Calculation Of Reaction Rates Research Articles

Reactions of Hydroperoxyl Radicals (HO2) with Oxygenated Aromatic Bio-oil Model Compounds

During thermal utilization of biomass, a complex array of reactions ensues in the oxidative environment between fragments of the biomass and reactive species. In the low-temperature window, hydroperoxyl (HO2) radicals assume a central role prior to the establishment of the O/H radical pool. Anisole, cresol, guaiacol and vanillin are often utilized as representative model compounds to comprehend the combustion chemistry of the phenolic entities in biomass and oxygen-containing derived bio-oil. This paper reports thermo-kinetic parameters for the reactions of HO2 radicals with anisole, cresol, guaiacol and vanillin. Computed activation enthalpies entail facile values for H abstraction from the side-chain functional groups in the investigated compounds. H abstraction from the hydroxyl groups incurs lower activation energies in reference to methyl sites in cresol and guaiacol. Hence, H abstraction from the OH sites in these two molecules proceeds at a faster reaction rate constant when compared to abstraction from the methyl site. In the vanillin molecule, abstraction from the aldehydic and hydroxyl sites portrays comparable importance. The effect of scaling vibrational frequencies and the type of applied quantum tunneling on the computed reaction rate constants were thoroughly explored. Analysis of entropies of activation indicates that the transition states exhibit a product-like character. While ignition delay times of fuels often exhibit a profound sensitivity towards initial H abstraction reactions by HO2, we found that ignition delay times of the four title molecules remain almost unchanged when updating literature kinetics models with new reaction rate constants calculated herein. It is anticipated that reported outcomes from this study aid in formulating a better understanding of the complex chemical reactions that dictate oxidative decomposition of oxygenated bio-oil model compounds.

Study of the direct 16O(p,γ)17F astrophysical capture reaction within a potential model approach

A potential model is applied for the analysis of the astrophysical direct nuclear capture process 16O(p,γ)17F. The phase-equivalent potentials of the Woods-Saxon form for the p−16O interaction are examined which reproduce the binding energies and the empirical values of ANC for the 17F(5/2+) ground and 17F(1/2+) (E⁎=0.495 MeV) excited bound states from different sources. The best description of the experimental data for the astrophysical S factor is obtained within the potential model which yields the ANC values of 1.043 fm−1/2 and 75.484 fm−1/2 for the 17F(5/2+) ground and 17F(1/2+) excited bound states, respectively. The zero-energy astrophysical factor S(0)=9.321 KeV b is obtained by using the asymptotic expansion method of D. Baye. The calculated reaction rates within the region up to 1010 K are in good agreement with those from the R-matrix approach and the hierarchical Bayesian model in both absolute values and temperature dependence.

Controllable Assemblies of Au NPs/P5A for Enhanced Catalytic Reduction of 4-Nitrophenol

Efficient catalytic reduction of 4-nitrophenol (4-NP) is one focus of industry and practical engineering, because 4-NP is one of the most important sources of pollution of the ecological environment and human health. Here, coassembled hybrid composites of pillar[5]arene (P5A) and gold nanoparticles (Au NPs) were successfully developed by a one-step synthetic method as a type of water-insoluble catalyst for the reduction of 4-NP. The geometric and topological structures, as well as physiochemical properties of Au NPs/P5A composite catalyst, were fully characterized and analyzed through various tests such as transmission electron microscopy (TEM), X-ray diffraction (XRD), and Fourier-transform infrared spectroscopy (FTIR), indicating that Au NPs were well dispersed on the surface of the two-dimensional film of assembled P5A. The influence factors of the catalytic reduction of 4-NP were further investigated and discussed, confirming that the content of Au NPs and the concentration of 4-NP were very significant during the catalysis. The catalytic reaction was carried out at the catalyst concentration of 100 mg·L−1 and an initial 4-NP concentration of 90 mg·L−1 under 30 °C. The calculated reaction rate constant was 0.3959 min−1 and the reduction rate of 4-NP was more than 95% in 20 min. In addition, the as-prepared catalyst can maintain a high catalytic efficiency after five cycles. Thus, the easily recyclable composite catalyst with poor aqueous solution can exhibit prospective application to the treatment of 4-NP in water.

