Theoretical study on the H-atom abstraction reactions of pentanol + HȮ2, part I: five branched pentanol isomers.

The chemical kinetic studies of hydrogen atom (H-atom) abstraction reactions by hydroperoxyl (HȮ2) radicals from five branched pentanol isomers, including 3-methyl-1-butanol, 2-methyl-1-butanol, 1,1-dimethyl-1-propanol, 1,2-dimethyl-1-propanol, and 2,2-dimethyl-1-propanol were investigated systematically through high-level ab initio calculations. Geometry optimization, frequency analysis, and zero-point energy (ZPE) corrections were performed for six reactants, twenty-three transition states (TSs), and twenty-four products at the M06-2X/6-311++G(d,p) level of theory. The intrinsic reaction coordinate calculation was performed at the same level of theory to confirm the transition state connection. The one-dimensional hindered rotor treatment for low-frequency torsional modes was also treated at the M06-2X/6-311++G(d,p) level of theory. The QCISD(T)/CBS level of theory was used to calculate the single-point energies for the species whose T1 diagnostic value was lower than 0.035. At the same time, the CASPT2/CBS level of theory was used to calculate the single-point energies for the channel in which the T1 diagnostic value of transition states was greater than 0.035. Rate constants for the H-atom abstraction reactions from the five branched pentanol isomers by HȮ2 radicals were calculated by using conventional transition state theory with asymmetric Eckart tunneling corrections in the temperature range of 500-2000 K. Rate constants and branching ratios for the title reactions and the rate rules for ten different H-atom abstraction types were investigated. Temperature-dependent thermochemistry properties for all reactants and products were calculated by the composite methods of G3/G4/CBS-QB3/CBS-APNO, which were in good agreement with the data available in the literature. Rate constants for the H-atom abstraction reactions by HȮ2 radical from branched pentanol isomers were investigated in this work as part I, and those for linear pentanol isomers will be analyzed in part II. All the calculated kinetics and thermochemistry data can be utilized in the model development for branched pentanol isomers oxidation.

Theoretical investigation on isomerization and decomposition reactions of pentanol radicals-part II: linear pentanol isomers.

High-level ab initio calculations are conducted for studying the kinetics of three linear pentanol radicals generated through H-atom abstraction reactions. The species involved are optimized using the M06-2X/6-311++G(d,p) level of theory, while a relaxed scan at the M06-2X/6-31g level of theory with 10° increments is used for the hindrance potential for low-frequency torsional modes. Single-point energies for all stationary points are obtained through the QCISD(T) and MP2 methods in combination with cc-pVDZ, cc-pVTZ, and cc-pVQZ basis sets, which can be extrapolated to the complete basis set (CBS) limit. The rate constants and branching ratios for isomerization and decomposition reactions are computed over a temperature range of 250-2000 K and a pressure range of 0.01-100 atm. Isomerization reactions are dominant at low temperatures, while decomposition reactions are more dominant at high temperatures. The branching ratio of the isomerization reaction exhibits a slight decrease with increasing pressure, while the trend for decomposition reactions depends on the type of the breaking bond. Based on the calculations for five branched pentanol radicals in part I, kinetics of linear and branched pentanol radicals are compared in this work and the results reveal that, for the same kind of ß-scission reaction at similar positions of linear and branched pentanol radicals, the rate constants of branched ones are faster than those of linear ones at low temperatures. The hydroxyl group adjacent to the breaking bond can increase the ß-scission reaction rate constants, while the effect can be ignored when the hydroxyl group is not adjacent to the breaking bond. Moreover, compared to when the hydroxyl group is located in the middle of the carbon chain, its positioning at the chain's end yields a more noticeable impact on the products and rate constants of C-O bond and O-H bond ß-scission reactions. Besides, when incorporating calculated rate constants into the CRECK model, the updated mechanism shows a better performance for ignition delay times of 1-pentanol in the NTC range but exhibits lower reactivity at higher temperatures. The simulation of speciation profiles also shows better agreement with the experimental data obtained using a flow reactor.

Theoretical Investigation on the H Atom Abstraction Reaction from C1-C4 Alkanes and Alkenes by NH2 Radicals.

