Chemical Rate Coefficients Research Articles

Uncertainty in phosphine photochemistry in the Venus atmosphere prevents a firm biosignature attribution

Context. The possible detection of phosphine (PH3) in the clouds of Venus has raised the question as to which processes could produce such large abundances of PH3. Previous studies suggested that abiotic processes including photochemical production cannot explain the claimed PH3 concentrations. However, the photochemistry of phosphorus-bearing species in the atmosphere of Venus is not well known. Aims. We aim to assess the abiotic production of PH3 considering the effect of uncertainties in the chemical rate coefficients of phosphorus-containing reactions. Methods. Using a photochemical column model, we simulated Venus-like conditions and varied the chemical rate coefficients with a Monte Carlo (MC) approach in order to estimate the associated error in the PH3 abundances throughout the atmosphere. Results. Current uncertainties and missing data in photochemical rate coefficients lead to a variation of about six orders of magnitude in the modelled PH3 abundance on Venus, assuming photochemical production of PH3 from tetraphosphorus hexoxide (P4O6) pathways. Our results suggest an abiotically produced upper limit of 2 ppb PH3 between 50 and 60 km. These concentrations are in the range of a recent reanalysis of Atacama Large Millimeter Array (ALMA) data, suggesting planet-averaged abundances in PH3 of 1–4 ppb above 55 km. Future observations of phosphorus monoxide (PO) on Venus would be beneficial for increasing our confidence in assessing PH3 as a biosignature. Conclusions. We conclude that due to the large uncertainties in phosphorus chemistry, even a firm detection of several ppb PH3 in the Venus atmosphere would not necessarily mean a biological origin.

Revisiting the Gas-phase Chemical Rate Coefficients at High Temperatures in CLOUDY

A two-body gas-phase reaction rate coefficient can be given by the usual Arrhenius-type formula which depends on temperature. The UMIST Database for Astrochemistry is a widely used database for reaction rate coefficients. They provide fittings for coefficients valid over a particular range of temperatures. The permissible upper-temperature limits vary over a wide range: from 100 to 41,000 K. A wide range of temperatures occurs in nature; thus, it requires evaluating the rate coefficients at temperatures outside the range of validity. As a result, a simple extrapolation of the rate coefficients can lead to unphysically large values at high temperatures. These result in unrealistic predictions. Here we present a solution to prevent the gas-phase reaction coefficients from diverging at a very high temperature. We implement this into the spectral synthesis code CLOUDY which operates over a wide range of temperatures from CMB to 1010 K subject to different astrophysical environments.

Diffusion combustion of NH3 in a single bubble of fluidized bed

Fluidized bed is a potential equipment for NH3 combustion due to its efficient gas–solid contact and high temperature particles as heat source for ignition. This paper studies the diffusion combustion of NH3 in a single bubble of fluidized bed, using an experimental approach and CFD-DEM simulation incorporated with a skeleton mechanism of 98 elementary reactions. The results show that the diffusion combustion of NH3 intermittently occurs in the bubble injection period and the oxygen is mainly consumed by H + O2 = OH + O. Slow oxidation, instead of combustion, takes place in the bubble rising period and the oxygen is mainly consumed by NNH + O2 = N2 + HO2. With the rupture of the bubble, unreacted NH3 re-burns, generating flames in the freeboard of the bed. The chemical reaction in the bubble is highly correlated to the mass transfer between the emulsion phase and bubble phase. Increasing the fluidization gas velocity promotes the accumulation of oxygen and enhances the reaction rate of slow oxidation of NH3 in the bubble due to the increasing inter-phase mass transfer. The increase of the bed temperature reduces the ignition delay time, and increases the chemical reaction rate and mass transfer coefficient. The changes in oxygen concentration of fluidizing gas not only changes the chemical reaction rate, but also affects the oxygen consumption path. The fraction of NH3 oxidized in the dense bed can be enhanced by increasing the fluidization gas velocity, bed temperature and oxygen concentration of the fluidizing gas, the latter exerting the greatest influence.