Calculation of Isotope-Specific Fission Rates for Neutrino Source Calculation in PWR Fuel Diversion Safeguarding

The emission of antineutrinos from nuclear reactors offers a potential avenue for the international enforcement of reactor safeguards. A variety of frameworks have been proposed for detecting these particles, with the objective of verifying an agreed-upon composition of fuel in the operating reactor. More specifically, these frameworks should identify the diversion of a “significant quantity” of fissile material from an agreed upon core loading. For any quantitative analysis of these frameworks, isotope-specific fission rates of a nuclear reactor are required to calculate the reactor neutrino source. Unfortunately, the calculation of isotope-specific fission rates for a realistic core is nontrivial and can require significant simulation efforts. Therefore, this work uses industry-standard simulation tools (CASMO-4/SIMULATE-3) to provide isotope-specific fission rates for a set of 15 plutonium diversion scenarios for a mixed-oxide-loaded pressure water reactor. These diversion scenarios span a wide range of diverted fuel amounts, from 2.17 to 655.19 kg of fissile plutonium. The isotope-specific fission rates reported in this paper can be combined with a neutrino emission model for the direct calculation of the reactor neutrino source. This work can be considered a dedicated effort toward the calculation of realistic isotope-specific reaction rates for use in the development and analysis of safeguarding frameworks. As such, these isotope-specific fission rates are provided over three cycles with realistic fuel loading and shuffling patterns. In this way, this work can act as a standard neutrino source reference for the development and comparison of safeguarding frameworks.

Investigation of the kinetics of methanation of a post-coelectrolysis mixture on a Ni/CZP oxide catalyst

The use of synthetic natural gas (SNG) as a plug-and-play fuel coming from renewables can help to overcome the limitations given by the intermittency of renewable energy. A way to implement the production of SNG pass through the co-electrolysis of CO2 to a mixture of hydrogen, carbon monoxide and carbon dioxide, steam and small amounts of methane, followed by CO and CO2 methanation. The presence of different reactants and processes requires the comprehension and quantification of the kinetics of the reactions involved with the aim of optimizing methanation. In this work a kinetic model that considers both the direct CO2 methanation and the indirect RWGS + CO methanation pathways has been developed over a Ni(10 %wt)/Ce0.33Zr0.63Pr0.04O2. The kinetic study made it possible to understand the influence of the reactants and products on the reactions through the calculation of reaction rates. This allowed to test, by linearization, the models found in the literature and their adjustment permitted to calculate sixteen kinetic parameters (activation energies, heats of adsorption and pre-exponential factors) present in the rate laws of methanation of CO2, CO and the Reverse Water Gas Shift reaction. The models then made it possible to simulate the evolution of partial flow rates in an isothermal plug flow reactor and were compared to experimental data.

The reactivity of organic radicals in the performic, peracetic, perpropionic acids-based advanced oxidation process: A case study of sulfamethoxazole

Advanced oxidation processes (AOPs) based on peracetic acid (PAA) displayed great potential in removing emerging contaminants by generating HO• and organic radicals. Performic and perpropionic acids (PFA and PPA) also act as disinfectants, but their application potential has not been investigated yet. Here, we investigated the degradation mechanism and kinetics of sulfamethoxazole (SMX) by HO•, RC(O)O• species (including HC(O)O•, CH3C(O)O• and CH3CH2C(O)O•) and RC(O)OO• species (including HC(O)OO•, CH3C(O)OO• and CH3CH2C(O)OO•). The results show that the calculated reaction rate constants of SMX follow the order of HC(O)O• > CH3C(O)O• > CH3CH2C(O)O• > HO• > HC(O)OO• > CH3C(O)OO• > CH3CH2C(O)OO•. The reactivity towards SMX is strongly correlated with the redox potentials of reactive radicals. Hence, the RCOO• species play dominant roles in the purification of SMX in PFA/PAA/PPA-based AOPs. The degradation of SMX mainly proceeds via addition at the benzene ring, the hydrogen abstraction from the -NH2 group as well as the single electron transfer reaction. This study highlights the fundamental aspects of PFA, PAA, and PPA in the purification of sulfamethoxazole and enhances the role of organic radicals in the AOPs based on organic peracetic acids.

