Chemical Reaction Rate Research Articles

Pengembangan Petunjuk Praktikum Laju Reaksi Kimia Berbasis Green Chemistry bagi Peserta Didik SMA/MA

This research is development research which aims to develop a green chemistry-based chemical reaction rate practicum instruction that is valid, practical and effective. The research procedure follows the 4D development model which is simplified to 3D, which consists of define, design and develop.The practicum instruction was validated by two experts. Next, it was tested in class XI IPA 3 of SMA Negeri 9 Bulukumba. The research results show that the level of validity of the Green Chemistry-based chemical reaction rate practicum instruction is declared valid and very suitable for use. Practicality is seen from: (1) the implementation of the green chemistry-based reaction rate practicum instruction is in the very practical category. Apart from that, the green chemistry-based reaction rate practicum instruction that was developed was effective in terms of the learning outcomes of class XI IPA 3 students that met the criteria for effectiveness.

A Boltzmann model equation synchronously involving molecular internal energy, dissociation and recombination effects for multicomponent gases

On the basis of previous work, we propose a phenomenological computable Boltzmann model equation synchronously involving polyatomic molecular internal energies, dissociation and recombination effects for multicomponent gases in this paper. Here, the distribution functions of each species have nine independent variables, which are time, physical space, molecular velocity, rotational energy and vibrational energy, if this component is a polyatomic gas. In this model equation, the concept of ‘chemical reaction rate’ is introduced in the chemical collision term to characterize the affect of chemical reactions. In order to make this complex model equation being ‘computable’, reduced distribution functions are adopted to get rid of two independent variables about rotational energy and vibrational energy of polyatomic component. We prove the conservation of this model equation, and then numerically solve it by the framework of gas-kinetic unified algorithm (GKUA), which is one kind of discrete velocity method (DVM). Here, non-catalytic boundary condition is adopted. Finally, a simple hypersonic flow around a cylinder with Mach number being 24.85 is numerically simulated to verify this model equation. In this case, four different components and eight chemical reactions are considered. It is shown that, this proposed Boltzmann model equation has the potential to be used to simulate thermochemical non-equilibrium effects of hypersonic flows covering various regimes.

A chemical kinetics theory for interpreting the non-monotonic temperature dependence of enzymatic reactions

Abstract. One notable observation of enzymatic chemical reactions is that, for a given abundance of enzymes and substrates, temperature increases cause reaction rates to first increase consistent with the Arrhenius relationship, then plateau, and finally fall off quickly to zero at high temperatures. While many mathematical functions have been used to describe this pattern, we here propose a chemical kinetics theory which successfully replicates this observation and provides insights into the processes responsible for these dynamics. The chemical kinetics theory combines the law of mass action, von Smoluchowski's diffusion-limited chemical reaction theory, and Eyring's transition state theory. This new theory reveals that the thermally reversible enzyme denaturation ensured by the ceaseless thermal motion of molecules and ions in an enzyme solution explains the plateau and subsequent decrease in chemical reaction rates with increasing temperature. The temperature-dependent affinity parameter (K) that relates enzymes and substrates through their binding also affects the shape of the emergent temperature response. We demonstrate that with an increase in substrate availability, K shifts the optimal temperature, where reaction rates plateau, towards higher values. Further, we show that the chemical kinetics theory accurately represents 12 sets of published enzyme assay data and includes the popular mechanistic model by Ratkowsky et al. (2005) as a special case. Given its good performance and solid theoretical underpinning, we believe this new theory will facilitate the construction of more mechanistic-based environmental biogeochemical models.