Numerical Study of Random Corrosion Characteristics of Metal Based On the Cellular Automata Method

In the production process of coal chemical companies, the corrosion of metal equipment and the resulting shortening of its service life can cause safety hazards. Simulation modeling of pit emergence and development during corrosion evolution provides a newapproach to corrosion research. By analyzingthe effect of different parameters on causing corrosion to occur, it is possible to reflect the influence of complex physico-chemical systems. In this paper, the simulation of a meta-cellular automaton model ofpit growth under diffusion and the introduction of a passivation probability to correct the chemical reaction rate are developed; The effect of reaction passivation probability, chemical reaction rate and diffusion coefficient on the degree of corrosion was also analyzedby means of quantitative analysis. The results show that for metal corrosion loss processes, the degree of corrosion damage decreases with increasing probability of reactive passivation and increases with increasing chemical reaction rate,increasing electrolyte concentration and increasing time step. The CA model was applied to simulate the growth and change of pitting corrosion of metal materials with their corrosion protection layer under damaged conditions. The corrosion model can simulate the corrosion morphology change characteristics similar to the real metal to the corrosion pit evolution simulation related research has certain scientific, validity, reference.

Modeling Potassium Capture by Aluminosilicate, Part 1: Kaolin

Additives rich in Si and Al such as kaolin may be applied in PF biomass boilers to fix alkali metals in species that are more benign than the alkali salts released in biomass combustion. In this study, models for the reaction of gas-phase potassium salts with kaolin particles are developed for the conditions appearing in PF boilers such as short residence times, high temperatures, and small size of the additive particles. The reaction between gaseous potassium components and kaolin particles has been modeled with a shrinking core model (SCM) and a uniform conversion model (UCM). The SCM takes into account the effects of chemical kinetics, diffusion in a gas film surrounding the particle, diffusion in a product layer, and thermochemical equilibrium on the reaction progress. The UCM covers diffusion in a gas film surrounding the particles, chemical kinetics, and thermochemical equilibrium. Both models are able to accommodate the effects of change in temperature, particle size, reaction time, and potassium component concentration. Literature data from experiments in an entrained flow-reactor (EFR) at 800–900 °C were used to derive the chemical kinetic rate coefficients of the reaction between kaolin and KOH. The models were then evaluated against experimental data for alkali salts of KCl, KOH, K2CO3, and K2SO4 covering temperatures of 800–1450 °C, kaolin particle sizes of 4–14 μm, residence times of 0.8–1.9 s, and salt/additive molar ratios of 0.05–0.96. The evaluation indicated that both SCM and UCM were suitable for a wide range of conditions, but the UCM captured the effect of particle size better. The modeling outcomes suggested that if the reaction time was long enough, the thermochemical equilibrium would be the major limitation in capturing potassium by kaolin at high temperatures and high potassium concentrations. At lower temperatures, however, the conversion was mainly limited by chemical kinetics. The mass-transfer limitation was less critical under the investigated conditions. The developed models can account for the reaction of gas-phase potassium salts with kaolin at local conditions relevant to PF boilers using biomass.

Apparent Activation Energy in Electrochemical Multistep Reactions: A Description via Sensitivities and Degrees of Rate Control

Activation energy is a well-known empirical parameter in chemical kinetics that characterizes the dependence of the chemical rate coefficients on the temperature and provides information to compare...

Oxidation kinetics of biochar from woody and herbaceous biomass

The goal of this study was to determine oxidation kinetics for biochar produced from fast pyrolysis of various biomass feedstocks. In particular, the role of inherent ash content on the oxidation rate was evaluated. Thermogravimetric analysis (TGA) and fluidized bed combustion experiments were used to explore oxidation kinetics of six fast pyrolysis produced biochars with diverse ash content. Reaction rates varied by a factor of three under chemical kinetic-limited conditions, demonstrating inorganic content impacts oxidation rate. Chemical kinetic rate coefficients were proposed as a function of compositional parameters to determine overall fit and impact. Potassium content was found to have a positive correlation, best describing the differences in the oxidation kinetic rate coefficients. Additionally, feedstocks were subjected to a 1 M HCl acid wash mitigating the catalytic activity of the metals. Acid washed biochars had lower oxidation kinetic rates compared to their unwashed counterparts, indicating the removal of catalytically active metals reduced oxidation rate. Gas composition (CO/CO2) was measured during fluidized bed experiments for both acid-washed and unwashed biochars, which varied between the six biochars. Formation of CO2 was greatly affected by catalytic metals, finding potassium content to correlate well with a higher percentage of CO2 formation as compared to CO. Comparison of oxidation rates were made between the two experimental apparatuses to measure the effect of attrition on biochar oxidation.