Magnetic dipole transition in proton-deuteron radiative capture at BBN energies within potential model

The pd radiative capture reaction plays a vital role in Big Bang nucleosynthesis and stellar proton-proton chain. The study of the low-energy reaction is challenging in both experiments and theories. Using the framework of potential model, we analyze pd radiative capture below 1 MeV for both electric dipole (E1) and magnetic dipole (M1) transitions. The obtained astrophysical S factors agree well with recent results, especially at energies relevant to sensitive deuterium abundance. The calculated reaction rate shows good agreement, with less than a 5% difference compared to recent works. The extrapolated value for S(0) including both transitions is determined to be 0.211 ± 0.016 eV b. A comparison with experimental data using the χ 2 test reveals the sensitivity of the M1 cross section at low energies to the scattering potential depth.

Graphics processing unit/artificial neural network-accelerated large-eddy simulation of swirling premixed flames

Within the scope of reacting flow simulations, the real-time direct integration (DI) of stiff ordinary differential equations for the computation of chemical kinetics stands as the primary demand on computational resources. Meanwhile, as the number of transport equations that need to be solved increases, the computational cost grows more substantially, particularly for those combustion models involving direct coupling of chemistry and flow such as the transported probability density function model. In the current study, an integrated graphics processing unit-artificial neural network (GPU-ANN) framework is introduced to comply with heavy computational costs while maintaining high fidelity. Within this framework, a GPU-based solver is employed to solve partial differential equations and compute thermal and transport properties, and an ANN is utilized to replace the calculation of reaction rates. Large eddy simulations of two swirling flames provide a robust validation, affirming and extending the GPU-ANN approach's applicability to challenging scenarios. The simulation results demonstrate a strong correlation in the macro flame structure and statistical characteristics between the GPU-ANN approach and the traditional central processing unit (CPU)-based solver with DI. This comparison indicates that the GPU-ANN approach is capable of attaining the same degree of precision as the conventional CPU-DI solver, even in more complex scenarios. In addition, the overall speed-up factor for the GPU-ANN approach is over two orders of magnitude. This study establishes the potential groundwork for widespread application of the proposed GPU-ANN approach in combustion simulations, addressing various and complex scenarios based on detailed chemistry, while significantly reducing computational costs.

Kinetics mechanism of pore pressure effect on CO2-water-rock interactions: An experimental study

Carbon capture, utilization and storage (CCUS) is an effective technology to reduce carbon dioxide (CO2) content in atmosphere, while due to the insufficient mastery of deterioration laws of reservoir rocks caused by CO2, the extensive application of carbon storage projects is hindered by the leakage risk. Therefore, it was aimed to study the kinetics mechanism of pore water pressure on CO2-water–rock interactions. First, the pressure effect on water–rock interactions was studied to obtain the relationship between ratio of solid–liquid contact area Ψ and pore pressure, and the controlling mechanism of Ψ on reaction rate ri was verified. On this basis, the pressure effect on CO2-water–rock interactions was further studied. Considering the effects on Ψ and solution acidity, the original CO2-applicable kinetics equation was modified to reduce the error of calculating reaction rate by 33.60% on average. Meanwhile, a forecast method was proposed for the reaction rate under different pressure conditions, and the average calculation error was 41.00% lower than that of original kinetics equation. After verifying the accuracy of these two theoretical methods to calculate reaction rate, the reliability to calculate porosity evolution process was further verified, and the calculation errors could be reduced by 29.52% and 31.81%, respectively.

