Reaction Rate Coefficients Research Articles

Dissociative recombination of NS+ in collision with slow electrons

Cross sections and rate coefficients for the dissociative recombination (DR) of the NS+ ion induced by collisions with low-energy electrons are reported for temperatures between 10 and 1000 K, relevant to a large range of interstellar cloud temperatures. Uncertainties are discussed for these rates. Comparisons are made with DR rates for the isovalent NO+ molecular ion which are found to be much faster. The present findings lead to a moderate dissociative reaction rate coefficient, smaller by a factor of 2 than the current estimates reported in the different kinetic databases for a temperature of 10 K. We consider that our rate coefficients obtained through multichannel quantum defect theory for NS+ are likely to be better than those displayed in the different kinetic databases.

High-Temperature Pyrolysis Study of 2-Methyl-2-butanol behind Reflected Shock Wave: Shock Tube and Computational Study.

Pyrolysis of a branched alcohol, 2-methyl-2-butanol (2M2BOH), was carried out behind the reflected shock wave in the temperature range of 1011-1303 K and under pressures varying from 9.3 to 14.6 atm. Qualitative and quantitative analysis of the postshock mixture was performed using gas chromatography-mass spectrometry and gas chromatography with a flame ionization detector, respectively. The rate coefficients for the C-C and C-O bond cleavage reaction pathways were calculated using the variational transition-state theory. The Rice-Ramsperger-Kessel-Marcus/Master equation was employed to calculate the rate coefficients for the H2O-elimination reactions, unimolecular dissociation, and isomerization reaction pathways. The overall decomposition rate coefficient for the 2-methyl 2-butanol (2M2BOH) was estimated to be , where activation energy is given in kcal mol-1. The reaction path analysis was performed, which gives information regarding the contribution of individual intermediate species toward the decomposition of 2M2BOH. A set of reactions was proposed and used to simulate the combustion chemistry of 2M2BOH, which consists of 48 reactions and 39 species. The experimentally measured and simulated mole fractions for the reactant and products showed reasonably good agreement. This work additionally investigates the effect of branching on the decomposition kinetics of long-chain alcohols.

Experimental and chemical kinetic analysis to evaluate CO2 dilution on laminar combustion characteristics of C2H5OH/air blends under normal pressure

Based on a constant volume combustion system, the effect of dilution ratio changes on the laminar combustion characteristics of C2H5OH/air mixture was studied under an initial pressure of 1 bar, initial temperatures of 370 K, 400 K, 450 K, and equivalence ratios of 0.7–1.4. A chemical kinetic mechanism for ethanol-carbon dioxide was established, and the combined physical and chemical effects of carbon dioxide were separated. An independent parameter control method was proposed, introducing virtual species FN2, ICO2, FCO2, and KCO2, to isolate the dilution effect, thermal effect, direct reaction effect, third-body effect, and transport effect. Simulation analysis using the modified chemical kinetic mechanism revealed that various impacts of CO2 reduce the peak progress rate and sensitivity coefficient of key elementary reactions. Furthermore, the dilution effect of CO2 has the greatest influence on the sensitivity coefficients and net progress rates of important elementary reactions. Based on the results of the chemical kinetic simulations, a new global reaction pathway analysis method was created, overcoming the limitations of the Chemkin-pro method. The decomposition pathway of C2H5OH throughout the combustion process was calculated as C2H5OH → SC2H4OH → CH3CHO → CH3CO → CH3 → CH2O → HCO → CO → CO2. Changes in initial temperature and dilution ratio do not alter the main decomposition pathway of C2H5OH. Detailed chemical kinetics and free radical behavior analysis indicate that the LBV of the C2H5OH/CO2/air blends has a linear correlation with [H + O + OH]max.