Fire-Extinguishing Dibromomethane Mixtures with Fluorinated Alkanes for Fire and Explosion Protection of Oil and Gas Industry Facilities

The high fire hazard level is specific to the oil and gas industry due to the circulation of large volumes of flammable gases and liquids. To ensure fire protection at the oil and gas industry facilities, automated gaseous fire extinguishing is widely used. The main fire-extinguishing agents in automated gaseous fire-extinguishing systems are refrigerants HFC 23, 125, 227еа, FC 318c, and fluorinated ketone FK 5-1-12. Upon the adoption of the international agreements on combating global warming, most fluorinated gaseous fire-extinguishing agents currently used for fire extinguishing fell under restrictions. The article indicates the importance of refrigerants HFC 23, 125, 227еа, and FC 318c, whose production volume must be reduced by 85 % by 2036 to ensure the required level of fire and explosion protection of oil and gas industry facilities. A method to reduce the volumes of used fluorinated alkanes by producing highly efficient fire-extinguishing mixtures, one of the components of which is an agent of high global warming potential (GWP) and the other is a chemical compound with a short atmospheric lifetime, has been proposed. Dibromomethane, which fully meets the latest environmental requirements, is to be considered a short-lived component. Based on the well-known kinetic data, the rates of elementary chemical reactions generated in the flame of the methane-oxygen mixture when contacting with refrigerants HFC 23, 227еа, and dibromomethane, have been calculated and compared. The efficiency of using dibromomethane to increase the fire-extinguishing efficiency of refrigerants HFC 23 and 227еа has been substantiated. An experimental determination of the minimum fire-extinguishing efficiency of the generated mixed compositions is conducted to confirm the correctness of theoretical calculations. The obtained mixed gaseous fire-extinguishing agents enable the reduction of the volume of high global warming potential refrigerants by 1.5–2 times. It has been also demonstrated that the obtained mixed compositions have no toxic impact on a human.

Трудности и погрешни схващания на български ученици при изучаването на химична кинетика

Knowing the factors that affect the rate of chemical reactions is essential not only for the entire chemical industry, but also applicable in daily life. Understanding chemical kinetics has proven to be a challenge for students, and many misconceptions have been described in the scientific literature. The purpose of the present research is to to identify the difficulties that Bulgarian students encounter when studying chemical kinetics. The research was conducted using quantitative methods – testing and surveying. A diagnostic test was conducted with 17 eleventhgraders studying “Chemistry and environmental protection” at an advanced level. In addition, a survey was conducted with 39 teachers regarding the difficulties they observed students encounter in learning chemical kinetics. From the obtained results, it can be seen that the Bulgarian students encounter difficulties similar to those found in foreign studies when learning the content of chemical kinetics. It is much easier for students to reproduce presented facts than to work with data in graphical form and draw conclusions based on graphically presented data.

Preparation and application research of transition metal phosphides

Due to the serious environmental pollution in the world, the shortcut to harmonious development is to improve traditional disposable energy and identify new energy sources that can be utilized. The current problem that human society must solve is to discover and use efficient and inexhaustible new energy sources, among which electrolytic water technology is an effective way to develop clean energy. In recent years, researchers have focused on producing hydrogen by electrolyzed water, but the intermediate hydrogen evolution reaction and the oxygen evolution reaction are relatively slow kinetic processes, and they cannot give the factory a large range of electrolytic water hydrogen production work and push down the commercialization process, so improving the rate of electrolytic water process must be an efficient catalyst. Transition metal phosphide is one of the non-precious metal catalysts in the electrochemical hydrogen evolution reaction and oxygen evolution reaction. Transition metal phosphide can promote rapid change of chemical reaction rate, and it has the characteristics of being cheap and easy to operate so it has a great prospect in the electrolysis of water. In this experiment, the oxygen evolution performance was optimized based on the crystal surface regulation of cobalt-doped transition metal nickel phosphide. The optimal reduction time and a small overpotential (60 mV) were obtained by using sodium borohydride to reduce the sample.

Timescales Associated with the Evolution of Reactive Scalar Gradient in Premixed Turbulent Combustion: A Direct Numerical Simulation Analysis

The fractional change in the reaction progress variable gradient depends on the flow normal straining within the flame and also upon the corresponding normal gradients of the reaction rate and its molecular diffusion transport. The statistical behaviours of the normal strain rate and the contributions arising from the normal gradients of the reaction rate and molecular diffusion rate within the flame were analysed by means of a Direct Numerical Simulation (DNS) database of statistically planar turbulent premixed flames ranging from the wrinkled/corrugated flamelets regime to the thin reaction zones regime. The interaction of flame-normal straining with the flame-normal gradient of molecular diffusion rate was found to govern the reactive scalar gradient transport in the preheat zone, where comparable timescales for turbulent straining and molecular diffusion are obtained for small values of Karlovitz numbers. However, the molecular diffusion timescale turns out to be smaller than the turbulent straining timescale for high values of Karlovitz numbers. By contrast, the reaction and hot product zones of the flame remain mostly unaffected by turbulence, and the reactive scalar gradient transport in this zone is determined by the interaction between the flame-normal gradients of molecular diffusion and chemical reaction rates.