Calculation of Reaction Rate and Uncertainty for d(p,γ)3He and 3He(d,p)4He Using Bayesian Statistical Approach in Astrophysics

Calculation of Reaction Rate and Uncertainty for d(p,γ)3He and 3He(d,p)4He Using Bayesian Statistical Approach in Astrophysics

Chemically derived quinary Cu2Co1–xNaxSnS4 photon absorber material and its photocatalytic application

The solar absorbing materials attract attention for the opto-electronic device applications such as solar cells and photocatalysis. Interest in photocatalytic materials to clean up the wastewater has started to increase. Generally, semiconductors sensitive to UV region are used. However, most of the light from the sun is in the visible region. Cu2CoSnS4 is a promising material that exhibits superior photo-response in the visible regions with an appropriate band gap. In this study, Cu2CoSnS4 films were prepared by the sol–gel method. Cu2Co1–xNaxSnS4 was synthesized for the first time by partly substituting sodium with cobalt. With this approach, noticeable improvements were observed in the physical properties of the material. With the sodium replacement, the Cu2Co1–xNaxSnS4 exhibited high photocatalytic performance toward the degradation of methylene blue (MB) under visible-light irradiation. According to the results, Cu2CoSnS4 and Cu2Co1–xNaxSnS4 samples degraded the MB solution by degradation efficacy values of 89.69% and 94.57%, respectively, in a short time like 40 min under visible light. This study shows that the substitution of sodium boosted the degradation efficiency by 5.4%. For the Cu2CoSnS4 and Cu2Co1–xNaxSnS4 samples, the computed reaction rate constants are 0.059 min−1 and 0.077 min−1, respectively.

Probing time-resolved plasma-driven solution electrochemistry in a falling liquid film plasma reactor: Identification of HO2- as a plasma-derived reducing agent.

Many applications involving plasma-liquid interactions depend on the reactive processes occurring at the plasma-liquid interface. We report on a falling liquid film plasma reactor allowing for in situ optical absorption measurements of the time-dependence of the ferricyanide/ferrocyanide redox reactivity, complemented with ex situ measurement of the decomposition of formate. We found excellent agreement between the measured decomposition percentages and the diffusion-limited decomposition of formate by interfacial plasma-enabled reactions, except at high pH in thin liquid films, indicating the involvement of previously unexplored plasma-induced liquid phase chemistry enabled by long-lived reactive species. We also determined that high pH facilitates a reduction-favoring environment in ferricyanide/ferrocyanide redox solutions. In situ conversion measurements of a 1:1 ferricyanide/ferrocyanide redox mixture exceed the measured ex situ conversion and show that conversion of a 1:1 ferricyanide/ferrocyanide mixture is strongly dependent on film thickness. We identified three dominant processes: reduction faster than ms time scales for film thicknesses >100 µm, •OH-driven oxidation on time scales of <10ms, and reduction on 15ms time scales for film thickness <100 µm. We attribute the slow reduction and larger formate decomposition at high pH to HO2- formed from plasma-produced H2O2 enabled by the high pH at the plasma-liquid interface as confirmed experimentally and by computed reaction rates of HO2- with ferricyanide. Overall, this work demonstrates the utility of liquid film reactors in enabling the discovery of new plasma-interfacial chemistry and the utility of atmospheric plasmas for electrodeless electrochemistry.

Theoretical study on the kinetics and reaction mechanism involved in the reduction of quinone by 1‐benzyl‐1,4‐dihydronicotinamide

AbstractAlthough it is well known that coenzyme NAD(P)H is involved in anabolic and catabolic reactions in the living organism, there is still significant controversy over the reaction mechanism involved in this biochemical transformation. Thus, 1‐benzyl‐1,4‐dihydronicotinamide was used as a NAD(P)H model in the reduction reaction of 1,4‐benzoquinone (Q), 2,3,5,6‐tetrachloro‐1,4‐benzoquinone, and 2,3‐dicyano‐1,4‐benzoquinone in acetonitrile medium. The kinetic calculations support that formal hydride transfer is the main mechanism promoting Q reduction, while the two‐step process dominates 2,3‐dicyano‐1,4‐benzoquinone reduction. Interestingly, only the single‐electron transfer mechanism takes place when 2,3,5,6‐tetrachloro‐1,4‐benzoquinone is used, affording the corresponding semiquinone derivative as the main product. This mechanistic behavior is related to the presence or absence of electron‐withdrawing groups in the quinones used. Furthermore, the kinetic study results showed that calculated reaction rate constants are in close agreement with experimental results. The results support that formal hydride transfer on the reduction reaction of Q by 1‐benzyl‐1,4‐dihydronicotinamide in acetonitrile proceeds through a hydrogen coupled electron transfer mechanism. This theoretical analysis provides valuable knowledge that can be extrapolated to study the reduction of quinones performed by NADH and NADPH in physiological media.