Global Warming Potential (GWP) for Methane: Monte Carlo Analysis of the Uncertainties in Global Tropospheric Model Predictions

Estimates of the global warming potential (GWP) of methane rely on the predictions from global chemistry-transport models. These models employ many uncertain input parameters representing the sources and sinks for methane and those for the tropospheric ozone, which is formed as a by-product of the methane sink process. Five thousand quasi-randomly Monte Carlo sampled model runs employing a zonally averaged global model were completed, each with a base case and a pulse case that differed from the base case only in having an additional 149 Tg (1Tg = 109 kg) emission pulse of methane. Each of the five thousand pulse case experiments had a small excess of methane that decayed away throughout the twenty-year model experiment. The radiative forcing consequences of this excess methane, and the excess tropospheric ozone formed from it, were integrated over a 100-year time horizon. The GWP was calculated in each of the five thousand model experiments from the sum of the radiative forcing consequences of methane and tropospheric ozone, by expressing them relative to the radiative forcing consequences of an identical emission pulse of carbon dioxide. The 2-sigma confidence range surrounding the methane atmospheric lifetime estimated in the Monte Carlo analysis was considerably wider than that derived from observations, suggesting that some of the input parameter combinations may have been unrealistic. The rejection of the unrealistic Monte Carlo replicates increased the mean methane GWP and narrowed its 2-sigma confidence interval to 37 ± 10 over a 100-year time horizon for emission pulses of the order of 1 Tg. Multiple linear regression was used to attribute the uncertainty in the output GWPs to each of the 183 uncertain input parameters, which represented emission source sectors, chemical kinetic rate coefficients, dry deposition velocities and biases in temperature and water vapour concentrations. Overall, the only significant contributions to the uncertainty in the methane GWP came from the chemical kinetic parameters representing the CH4 + OH, CH3O2 + HO2, CH3O2 + NO and the terpene + O3 reaction rate coefficients.

Monte Carlo analyses of the uncertainties in the predictions from global tropospheric ozone models: Tropospheric burdens and seasonal cycles

Abstract Because ozone is a highly reactive trace gas, estimates of its contribution to climate forcing must rely on global chemistry-transport models. These models employ many uncertain input parameters representing the sources and sinks for tropospheric ozone. Ten thousand quasi-randomly Monte Carlo sampled model runs employing a zonally-averaged global ozone model were completed and the output uncertainties were estimated in the burdens and turnovers of methane, carbon monoxide and ozone, together with the uncertainties in the ozone seasonal cycles. Multiple regression was then used to attribute the uncertainty in each output metric to each of the 183 uncertain input parameters which represented emission source sectors, chemical and photochemical rate coefficients, dry deposition velocities and biases in temperature and water vapour concentrations. We have tentatively identified sixteen chemical and photochemical rate coefficients, eight emission source sectors, ozone dry deposition and biases in temperature and water vapour as contributing most to the uncertainties in our chosen output metrics. Ten out of the sixteen chemical processes turned out to be the most important processes in the fast, photochemical balance of the troposphere. Emissions from NOx, methane, carbon monoxide and isoprene had the potential to contribute in a major way to model output uncertainties. There are, however, many limitations to our study, not the least being our use of a two-dimensional (altitude-latitude) ozone model. We have not been able to resolve the apparent conflicts between our model and the observations of ozone seasonal cycles and these must await a more rigorous treatment of tropospheric ozone sources and sinks before they can be resolved.

A continuous time random walk (CTRW) integro-differential equation with chemical interaction

A nonlocal-in-time integro-differential equation is introduced that accounts for close coupling between transport and chemical reaction terms. The structure of the equation contains these terms in a single convolution with a memory function M (t), which includes the source of non-Fickian (anomalous) behavior, within the framework of a continuous time random walk (CTRW). The interaction is non-linear and second-order, relevant for a bimolecular reaction A + B → C. The interaction term ΓP A (s, t) P B (s, t) is symmetric in the concentrations of A and B (i.e. P A and P B ); thus the source terms in the equations for A, B and C are similar, but with a change in sign for that of C. Here, the chemical rate coefficient, Γ, is constant. The fully coupled equations are solved numerically using a finite element method (FEM) with a judicious representation of M (t) that eschews the need for the entire time history, instead using only values at the former time step. To begin to validate the equations, the FEM solution is compared, in lieu of experimental data, to a particle tracking method (CTRW-PT); the results from the two approaches, particularly for the C profiles, are in agreement. The FEM solution, for a range of initial and boundary conditions, can provide a good model for reactive transport in disordered media.