Hydrogen isotope effects on recombination dominant plasmas in NAGDIS-II

The detachment processes of the hydrogen (H) and deuterium (D) plasmas are comparatively investigated in the linear plasma device NAGDIS-II. The laser Thomson scattering measurements demonstrate that the recombination rate of the H plasma is greater than that of the D plasma as the neutral pressure increases in the molecular activated recombination (MAR) dominant detachment phase. As the recombination process by MAR is strongly dependent on the vibrational and rotationally excited states of the molecule, the rovibrational quantum state populations of the H and D molecules are measured using the Fulcher-α band spectroscopy. The results indicate that the vibrational temperature in the electronic ground state is considerably higher than the rotational temperature during detachment. The reaction rate coefficients for MARs due to charge exchange chains (CX-MAR) and dissociative attachment chains (DA-MAR) are calculated by the collision-radiation model under the measured temperature conditions. It can be observed that the CX-MAR is larger than the DA-MAR for both H and D, and that the CX-MAR of H is larger than the CX-MAR of D at electron temperatures T e above 1 eV. In consideration of the experimentally observed vibrational and rotational excitation temperatures, the reaction rate coefficients of CX-MAR and DA-MAR are increasing in the low T e region. These calculations are in accordance with the experimental results, which indicate that recombination processes due to MAR are more predominant in the H plasma compared to the D plasma. Furthermore, a transition from MAR to electron–ion recombination processes is observed in the D plasma at T e below 0.5 eV.

Causal prior-embedded physics-informed neural networks and a case study on metformin transport in porous media

This study introduces a novel approach to transport modelling by integrating experimentally derived causal priors into neural networks. We illustrate this paradigm using a case study of metformin, a ubiquitous pharmaceutical emerging pollutant, and its transport behaviour in sandy media. Specifically, data from metformin's sandy column transport experiment was used to estimate unobservable parameters through a physics-based model Hydrus-1D, followed by a data augmentation to produce a more comprehensive dataset. A causal graph incorporating key variables was constructed, aiding in identifying impactful variables and estimating their causal dynamics or “causal prior.” The causal priors extracted from the augmented dataset included underexplored system parameters such as the type-1 sorption fraction F, first-order reaction rate coefficient α, and transport system scale. Their moderate impact on the transport process has been quantitatively evaluated (normalized causal effect 0.0423, -0.1447 and -0.0351, respectively) with adequate confounders considered for the first time. The prior was later embedded into multilayer neural networks via two methods: causal weight initialization and causal prior regularization. Based on the results from AutoML hyperparameter tuning experiments, using two embedding methods simultaneously emerged as a more advantageous practice since our proposed causal weight initialization technique can enhance model stability, particularly when used in conjunction with causal prior regularization. amongst those experiments utilizing both techniques, the R-squared values peaked at 0.881. This study demonstrates a balanced approach between expert knowledge and data-driven methods, providing enhanced interpretability in black-box models such as neural networks for environmental modelling.

The reaction of methylidyne with methane: role of the quartet electronic state

The reaction of methylidyne (CH) with methane, which plays an important role in combustion and planetary atmospheres, is characterised with high accuracy coupled-cluster calculations. The reaction on the quartet state potential energy surface (PES) is predicted to lead to direct H-abstraction with a small barrier of 2.2 kcal mol−1, yielding triplet CH2 and CH3. The reaction on the doublet state PES is barrierless, involving an insertion/elimination mechanism that leads to the vibrationally excited (hot) intermediate C2H5, which promptly dissociates to H + C2H4. The results obtained from a statistical chemical kinetics analysis show that the quartet channel makes a negligible contribution to the overall kinetics below 500 K, but becomes important at the higher temperatures characteristic of hydrocarbon flames. Reaction rate coefficients calculated from first principles are in good agreement (within 20%) with experimental values where they are available (200–800 K). For the higher temperatures of combustion environments (where experimental data are lacking), the present study provides high-level results for kinetics modelling purposes.

Gas-Phase Kinetic Investigation of the OH-Initiated Oxidation of a Series of Methyl-Butenols under Simulated Atmospheric Conditions.