Reaction Rates of OH Radicals with CH3OCF2CHFCF3 and CHF2CF2OCH2CF2CHF2: Measurements and Estimation Using Neural Network Method.

The reaction rates of OH radicals with CH3OCF2CHFCF3 (k1) and CHF2CF2OCH2CF2CHF2 (k2) were measured over a temperature range of 250-430 K. Kinetic measurements were performed using the flash and laser photolysis methods combined with a laser-induced fluorescence technique. The Arrhenius rate parameters were determined as k1 = (2.52 ± 0.25) × 10-12·exp[-(1390 ± 30)/T], k2 = (1.83 ± 0.20) × 10-12·exp[-(1420 ± 35)/T] cm3 molecule-1 s-1. The infrared absorption spectra of the two hydrofluoroethers were measured at approximately 298 K in 760 Torr of N2. The atmospheric lifetimes of CH3OCF2CHFCF3 and CHF2CF2OCH2CF2CHF2 have been estimated as 2.5 and 3.8 years, respectively, and their global warming potentials were determined as 245 and 405, respectively. Additionally, a method, using a three-layered feed-forward neural network, for estimating the rates of the reaction of the OH radicals with alkanes, ethers, and alcohols was investigated. The ratios of the calculated reaction rates to the observed ones agreed within a factor of 2. The ability of the neural network method to predict reaction rates was examined by using a leave-one-out test.

A novel method for predicting the thermal stabilization temperature of organic Rankine cycle system working fluids based on transition state theory

The use of organic working fluids in organic Rankine cycle (ORC) systems may lead to thermal decomposition, which negatively impacts system performance and safety. In this work, a simplified theoretical method based on the transition state theory is proposed to predict the ideal maximum thermal stabilization temperature of organic working fluids. This method involves considering the initial decomposition reaction of the working fluids and calculating the total reaction rate of the initial decomposition. By setting an acceptable decomposition rate, the ideal maximum thermal stabilization temperature of the working fluid can be determined. Using this method, the total reaction rate constants of several typical hydrocarbon, hydrofluorocarbon and siloxane working fluids were obtained in the temperature range of 300∼700 K. The predicted maximum operational temperatures were in good agreement with most experimental results. The branch ratio analyses show that C–C bond cleavage contributed mainly to the decomposition of hydrocarbons, the removal of HF and C–C bond cleavage contributed mainly to that of HFCs, and the Si–C bond cleavage contributed mainly to that of siloxanes. Only considering these main reactions in the reaction rate calculation can greatly reduce calculation cost without significantly impacting the prediction accuracy.

Improved numerical simulation model for nuclear reaction rate calculations in high-speed plasma collisions

Beam–target reactions in fusion plasmas play an important role in both magnetic confinement fusion and inertial confinement fusion in the condition of low-density plasmas with high-velocity interactions. The traditional method for calculating beam–target reaction rate neglects the transport process of incident particles in inhomogeneous plasmas, leading to errors providing that the temperature and density in the transport path of incident particles vary obviously. An improved method considering the transport process is proposed in this paper to eliminate the deficiencies. Then the method is employed in high-speed plasma collision studies. When the initial plasma density and temperature are set to $0.5\,{\rm g}\,{\rm cm}^{-3}$ and 100 eV, it is found that the beam–target reaction rate calculated by the traditional method is almost identical to that by our method if the collision velocity is less than 600 km s $^{-1}$ . However, the traditional method is not suitable for study as the collision velocity gets higher, inducing obvious differences, which can reach 70 % at 1000 km s $^{-1}$ . The improved method will make large corrections to evaluate the importance of the non-negligible beam–target reaction for inertial confinement fusion schemes with large implosion velocity such as double-cone ignition and impact ignition, in which the high-speed plasmas collide with each other to realize plasma ignition.

