Slow Coagulation Rate Coefficient

AbstractMethyl-Crotonate (MC, (E)-methylbut-2-enoate, CH3CHCHC(O)OCH3) is a potential component of surrogate fuels that aim to emulate the combustion of fatty acid methyl ester (FAME) biodiesels with significant unsaturated FAME content. MC has three allylic hydrogens that can be readily abstracted under autoignition and combustion conditions to form a resonantly-stabilized CH2CHCHC(O)OCH3 radical. In this study we have utilized photoionization mass spectrometry to investigate the O2 addition kinetics and thermal unimolecular decomposition of CH2CHCHC(O)OCH3 radical. First we determined an upper limit for the bimolecular rate coefficient of CH2CHCHC(O)OCH3 + O2 reaction at 600 K (k ≤ 7.5 × 10−17 cm3 molecule−1 s−1). Such a small rate coefficient suggest this reaction is unlikely to be important under combustion conditions and subsequent efforts were directed towards measuring thermal unimolecular decomposition kinetics of CH2CHCHC(O)OCH3 radical. These measurements were performed between 750 and 869 K temperatures at low pressures (<9 Torr) using both helium and nitrogen bath gases. The potential energy surface of the unimolecular decomposition reaction was probed at density functional (MN15/cc-pVTZ) level of theory and the electronic energies of the stationary points obtained were then refined using the DLPNO-CCSD(T) method with the cc-pVTZ and cc-pVQZ basis sets. Master equation simulations were subsequently carried out using MESMER code along the kinetically important reaction pathway. The master equation model was first optimized by fitting the zero-point energy corrected reaction barriers and the collisional energy transfer parameters $\Delta{E_{{\text{down}},\;{\text{ref}}}}$ and n to the measured rate coefficients data and then utilize the constrained model to extrapolate the decomposition kinetics to higher pressures and temperatures. Both the experimental results and the MESMER simulations show that the current experiments for the thermal unimolecular decomposition of CH2CHCHC(O)OCH3 radical are in the fall-off region. The experiments did not provide definite evidence about the primary decomposition products.

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Stationary Non-equilibrium Solutions for Coagulation Systems

Archive for Rational Mechanics and Analysis ◽

10.1007/s00205-021-01623-w ◽

2021 ◽

Vol 240 (2) ◽

pp. 809-875

Author(s):

Marina A. Ferreira ◽

Jani Lukkarinen ◽

Alessia Nota ◽

Juan J. L. Velázquez

Keyword(s):

Power Law ◽

Source Term ◽

Continuous Model ◽

Stationary Solutions ◽

Weight Functions ◽

Equilibrium Solutions ◽

Coagulation Rate ◽

Diffusion Limited Aggregation ◽

Coagulation Equations ◽

Non Equilibrium

AbstractWe study coagulation equations under non-equilibrium conditions which are induced by the addition of a source term for small cluster sizes. We consider both discrete and continuous coagulation equations, and allow for a large class of coagulation rate kernels, with the main restriction being boundedness from above and below by certain weight functions. The weight functions depend on two power law parameters, and the assumptions cover, in particular, the commonly used free molecular and diffusion limited aggregation coagulation kernels. Our main result shows that the two weight function parameters already determine whether there exists a stationary solution under the presence of a source term. In particular, we find that the diffusive kernel allows for the existence of stationary solutions while there cannot be any such solutions for the free molecular kernel. The argument to prove the non-existence of solutions relies on a novel power law lower bound, valid in the appropriate parameter regime, for the decay of stationary solutions with a constant flux. We obtain optimal lower and upper estimates of the solutions for large cluster sizes, and prove that the solutions of the discrete model behave asymptotically as solutions of the continuous model.

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Effect of ammonia and water molecule on OH + CH3OH reaction under tropospheric condition

Scientific Reports ◽

10.1038/s41598-021-90640-6 ◽

2021 ◽

Vol 11 (1) ◽

Author(s):

Mohamad Akbar Ali ◽

M. Balaganesh ◽

Faisal A. Al-Odail ◽

K. C. Lin

Keyword(s):

Water Molecule ◽

Energy Surface ◽

Rate Coefficient ◽

Water Concentration ◽

State Theory ◽

Rate Coefficients ◽

Hydrogen Atoms ◽

Experimental And Theoretical Studies ◽

Effective Reaction ◽

Effective Reaction Rate

AbstractThe rate coefficients for OH + CH3OH and OH + CH3OH (+ X) (X = NH3, H2O) reactions were calculated using microcanonical, and canonical variational transition state theory (CVT) between 200 and 400 K based on potential energy surface constructed using CCSD(T)//M06-2X/6-311++G(3df,3pd). The results show that OH + CH3OH is dominated by the hydrogen atoms abstraction from CH3 position in both free and ammonia/water catalyzed ones. This result is in consistent with previous experimental and theoretical studies. The calculated rate coefficient for the OH + CH3OH (8.8 × 10−13 cm3 molecule−1 s−1), for OH + CH3OH (+ NH3) [1.9 × 10−21 cm3 molecule−1 s−1] and for OH + CH3OH (+ H2O) [8.1 × 10−16 cm3 molecule−1 s−1] at 300 K. The rate coefficient is at least 8 order magnitude [for OH + CH3OH(+ NH3) reaction] and 3 orders magnitude [OH + CH3OH (+ H2O)] are smaller than free OH + CH3OH reaction. Our calculations predict that the catalytic effect of single ammonia and water molecule on OH + CH3OH reaction has no effect under tropospheric conditions because the dominated ammonia and water-assisted reaction depends on ammonia and water concentration, respectively. As a result, the total effective reaction rate coefficients are smaller. The current study provides a comprehensive example of how basic and neutral catalysts effect the most important atmospheric prototype alcohol reactions.

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