Five biogenic unsaturated alcohols have been investigated under simulated atmospheric conditions regarding their gas-phase OH reactivity. The gas-phase rate coefficients of OH radicals with 2-methyl-3-buten-2-ol (k1), 3-methyl-2-buten-1-ol (k2), 3-methyl-3-buten-1-ol (k3), 2-methyl-3-buten-1-ol (k4), and 3-methyl-3-buten-2-ol (k5) at 298 ± 2 K and 1000 ± 10 mbar total pressure of synthetic air were determined under low- and high-NOx conditions using the relative kinetic technique. The present work provides for the first time the rate coefficients of gas-phase reactions of hydroxyl radicals with 2-methyl-3-buten-1-ol and 3-methyl-3-buten-2-ol. The following rate constants were measured (in 10-11 cm3 molecule-1 s-1): k1 = 6.32 ± 0.49, k2 = 14.55 ± 0.93, k3 = 10.04 ± 0.78, k4 = 5.31 ± 0.37, and k5 = 11.71 ± 1.29. No significant differences in the measured rate coefficients were obtained when either 365 nm photolysis of CH3ONO in the presence of NO or 254 nm photolysis of H2O2 was used as a source of OH radicals. Reactivity toward other classes of related compounds such as alkenes and saturated alcohols is discussed. A comparison of the structure-activity relationship (SAR) estimates derived from the available accepted methodologies with experimental data available for unsaturated alcohols is provided. Atmospheric lifetimes for the investigated series of alkenols with respect to the main atmospheric oxidants are given and discussed.

Two Film Approach to Continuum Scale Mixing and Dispersion with Equilibrium Bimolecular Reaction

Reliable reactive transport models require careful separation of mixing and dispersion processes. Here we treat displacing and displaced fluids as two separate fluid phases and invoke Whitman’s classical two-film theory to model mass transfer between the two phases. We use experimental data from Gramling’s bimolecular reaction experiment to assess model performance. Gramling’s original model involved just three coupled PDEs. In this context, our new formulation leads to a set of seven coupled PDEs but only requires the specification of two extra parameters, associated with the mass transfer coefficient and its dependence on time. The two film mass transfer model provides a simple and theoretically based method for separating mixing from dispersion in Eulerian continuum-scale methods. The advantage of this approach over existing methods is that it enables the simulation of equilibrium chemical reactions without having to invoke unrealistically small reaction rate coefficients. The comparison with Gramling’s experimental data confirms that our proposed method is suitable for simulating realistic and complicated bimolecular reaction behaviour. However, further work is needed to explore alternative methods for avoiding the need of a time-dependent mass transfer rate coefficient.

Direct Measurements of Covalently Bonded Sulfuric Anhydrides from Gas-Phase Reactions of SO3 with Acids under Ambient Conditions.

Sulfur trioxide (SO3) is an important oxide of sulfur and a key intermediate in the formation of sulfuric acid (H2SO4, SA) in the Earth's atmosphere. This conversion to SA occurs rapidly due to the reaction of SO3 with a water dimer. However, gas-phase SO3 has been measured directly at concentrations that are comparable to that of SA under polluted mega-city conditions, indicating gaps in our current understanding of the sources and fates of SO3. Its reaction with atmospheric acids could be one such fate that can have significant implications for atmospheric chemistry. In the present investigation, laboratory experiments were conducted in a flow reactor to generate a range of previously uncharacterized condensable sulfur-containing reaction products by reacting SO3 with a set of atmospherically relevant inorganic and organic acids at room temperature and atmospheric pressure. Specifically, key inorganic acids known to be responsible for most ambient new particle formation events, iodic acid (HIO3, IA) and SA, are observed to react promptly with SO3 to form iodic sulfuric anhydride (IO3SO3H, ISA) and disulfuric acid (H2S2O7, DSA). Carboxylic sulfuric anhydrides (CSAs) were observed to form by the reaction of SO3 with C2 and C3 monocarboxylic (acetic and propanoic acid) and dicarboxylic (oxalic and malonic acid)-carboxylic acids. The formed products were detected by a nitrate-ion-based chemical ionization atmospheric pressure interface time-of-flight mass spectrometer (NO3--CI-APi-TOF; NO3--CIMS). Quantum chemical methods were used to compute the relevant SO3 reaction rate coefficients, probe the reaction mechanisms, and model the ionization chemistry inherent in the detection of the products by NO3--CIMS. Additionally, we use NO3--CIMS ambient data to report that significant concentrations of SO3 and its acid anhydride reaction products are present under polluted, marine and polar, and volcanic plume conditions. Considering that these regions are rich in the acid precursors studied here, the reported reactions need to be accounted for in the modeling of atmospheric new particle formation.