Recent results and future perspectives with solid targets at LUNA

The stellar evolution and chemical make-up of the Universe are determined by nuclear reactions occurring in a wide variety of stellar sites. Precise determinations of the cross sections of these reactions are crucial for the calculation of reaction rates and for the development of stellar evolution models. The Laboratory for Underground Nuclear Astrophysics (LUNA) collaboration has been at the forefront of the direct measurement of nuclear reactions at the low energies of astrophysical interest for the last 35 years. The many significant results achieved at LUNA have been made possible due to the low background conditions uniquely available thanks to its location deep underground at the Laboratori Nazionali del Gran Sasso. Another key aspect of these successes is due to the experience of the LUNA collaboration in the production and characterization of a variety of solid targets used in reaction measurements. In this review, the main production techniques of solid targets are described, as well as the common methods adopted for target degradation monitoring. We also present the results of recent measurements using these targets and the future plans of the LUNA collaboration for measurements using solid targets at the LUNA400 kV and the new Ion Beam Facility (IBF) 3.5 MV are also presented.

Theoretical and kinetic study of the thermal decomposition mechanism of long chain aldehydes

The mechanism of decomposition of the butanal and pentanal long chain aldehydes was investigated using the ab initio transition state theory-based master equation approach. The rate constants of the homolytic bond scission reactions of butanal and pentanol leading to the formation of CHO+C3H7, CH2CHO+C2H5, C2H4CHO+CH3, C3H7CO+H, C2H5ĊHCHO+H and CH2CHO+C3H7, C2H4CHO+C2H5, C3H6CHO+CH3, C4H9CO+H, C3H7ĊHCHO+H, respectively, as well as of the reverse barrierless recombination channels, were determined using Variable Reaction Coordinate Transition State Theory. The potential energy surfaces were determined at the multireference CASPT2/aug-cc-pVTZ level on ωB97X-D/jun-cc-pVTZ structures, while stochastic samplings were performed at the CASPT2 level using a (4e,4o) active space. Rate laws for the alkyl+R-CHO, H+R-ĊHCHO, and H+R-ĊO classes of reactions were then determined. Rate constants of H-abstraction reactions and of the three body butanal →CO+H2+C3H6 channel were determined using ωB97X-D/jun-cc-pVTZ structures and Hessians and CCSD(T) energies, extrapolated to the complete basis set. It was found that the calculated homolytic bond scission reactions are faster by a factor of 2–3 with respect to literature previous estimates. The calculated reaction rates were inserted in the CRECK kinetic scheme and used to simulate literature speciation data of butanal and pentanal pyrolysis in shock tubes and ignition delay times, finding that their inclusion into the kinetic scheme enhances the predictive capabilities of the mechanism. The aldehyde decomposition mechanism and the rate constants determined in this study are suitable to be used to interpret and predict the reactivity of aldehydes in a wide range of temperatures and pressures.

Calculation of astrophysical reaction rate and uncertainty for T(d,n)4He using Bayesian statistical approach

Abstract One of the best methods to investigate and calculate a desired quantity using available limited data is the Bayesian statistical method, which has been recently entered the field of nuclear astrophysics and can be used to evaluate the astrophysical S-factors, the cross sections and, as a result, the nuclear reaction rates of Big Bang Nucleosynthesis. This study tries to calculate the astrophysical S-factor and the rate of reaction T(d,n)4He as an important astrophysical reaction with the help of this method in energies lower that electron repulsive barrier, and for this purpose, it uses the R-Software, which leads to improved results in comparison with the non-Bayesian methods for the mentioned reaction rate.

Neutron source strength verification via reaction rate measurement and Monte Carlo simulation

Determining the neutron source strength is essential to ensure optimal use of the source and to implement adequate radiation protection measures. In this study, the source strength of two (α,n) neutron sources – a newly acquired 185 GBq 241AmBe and a legacy source 74 GBq 239PuBe – were verified. Source strength verification was performed by measuring the induced activities in irradiated 115In foils and comparing the results to MCNP calculated reaction rates. The results for 241AmBe agree well with a maximum and average deviations of 8.1% and 4.1%, respectively. While for 239PuBe the maximum deviation is 11.7% and the average deviation is 6.3%. Results of this study provide a reliable reference for the application of the sources, in particular, for the 241AmBe which is used as the external neutron source of the PRR1-Subcritical Assembly for Training, Education, and Research (PRR1-SATER), and for the design of a neutron irradiator that will repurpose the 239PuBe.