The H atom abstraction reactions from alkanes and alkenes by NH2 are decisive in predicting the combustion characteristics of NH3/CxHy binary fuels. Theoretical investigation is carried out on the energy barriers of H atom abstraction reactions from C1-C4 alkanes/alkenes by NH2 radicals at the QCISD(T)/CBS//M06-2X/6-311++G(d,p) level of theory. Single-point energies of each species are computed using QCISD(T)/cc-pVDZ, TZ level of theories with basis set corrections from MP2/cc-pVDZ, TZ, and QZ methods. One-dimensional hindered rotor potentials are obtained by the M06-2X/cc-pVTZ method with 10° increment. Rate constants of each channel across temperatures of 298.15-2000 K are calculated by solving the RRKM/Master Equation with conventional transition state theory. For alkanes, rate constants order follows ktertiary> ksecondary> kprimary, while for alkenes the order follows kallylic> kprimary> kvinylic. Among the vinylic carbon sites within the same alkene species, the hydrogen atom sharing the same carbon with the allylic carbon on the C-C double bond is the preferred site for the H atom abstraction reaction. The branching ratio results indicate that the abstraction from tertiary or secondary carbon sites on alkanes and allylic carbon sites on alkenes are dominating during the investigated temperature range but become less important as the temperature increases. The data provided in this work are in good agreement with the literature data, but for the NH2+alkenes system, the literature data are scarce and further investigation is needed.

Battery-SOC Estimation for Hybrid-Power UAVs Using Fast-OCV Curve with Unscented Kalman Filters.

Unmanned aerial vehicles (UAVs) have drawin increasing attention in recent years, and they are widely applied. Nevertheless, they are generally limited by poor flight endurance because of the limited energy density of their batteries. A robust power supply is indispensable for advanced UAVs; thus hybrid power might be a promising solution. State of charge (SOC) estimation is essential for the power systems of UAVs. The limitations of accurate SOC estimation can be partly ascribed to the inaccuracy of open circuit voltage (OCV), which is obtained through specific forms of identification. Considering the actual operation of a battery under hybrid conditions, this paper proposes a novel method, "fast OCV", for obtaining the OCVs of batteries. It is proven that fast OCV offers great advantages, related to its simplicity, duration and cost, over traditional ways of obtaining OCV. Moreover, fast-OCV also shows better accuracy in SOC estimation than traditional OCV. Furthermore, this paper also proposes a new method, "batch mode", for talking-data sampling for battery-parameter identification with the limited-memory recursive least-square algorithm. Compared with traditional the "single mode", it presents good de-noising effect by making use of all the sampled battery's terminal current and voltage data.

Theoretical investigation on isomerization and decomposition reactions of pentanol radicals-part I: branched pentanol isomers.

Theoretical investigations on the kinetics of decomposition and isomerization reactions for five types of branched pentanol radicals are carried out in this work. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all reactants, transition states, and products, while the hindrance potentials for the lower frequency modes in all of the species were obtained through a relaxed scan with an increment of 10° at the M06-2X/6-31G level of theory. Single-point energies of all species were determined at the QCISD(T)/cc-pVDZ, TZ level of theories with basis set corrections from MP2/cc-pVDZ, TZ, QZ methods. The RRKM/master equation was solved to calculate the pressure- and temperature-dependent rate coefficients for all channels in the pressure range of 0.01-100 atm over 250-2000 K. Pressure and temperature-dependent branching fractions of key species produced from pentanol radicals show that most of the pentanol radical isomers tend to isomerize to alkoxy radicals via a six-membered-ring or five-membered-ring transition state at low temperatures, producing ketones or aldehydes. At higher temperatures, the ß-scission reactions are the main reaction channels for the consumption of pentanol radicals. A weak pressure dependence has been found for all isomerization reactions, and it becomes more and more important as pressure increases. The pressure dependence trends are different for the ß-scission reactions of different branched pentanol radicals. In part I, the results for branched pentanol radical isomers are presented in detail, while in part II the results for linear pentanol radical isomers will be discussed.

Theoretical and Experimental Study of 3-Pentanol Autoignition: Ab Initio Calculation, Shock Tube Experiments, and Kinetic Modeling.