Direct Kinetic Measurements of a Cyclic Criegee Intermediate; Unimolecular Decomposition of c-(CH2)5COO.

We report the first direct kinetic measurements of a cyclic stabilized Criegee Intermediate. We have measured the unimolecular reaction rate coefficient of cyclohexanone oxide (c-(CH2)5COO) in the temperature 213-296 K and pressure 7-50 Torr ranges using absorption spectrometry. The c-(CH2)5COO was produced by the photolysis of c-(CH2)5CIBr at 213 nm in the presence of O2. We compare the measured fast c-(CH2)5COO unimolecular rate coefficient, 1998 ± 147 s-1 at 296 K, with the literature calculations for the structurally similar E-nopinone oxide formed in β-pinene ozonolysis. The kuni(c-(CH2)5COO)/kuni(E-nopinone oxide) ratio calculated using transition-state theory and density functional theory agrees well with this comparison. We have also measured the bimolecular rate coefficient of the reaction between c-(CH2)5COO and trifluoroacetic acid at 253 K and 10 Torr and obtained the value (8.7 ± 1.0) × 10-10 cm3 molecule-1 s-1. This very large value agrees with previous kinetic measurements for reactions between stabilized Criegee intermediates and halogenated organic acids.

The chemistry and excitation of H2 and HD in the early Universe

ABSTRACT We have critically reviewed the literature pertaining to reactions that are significant for the chemistry of hydrogen-, deuterium-, and helium-bearing species in the homogeneous early Universe. For each reaction rate coefficient, we provide a fit in the modified-Arrhenius form, specifying the corresponding uncertainty and temperature range. This new network, limited to 21 reactions, should be the most reliable to date. Combined with accurate state-to-state rate coefficients for inelastic and reactive collisions involving H2 and HD, it allows us for the first time to follow the evolution of the abundances of atomic and molecular species, level populations of H2 and HD, and the ortho:para ratio (OPR) of H2, in a self-consistent fashion during the adiabatic expansion of the universe. The abundances of H2 and HD change only marginally compared to previous models, indicating that the uncertainties on the main reaction rate coefficients have essentially been removed. We also find that the adiabatic expansion has a dramatic effect on the OPR of H2, which freezes-out at redshifts z ≲ 50. In contrast, at higher redshifts, the populations of the rotational levels of H2 and HD are predicted to be fully thermalized at the temperature of the cosmic background radiation field, a result that conflicts with some recent, independent calculations. This new network allows the chemistry of primordial gas to be followed during the early phase of collapse towards Population III star progenitors.

Chemical Kinetic Study of the Reaction of CH2OO with CH3O2.