Analyzing thermophoresis phenomenon in a transient free convective MHD chemically radioactive fluid over oscillatory permeable media

A numerical observation of chemically radioactive free convective magneto hydrodynamics fluid passing through a vertical permeable medium with fluctuating mass and heat transfer with thermophoresis is studied here. The fluid type is assumed to be a suspended mixture of particles that are incompressible, chemically strong, ionized, and viscous with some mass infusibility. The model pertaining to this problem is resolved through the application of a highly stable implicit finite difference method. The method is used for small and large deflections of the physical parameters, which result in a noticeable fluid flow behavior depicted graphically. The momentum, energy, concentration, skin friction, Nusselt and Sherwood number are investigated for various factors such as the thermophoresis effect, magnetic field, permeability, and chemical reaction rate. The substantial findings of the present investigation indicate that the impact of thermophoresis is more pronounced in the diffusion of concentration as compared to the rate of chemical reactions. The concentration is considerably influenced by the permeability parameter, surpassing the influence of the chemical reaction rate. For higher radiation parameters and Prandtl number, the molecular interaction of liquids increases, which in turn constrains the extent of radiative heat exchange.

Dynamics of Taylor bubble under chemical reaction enhanced mass transfer in minichannel

Taylor bubble dynamic characteristics of CO2 chemical absorption into MEA aqueous solution in a vertical minichannel were systematically investigated in this study. The generation, movement, and shrinkage of bubbles in the minichannel were visualized and monitored using a high-speed camera, and their dynamic behaviors were characterized by image analysis method. The effects of gas and liquid Re numbers and absorbent concentration on two-phase flow patterns, bubble generation frequency, initial bubble length, bubble length decrease rate, and bubble velocity were examined and analyzed. Results showed that chemical reaction-enhanced mass transfer hindered the bubble cap penetration into the main channel, and alleviated the bubble neck thinning, both effects inhibiting the bubble generation. A new Damköhler number (Da)-based correlation has been proposed to predict the initial Taylor bubble length, showing good prediction accuracy for experimental data in the literature using different absorbents. Results also showed that before the formation of sphere bubble at the end of absorption, an approximate linear relationship exists between bubble length decrease rate and bubble velocity, with the slop decided by chemical reaction rate that could be characterized by the Da number. Finally, a simple model has been developed to determine the effective channel length at a given operating condition, providing design guidelines for microchannel-based miniaturized CO2 absorbers.

Interfacial chemical reactivity enhancement.

Interfacial enhancements of chemical reaction equilibria and rates in liquid droplets are predicted using a combined theoretical and experimental analysis strategy. Self-consistent solutions of reaction and adsorption equilibria indicate that interfacial reactivity enhancement is driven primarily by the adsorption free energy of the product (or activated complex). Reactant surface activity has a smaller indirect influence on reactivity due to compensating reactant interfacial concentration and adsorption free energy changes, as well as adsorption-induced depletion of the droplet core. Experimental air-water interfacial adsorption free energies and critical micelle concentration correlations provide quantitative surface activity estimates as a function of molecular structure, predicting an increase in interfacial reactivity with increasing product size and decreasing product polarity, aromaticity, and charge (but less so for anions than cations). Reactions with small, neutral, or charged products are predicted to have little reactivity enhancement at an air-water interface unless the product is rendered sufficiently surface active by, for example, interactions with interfacial water dangling OH groups, charge transfer, or voltage fluctuations.