ChemInform Abstract: Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications

AbstractReview: 109 refs.

Chemical Reaction Rate Coefficients from Ring Polymer Molecular Dynamics: Theory and Practical Applications.

This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.

General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures.

This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model's accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy relaxation model, which can only be applied to molecules, the new model is applicable to atoms, molecules, ions, and their mixtures. Numerical examples and model validations are carried out with two gas mixtures using the maximum entropy linear model: one mixture consists of nitrogen molecules undergoing internal excitation and dissociation and the other consists of nitrogen atoms undergoing internal excitation and ionization. Results show that the original hundreds to thousands of microscopic equations can be reduced to two macroscopic equations with almost perfect agreement for the total number density and total internal energy using only one or two groups. We also obtain good prediction of the microscopic state populations using 5-10 groups in the macroscopic equations.

Status and Prospects on Nonequilibrium Modeling of High Velocity Plasma Flow in an Arcjet Thruster

Accurate numerical modeling is prerequisite of predicting plasma behavior and understanding the complex physical and chemical processes in a plasma system. The evolution of nonequilibrium modeling of arcjet to its current state of development is traced, and some uncertainties in the way of further progress are discussed. It is demonstrated that the accuracy of two-temperature plasma transport coefficients can be improved by adopting more reasonable interatomic potentials. A comparison of the chemical kinetic rate coefficients for the same kinetic process shows some discrepancies, which further indicates that there exist some uncertainties on the inelastic cross sections obtained from experimental measurement or theoretic calculation. Application and extension of three-level atomic model of argon in nonequilibrium modeling are briefly reviewed, and the criteria required in the choice of chemical kinetic processes are discussed. The elementary processes involved in high velocity plasma flow can be investigated by collisional radiative model (CR model). The method of applying CR model on the analysis of nonequilibrium plasma processes in arcjet is presented as an example in some detail.

New transformation proposed for improving CFD simulation of free radical polymerization reactions in microreactors

A new yet simple transformation is proposed to significantly improve the accuracy of computational fluid dynamics (CFD) modeling and simulations of free radical polymerization (FRP) reactions carried out especially in flow microreactors. The new transformation makes the kinetic rate coefficients dimensionless in terms of concentration. To that extent, the chemical data (chemical species concentration and kinetic rate coefficients values) can be fed in original molar form instead of usual mass form to CFD software package while simulating chemical species as passive scalars. The normalization of various variables (passive scalars) helps in reducing the numerical stiffness as well as numerical errors during simulations. Another advantage of this new transformation is that the expression for transformed reaction rate equations remains unchanged thus enabling an easy coding and debugging process. The new transformation was first validated through numerical simulation against theoretical analytical solution of FRP for homogeneous batch reactor. It was then validated through CFD simulation against published experimental data for FRP in coiled tube microreactor under steady-state flow condition. It has also been demonstrated that in CFD simulations of FRP in flow microreactors, significant error arises for the prediction of number-average chain length (and thus $${\text{MW}}_{n}$$ , number-average molecular weight) from the use of chemical data in mass form instead of original molar form. This new transformation is thus found to be more suitable for CFD simulations in flow reactors compared to previous Zhu’s transformation.

Kinetic Modeling of Radical Thiol–Ene Chemistry for Macromolecular Design: Importance of Side Reactions and Diffusional Limitations

The radical thiol–ene coupling of thiol-functionalized polystyrene (PS-SH) with dodecyl vinyl ether (DVE) and the polystyrene-b-poly(vinyl acetate) (PS-b-PVAc) polymer–polymer conjugation using 2,2-dimethoxy-2-phenylacetophenone (DMPA) as photoinitiator are modeled to assess the importance of diffusional limitations and side reactions. Intrinsic chemical rate coefficients are determined based on a kinetic study of the coupling of benzyl thiol (BT) and DVE. The addition and transfer reactions are chemically controlled, whereas diffusional limitations on termination slightly increase the coupling efficiency. Termination by recombination of carbon-centered radicals and addition of DMPA derived radicals to DVE are shown to be mainly responsible for the reduced coupling efficiency in case polymeric species are involved. The obtained results confirm the idea to disregard radical thiol–ene chemistry as a true member of the family of “click” chemistry techniques for polymer–polymer conjugation and show that the initial conditions have a significant impact on the coupling efficiency.

