactions in predicting the combustion behavior of NH3/C3H8 blends was demonstrated by kinetic modeling.

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Section: Methodsmentioning

confidence: 99%

A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends’ Oxidation

et al. 2023

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“…The stability of the initial OH adduct will ultimately affect the overall reactivity of the alkene with ˙OH. 42 For example, in 1,3-pentadiene, the four pathways are grouped two by two, as IM1 and IM4 have similar potential heights and are lower than IM2 and IM3. For conjugated dienes, the pi-electron density overlap allows the electrons to “delocalise” over a larger area, 1,66 explaining why IM2 and IM3 are so similar.…”

Section: Discussionmentioning

confidence: 99%

“…20,41 An explanation of alkene reactivity has been studied and reported is that the more specic-addition sites an alkene can provide, the more reactive the alkene is for its reaction with cOH. 35,42 Cumulated diene, 12PD contains a propadiene group (C]C] C-), and the intermolecular addition of cOH to 12PD takes place at three potential sites due to the two tightly linked double bonds forming a unique p-bond structure. 43,44 In contrast, conjugated diene 3M13PD and isolated diene 14HD can provide four addition sites, which explains why 12PD is less reactive toward cOH than 3M13PD, 14HD, where k 12PD+OH is 3-5 times lower than k 3M13PD+OH and k 14HD+OH .…”

Section: Methodsmentioning

confidence: 99%

“…It will ultimately affect the overall reactivity of 1,4-pentadiene with cOH. 42,66 Generally, the overall rate coefficients of 1,4-pentadiene are expected to be equal to the sum of two corresponding mono-alkenes, but in fact, they are lower than the sum of rate coefficients of mono-alkenes, e.g., k 1,4-pentadiene of 5.41 × 10 −11 cm 3 per molecule per s is lower than k 1-pentene + k 1-pentene as 6.44 × 10 −11 cm 3 per molecule per s, and it is same for other isolated dienes (Table S3 †). This nding indicates that the interaction also exists between these two isolated C]C bonds, which was not expected before.…”

Section: -Hexadiene (C]cccc]c) and Cumulated Dienes: Propadiene (C]c]...mentioning

confidence: 99%

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Kinetic and reactivity of gas-phase reaction of acyclic dienes with hydroxyl radical in the 273–318 K temperature range

Xue,

Xu,

Lyu

et al. 2024

RSC Adv.

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“…1,4-cyclochexadiene [35], cyclopentadiene [36], 1,4-pentadiene [37], Truhlar's M06 functionals are known to predict structures and frequencies for several chemical systems accurately [28,29]. Particularly, the M06-2X/aug-cc-pVTZ level is widely used to predict the rate coefficients reliably for several chemical systems, e.g., OH-initiated oxidation kinetics of imidazole [30], pyrrole [31], trans-decalin [32], oxazole [33], aniline [34], 1,4-cyclochexadiene [35], cyclopentadiene [36], 1,4-pentadiene [37], monoethanolamine [38], and dipropyl thiosulfinate [39]. However, for higher accuracy, the energies of the stationary points were refined with more expensive CCSD(T) [40][41][42]/cc-pVTZ single-point calculations using the M06-2X/aug-cc-pVTZ optimized geometry.…”

Section: Computational Detailsmentioning

confidence: 99%

An Ab Initio RRKM-Based Master Equation Study for Kinetics of OH-Initiated Oxidation of 2-Methyltetrahydrofuran and Its Implications in Kinetic Modeling

et al. 2023

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Cyclic ethers (CEs) can be promising future biofuel candidates. Most CEs possess physico-chemical and combustion indicators comparable to conventional fuels, making them suitable for internal combustion engines. This work computationally investigates the kinetic behaviors of hydrogen abstraction from 2-methyl tetrahydrofuran (2MTHF), one of the promising CEs, by hydroxyl radicals under combustion and atmospheric relevant conditions. The various reaction pathways were explored using the CCSD(T)/cc-pVTZ//M06-2X/aug-cc-pVTZ level of theory. The Rice–Ramsperger–Kassel–Marcus-based master equation (RRKM-ME) rate model, including treatments for hindered internal rotation and tunneling, was employed to describe time-dependent species profiles and pressure and temperature-dependent rate coefficients. Our kinetic model revealed that the H-abstraction proceeds via an addition-elimination mechanism forming reaction complexes at both the entrance and exit channels. Eight different reaction channels yielding five radical products were located. The reaction exhibited complex kinetics yielding a U-shaped Arrhenius behavior. An unusual occurrence of negative temperature dependence was observed at low temperatures, owing to the negative barrier height for the hydrogen abstraction reaction from the C-H bond at the vicinity of the O-atom. A shift in the reaction mechanism was observed with the dominance of the abstraction at Cα-H of 2MTHF ring (causing negative-T dependence) and at CH3 (positive-T dependence) at low and high temperatures, respectively. Interestingly, the pressure effect was observed at low temperatures, revealing the kinetic significance of the pre-reaction complex. Under atmospheric pressure, our theoretical rate coefficients showed excellent agreement with the available literature data. Our model nicely captured the negative temperature-dependent behaviors at low temperatures. Our predicted global rate coefficients can be expressed as k (T, 760 Torr) = 3.55 × 101 × T−4.72 × exp [−340.0 K/T] + 8.21 × 10−23 × T3.49 × exp [918.8 K/T] (cm3/molecule/s). Our work provides a detailed kinetic picture of the OH-initiated oxidation kinetics of 2MTHF. Hence, this information is useful for building a kinetic me chanism for methylated cyclic ethers.

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Kinetic insights into the reaction of hydroxyl radicals with 1,4-pentadiene: A combined experimental and theoretical study

Cited by 9 publications

References 56 publications

A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends’ Oxidation

A Theoretical Study of NH2 Radical Reactions with Propane and Its Kinetic Implications in NH3-Propane Blends’ Oxidation

Kinetic and reactivity of gas-phase reaction of acyclic dienes with hydroxyl radical in the 273–318 K temperature range

An Ab Initio RRKM-Based Master Equation Study for Kinetics of OH-Initiated Oxidation of 2-Methyltetrahydrofuran and Its Implications in Kinetic Modeling

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