Multi-scale modeling of shock initiation of a pressed energetic material III: Effect of Arrhenius chemical kinetic rates on macro-scale shock sensitivity

Multi-scale predictive models for the shock sensitivity of energetic materials connect energy localization (“hotspots”) in the microstructure to macro-scale detonation phenomena. Calculations of hotspot ignition and growth rely on models for chemical reaction rates expressed in Arrhenius forms; these chemical kinetic models, therefore, are foundational to the construction of physics-based, simulation-derived meso-informed closure (reactive burn) models. However, even for commonly used energetic materials (e.g., HMX in this paper) there are a wide variety of reaction rate models available. These available reaction rate models produce reaction time scales that vary by several orders of magnitude. From a multi-scale modeling standpoint, it is important to determine which model best represents the reactive response of the material. In this paper, we examine three global Arrhenius-form rate models that span the range of reaction time scales, namely, the Tarver 3-equation, the Henson 1-equation, and the Menikoff 1-equation models. They are employed in a meso-informed ignition and growth model which allows for connecting meso-scale hotspot dynamics to macro-scale shock-to-detonation transition. The ability of the three reaction models to reproduce experimentally observed sensitivity is assessed by comparing the predicted criticality envelope (Walker–Wasley curve) with experimental data for pressed HMX Class V microstructures. The results provide a guideline for model developers on the plausible range of time-to-ignition that are produced by physically correct Arrhenius rate models for HMX.

Thermodynamic case study of boundary layer viscous nanofluid flow via a riga surface by means of finite difference method

The Riga plate is an electromagnetic actuator made out of permanent magnets and alternating electrodes on a flat surface. In the boundary layer flow across the Riga Plate, viscous dissipation is surveyed in this paper. The suitable boundary conditions have been assigned to the governing model for mass and heat convection phenomenon. A governing equation can be converted into non-dimensional form using similarity transformations. To create numerical solutions to physical phenomena, the finite difference approach can be utilized. Extensive graphical illustrations are provided for the effects of the buoyancy coefficient parameter, modified Hartmann number, parameter related to electrode and magnet width, Prandtl number, slip parameter, thermophoretic parameter, thermal radiation parameter, Schmidt number, chemical reaction rate parameter, suction parameter, Brownian motion parameter, volume fraction, Biot number, and Eckert parameter on velocity, temperature, and concentration distributions. By varying the Eckert number, the viscous dissipation effects can be obtained. Suction and slip parameters increase the velocity while decrease the temperature in both nanofluid cases. The high temperature and velocity of equally distributed nanofluids rise as the volume fraction increases. Thermal radiation promotes heat transport. The concentration of nanoparticles in the region around the plate increases as the chemical reaction parameter increases. The research findings are useful for thermal engineers and practitioners involved in the design and optimization of systems where boundary layer fluxes and heat transfer are important factors. Understanding the effects of viscous dissipation can lead to more reliable heat transfer estimates and more effective thermal management in real-world structures.

Dissolution of CaO in SiO2-CaO-Al2O3 Slag in Si Production

This work investigates the dissolution of CaO into three different compositions of SiO2-CaO-Al2O3 slag similar to those found in industrial Si furnaces. It was found that CaO dissolution into the slag is fast. During the dissolution process, a layer containing 35–42% CaO was formed between the CaO particle and the slag, which corresponded to the phases CaO·Al2O3·2SiO2 or 2CaO·Al2O3·SiO2 in this study. Two models were investigated to determine the dissolution rate of the three slags. In the first model, the CaO particle is assumed to be a smooth shrinking sphere, and the rate controlled by the chemical reaction rate. The second model assumes that the rate is controlled by mass transport and depends on the diffusion rate of CaO through a boundary layer on the surface of the CaO. Both models gave similar accuracy to the experimental values, and a proportional relationship between the rate constants and the viscosities was obtained. At 1500 °C, the diffusion coefficients were found to be in the order of 10−6 cm2/s.

Single-molecular diffusivity and long jumps of large organic molecules: CoPc on Ag(100).