Laboratory Astrochemistry: Gas-Phase Processes

A major aim of astrochemistry is to explain the nature and abundance of the molecules observed in the interstellar medium (ISM). Three kinds of activity are involved: (a) the spectroscopic identification of the species that are present in the ISM; (b) the construction of large chemical models that attempt to explain the syntheses of the observed molecules; and (c) efforts to measure or predict crucial information, such as rate coefficients for the chemical reactions that are included in the models. Models can also be employed to identify the processes that exert a major influence on the predicted abundances of observed species. Clearly, it is important that the fundamental aspects of these processes—for example, the chemical rate coefficients—are quantified as accurately as possible. This is the role of laboratory experiments, aided by theory, and this review provides a critical examination of the experimental methods that provide these data and summarizes both the results that have been obtained for gas-phase processes and their reliability.

Evaluation of simulated photochemical partitioning of oxidized nitrogen in the upper troposphere

Abstract. Regional and global chemical transport models underpredict NOx (NO + NO2) in the upper troposphere where it is a precursor to the greenhouse gas ozone. The NOx bias has been shown in model evaluations using aircraft data (Singh et al., 2007) and total column NO2 (molecules cm−2) from satellite observations (Napelenok et al., 2008). The causes of NOx underpredictions have yet to be fully understood due to the interconnected nature of simulated emission, transport, and chemistry processes. Recent observation-based studies, in the upper troposphere, identify chemical rate coefficients as a potential source of error (Olson et al., 2006; Ren et al., 2008). Since typical chemistry evaluation techniques are not available for upper tropospheric conditions, this study develops an evaluation platform from in situ observations, stochastic convection, and deterministic chemistry. We derive a stochastic convection model and optimize it using two simulated datasets of time since convection, one based on meteorology, and the other on chemistry. The chemistry surrogate for time since convection is calculated using seven different chemical mechanisms, all of which predict shorter time since convection than our meteorological analysis. We evaluate chemical simulations by inter-comparison and by pairing results with observations based on NOx:HNO3, a photochemical aging indicator. Inter-comparison reveals individual chemical mechanism biases and recommended updates. Evaluation against observations shows that all chemical mechanisms overpredict NOx removal relative to long-lived methanol and carbon monoxide. All chemical mechanisms underpredict observed NOx by at least 30%, and further evaluation is necessary to refine simulation sensitivities to initial conditions and chemical rate uncertainties.

Strong dependence of ultracold chemical rates on electric dipole moments

We use the quantum threshold laws combined with a classical capture model to provide an analytical estimate of the chemical quenching cross sections and rate coefficients of two colliding particles at ultralow temperatures. We apply this quantum threshold model (QT model) to indistinguishable fermionic polar molecules in an electric field. At ultracold temperatures and in weak electric fields, the cross sections and rate coefficients depend only weakly on the electric dipole moment d induced by the electric field. In stronger electric fields, the quenching processes scale as d^{4(L+1/2)} where L>0 is the orbital angular momentum quantum number between the two colliding particles. For p-wave collisions (L=1) of indistinguishable fermionic polar molecules at ultracold temperatures, the quenching rate thus scales as d^6. We also apply this model to pure two dimensional collisions and find that chemical rates vanish as d^{-4} for ultracold indistinguishable fermions. This model provides a quick and intuitive way to estimate chemical rate coefficients of reactions occuring with high probability.

QUANTUM CHEMICAL PREDICTIONS OF THE PROPERTIES OF KNOWN AND POSTULATED NEUTRAL INTERSTELLAR MOLECULES

In order to make new predictions for chemical rate coefficients for ion-molecule reactions, quantum chemical calculations were performed for about 200 neutral molecules with up to 12 atoms that are known or postulated to be present in interstellar or circumstellar sources. After optimizing equilibrium structures, dipole moment and dipole polarizability components were computed using the finite field approach. Properties were computed at the RCCSD(T) level with basis sets as large as aug-cc-pVTZ, depending upon the size of the molecule. Comparisons are made to existing experimental data, which are quite limited in the case of dipole polarizabilities.