3-Pentanol is a potential alternative fuel or a green fuel additive for modern engines. The H-abstraction reactions from 3-pentanol by H, CH3, HO2, and OH radicals are significant in the 3-pentanol oxidation process. However, corresponding rate constants are forced to rely on either analogy from sec-butanol or estimation from alkanes due to a lack of direct experimental and theoretical study. In this work, stationary points on the potential energy surfaces (PESs) were calculated with the high-level DLPNO-CCSD(T)/CBS(T-Q)//M06-2X/cc-pVTZ method, which is further used to benchmark against the CBS-QB3 method. Then, the high-pressure limit rate constants for target reactions, over a broad range of temperature (400-2000 K), were calculated with the phase-space theory and conventional transition state theory. A comparison was made between the calculated rate constants and the values available in Carbonnier et al. [ Proc. Combust. Inst. 2019, 37(1), 477-484]. The rate constants for the above H-abstraction reactions in the Carbonnier model were updated with the calculated results, followed by a modification based on the computed results of 3-pentanol + HO2 to obtain the revised model. Validation against the shock tube (ST) and the jet-stirred reactor (JSR) measurements from the literature proved the revised model an optimal one. Furthermore, using an ST, ignition delay times (IDTs) for the 3-pentanol/air mixtures were measured spanning a temperature range of 920-1450 K, pressures of 6, 10, and 20 bar, and equivalence ratios of 0.5, 1.0, and 1.5. Generally, IDTs decrease with increasing temperature and reflected shock pressure. Improved predictions to present experimental data were obtained by using the revised model as compared with the Carbonnier model. Finally, sensitivity analysis was conducted using the revised model to gain an in-depth comprehension of the 3-pentanol autoignition.

Impact of drivers on real-driving fuel consumption and emissions performance.

Eco-driving has attracted great attention as a cost-effective and immediate measure to reduce fuel consumption significantly. Understanding the impact of driver behaviour on real driving emissions (RDE) is of great importance for developing effective eco-driving devices and training programs. Therefore, this study was conducted to investigate the performance of different drivers using a portable emission measurement system. In total, 30 drivers, including 15 novice and 15 experienced drivers, were recruited to drive the same diesel vehicle on the same route, to minimise the effect of uncontrollable real-world factors on the performance evaluation. The results show that novice drivers are less skilled or more aggressive than experienced drivers in using the accelerator pedal, leading to higher vehicle and engine speeds. As a result, fuel consumption rates of novice drivers vary in a slightly greater range than those of experienced drivers, with a marginally higher (2%) mean fuel consumption. Regarding pollutant emissions, CO and THC emissions of all drivers are well below the standard limits, while NOx and PM emissions of some drivers significantly exceed the limits. Compared with experienced drivers, novice drivers produce 17% and 29% higher mean NOx and PM emissions, respectively. Overall, the experimental results reject the hypothesis that driver experience has significant impacts on fuel consumption performance. The real differences lie in the individual drivers, as the worst performing drivers have significantly higher fuel consumption rates than other drivers, for both novice and experienced drivers. The findings suggest that adopting eco-driving skills could deliver significant reductions in fuel consumption and emissions simultaneously for the worst performing drivers, regardless of driving experience.

Time-resolved measurements of a swirl flame at 4 kHz via computed tomography of chemiluminescence.

Computed tomography of a chemiluminescence (CTC) system was implemented to provide time-resolved 3D measurements of an unconfined turbulent swirl flame. This system was designed in a cost-effective manner and employed three customized view registration assemblies to simultaneously capture eight projections of the target flame at a repetition rate of 4 kHz. Both time-resolved and time-averaged tomographic reconstructions were performed based on data acquired for a duration of 250 ms. Both qualitative and quantitative validations suggested the correctness of our implementation. The time-resolved instantaneous reconstructions successfully captured the evolution of the structural features of the swirl flame such as local extinctions and the helical mode. Based on the reconstructions, the centroids of chemiluminescence for all the layers were calculated. The trajectory of these centroids provided insights into the flow motion and suggested a rotating helical structure of the swirl flame. These results demonstrated the feasibility of resolving the dynamics of turbulent swirl flames with a kHz temporal resolution using the relatively inexpensive CTC system.