Energy dissipation and the transfer rate of adsorbed molecules do not only determine the rates of chemical reactions but are also a key factor that often dictates the growth of organic thin films. Here, we present a study of the surface dynamical motion of cobalt phthalocyanine (CoPc) on Ag(100) in reciprocal space based on the helium spin-echo technique in comparison with previous scanning tunnelling microscopy studies. It is found that the activation energy for lateral diffusion changes from 150meV at 45-50K to ≈100meV at 250-350K, and that the process goes from exclusively single jumps at low temperatures to predominantly long jumps at high temperatures. We thus illustrate that while the general diffusion mechanism remains similar, upon comparing the diffusion process over widely divergent time scales, indeed different jump distributions and a decrease of the effective diffusion barrier are found. Hence a precise molecular-level understanding of dynamical processes and thin film formation requires following the dynamics over the entire temperature scale relevant to the process. Furthermore, we determine the diffusion coefficient and the atomic-scale friction of CoPc and establish that the molecular motion on Ag(100) corresponds to a low friction scenario as a consequence of the additional molecular degrees of freedom.

Carbon-Based Functional Nanomaterials as Tools for Controlling the Kinetics of Tribochemical Reactions.

The aim of this article is to experimentally determine the role of the environment, consisting of a base oil (PAO), carbon nanomaterials, and optional other additives, as well as the kind of metal in contact with the lubrication film, in the stimulation of zinc dialkyldithiophosphate (ZDDP) additives' effectiveness during protective film formation. This paper focuses on the role of carbon nanostructures in energy transportation and conversion during tribological processes. An antistatic additive (ASA) (not used in lubricating oils) for jet fuels was added to disturb the process of energy conduction (electric charges) through the lubricant film and thus determine how this disturbance affects the kinetics of the ZDDP triboreaction and, consequently, the linear wear. To achieve this research goal, two types of tribological testing devices were used: an Anton Paar tribometer (TRB) and a triboelectric tribometer (TET). The novelty of the present research is in the use of the method for disturbing the flow of charge/energy through the lubricant film with an antistatic additive for jet fuels, ASA, to influence the impact of this energy on the antiwear properties of ZDDP. The following conclusions were drawn: (1) carbon-based nanostructures, i.e., CNTs, AuCNTs, graphene, and fullerenes, are able to change the rate of chemical reactions of ZDDP during tribological processes; (2) CNTs have the ability to catalyze tribochemical reactions of ZDDP, while graphene and fullerenes are not able to perform this effectively; (3) AuCNT takes the role of an inhibitor during ZDDP's triboreaction; and (4) by discharging electric charge/energy, ASA, in cooperation with CNT and AuCNT significantly reduces the rate of the ZDDP reaction.

On the residence enhancement mechanism of the cavity-based dual-mode scramjet combustor through the Eulerian and Lagrangian analysis

The lower total temperature and pressure in a dual-mode scramjet engine lead to slower rates of evaporation and chemical reactions, while the inflow velocity is higher than that in a ramjet engine. Consequently, enhancing fuel residence time becomes a more critical challenge. The cavity is a crucial device for enhancing the residence time. However, the quantitative residence capacity and the mechanism have not yet been revealed, especially in wide-range speed inflow conditions. This work employs the delayed detached eddy simulation method to investigate the mass transport and fluid residence characteristics of the wide-range subsonic flow (Ma = 0.3, 0.4, 0.5, 0.6, 0.7) over the cavity. The Lagrangian coherent structure is utilized to characterize the dynamic evolution of the large-scale vortex in the cavity shear layer. Particle tracking is employed to delicately determine the net mass exchange rate and the quantitative cavity residence time. Based on the entrainment process of the large-scale vortex and mass exchange between the mainstream and cavity, this paper proposes a novel theoretical entrainment-impinging model of the large-scale vortex for calculating the residence enhancement coefficient (τr). The theoretical model demonstrates that the residence enhancement coefficient is a function of the cavity geometry (L, D), the vortex radius (rv), the shedding Strouhal number of the vortex (St), and the vortex/trailing edge interaction coefficient (η). Furthermore, it has been proven that the model proposed in this paper is applicable to a wide range of inflow turbulent conditions and cavity geometric configurations.

Forecasting and dynamical modeling of reversible enzymatic reactions with a hybrid proportional fractional derivative

Chemical kinetics is a branch of chemistry that investigates the rates of chemical reactions and has applications in cosmology, geology, and physiology. In this study, we develop a mathematical model for chemical reactions based on enzyme dynamics and kinetics, which is a two-step substrate–enzyme reversible reaction, applying chemical kinetics-based modeling of enzyme functions. The non-linear differential equations are transformed into fractional-order systems utilizing the constant proportional Caputo–Fabrizio (CPCF) and constant proportional Atangana–Baleanu–Caputo (CPABC) operators. The system of fractional differential equations is simulated using the Laplace–Adomian decomposition method at different fractional orders through simulations and numerical results. Both qualitative and quantitative analyses such as boundedness, positivity, unique solution, and feasible concentration for the proposed model with different hybrid operators are provided. The stability analysis of the proposed scheme is also verified using Picard’s stable condition through the fixed point theorem.

Temperature Dependence of Platelet Metabolism.

Temperature plays a fundamental role in biology, influencing cellular function, chemical reaction rates, molecular structures, and interactions. While the temperature dependence of many biochemical reactions is well defined in vitro, the effect of temperature on metabolic function at the network level is poorly understood, and it remains an important challenge in optimizing the storage of cells and tissues at lower temperatures. Here, we used time-course metabolomic data and systems biology approaches to characterize the effects of storage temperature on human platelets (PLTs) in a platelet additive solution. We observed that changes to the metabolome with storage time do not simply scale with temperature but instead display complex temperature dependence, with only a small subset of metabolites following an Arrhenius-type relationship. Investigation of PLT energy metabolism through integration with computational modeling revealed that oxidative metabolism is more sensitive to temperature changes than glycolysis. The increased contribution of glycolysis to ATP turnover at lower temperatures indicates a stronger glycolytic phenotype with decreasing storage temperature. More broadly, these results demonstrate that the temperature dependence of the PLT metabolic network is not uniform, suggesting that efforts to improve the health of stored PLTs could be targeted at specific pathways.

Analysis of unsteady MHD fluid flow across two parallel discs with uniform fluctuation subject to modified Hall and activation energy

This study intends to examine the consequences of the externally applied magnetic field and modified Hall effect on nanofluid flow across two symmetrically spinning and extending discs, where continuously the upper disc moves upward and downward. The lower disc is vertically fixed. The discs rotate and move vertically, generating a 3D flow. The mass density, heat transfer and flow motion have been evaluated and modeled in the form of the system of partial differential equations (PDEs) with an additional influence of activation energy, heat source and chemical reaction. The system of PDEs is modified to an ordinary set of differential equations by employing the resemblance substitution method. The obtained system of ODEs is further solved through the numerical approach (bvp4c). The results are compared to the bvp4c package and published work for validity purposes. In the case of downward displacement of the upper disc, magnetic and Hall characteristics have a significant impact on the velocity curve. The energy curve elevates with the upward movement of the disc, while it reduces with the downward fluctuation. Furthermore, the mass transmission rate enhances with the influence of hall current, while diminishing with the impact of chemical reaction rate.

Numerical simulations of entropy generation and Arrhenius activation energy on peristaltic transport of Prandtl‐Eyring fluid in a curved conduit

AbstractThe study aims to explore the combined impact of activation energy and entropy generation on Prandtl‐Eyring fluid flow within a curved channel, considering Hall and ion slip effects, alongside the influence of nonlinear thermal radiation on heat transfer. This research is pivotal as it delves into the multifaceted relationship among these factors, offering important implications spanning various fields, from engineering to physics. Notably, the findings highlight that heightened nonlinear thermal radiation does not solely elevate entropy generation but also amplifies the Bejan number, signifying a substantial effect on fluid flow dynamics. Furthermore, the investigation reveals an intriguing correlation: lower concentrations paired with higher Arrhenius activation energy values correspond to heightened chemical reaction rates, presenting valuable insights applicable to reaction engineering and material sciences. Additionally, exploring the impact of activation energy and entropy generation within this fluid model presents a unique approach to understanding complex fluid dynamics and heat transfer phenomena, offering insights crucial for various engineering applications, particularly in fluid dynamics, thermal sciences, and materials engineering.