Criegee intermediates play an important role in the oxidizing capacity of the Earth's troposphere. Although extensive studies have been conducted on Criegee intermediates in the past decade, their kinetics with radical species remain underexplored. We investigated the kinetics of the simplest Criegee intermediate, CH2OO, with the methyl peroxy radical, CH3O2, as a model system to explore the reactivities of Criegee intermediates with peroxy radicals. Using a multipass UV-Vis spectrometer coupled to a pulsed-laser photolysis flow reactor, CH2OO and CH3O2 were generated simultaneously from the photolysis of CH2I2/CH3I/O2/N2 mixtures with CH2OO measured directly near 340 nm. We determined a reaction rate coefficient kCH2OO+CH3O2 = (1.7 ± 0.5) × 10-11 cm3 s-1 at 294 K and 10 Torr, where the influence of iodine adducts is reduced. This rate coefficient is faster than previous theoretical predictions, highlighting the challenges in accurately describing the interaction between zwitterionic and biradical characteristics of Criegee intermediates.

Improved Approach for ab Initio Calculations of Rate Coefficients for Secondary Reactions in Acrylate Free-Radical Polymerization.

Secondary reactions in radical polymerization pose a challenge when creating kinetic models for predicting polymer structures. Despite the high impact of these reactions in the polymer structure, their effects are difficult to isolate and measure to produce kinetic data. To this end, we used solvation-corrected M06-2X/6-311+G(d,p) ab initio calculations to predict a complete and consistent data set of intrinsic rate coefficients of the secondary reactions in acrylate radical polymerization, including backbiting, β-scission, radical migration, macromonomer propagation, mid-chain radical propagation, chain transfer to monomer and chain transfer to polymer. Two new approaches towards computationally predicting rate coefficients for secondary reactions are proposed: (i) explicit accounting for all possible enantiomers for reactions involving optically active centers; (ii) imposing reduced flexibility if the reaction center is in the middle of the polymer chain. The accuracy and reliability of the ab initio predictions were benchmarked against experimental data via kinetic Monte Carlo simulations under three sufficiently different experimental conditions: a high-frequency modulated polymerization process in the transient regime, a low-frequency modulated process in the sliding regime at both low and high temperatures and a degradation process in the absence of free monomers. The complete and consistent ab initio data set compiled in this work predicts a good agreement when benchmarked via kMC simulations against experimental data, which is a technique never used before for computational chemistry. The simulation results show that these two newly proposed approaches are promising for bridging the gap between experimental and computational chemistry methods in polymer reaction engineering.

A numerical compass for experiment design in chemical kinetics and molecular property estimation

Kinetic process models are widely applied in science and engineering, including atmospheric, physiological and technical chemistry, reactor design, or process optimization. These models rely on numerous kinetic parameters such as reaction rate, diffusion or partitioning coefficients. Determining these properties by experiments can be challenging, especially for multiphase systems, and researchers often face the task of intuitively selecting experimental conditions to obtain insightful results. We developed a numerical compass (NC) method that integrates computational models, global optimization, ensemble methods, and machine learning to identify experimental conditions with the greatest potential to constrain model parameters. The approach is based on the quantification of model output variance in an ensemble of solutions that agree with experimental data. The utility of the NC method is demonstrated for the parameters of a multi-layer model describing the heterogeneous ozonolysis of oleic acid aerosols. We show how neural network surrogate models of the multiphase chemical reaction system can be used to accelerate the application of the NC for a comprehensive mapping and analysis of experimental conditions. The NC can also be applied for uncertainty quantification of quantitative structure–activity relationship (QSAR) models. We show that the uncertainty calculated for molecules that are used to extend training data correlates with the reduction of QSAR model error. The code is openly available as the Julia package KineticCompass.Graphical

Atmospheric chemistry of trifluorodicarbonyls initiated by Cl atoms: Reactivity trends, mechanism, and acid formation yields

Rate coefficients of the gas-phase reactions of Cl atoms with a series of fluorinated diketones (FDKs): CF3C(O)CH2C(O)CH3 (TFP), CF3C(O)CH2C(O)CH2CH3 (TFH) and CF3C(O)CH2C(O)CH(CH3)2 (TFMH), have been measured at (298 ± 2) K and under atmospheric pressure. The experiments were performed using the relative-rate method with a GC-FID detection system. From different determinations and references used, the following rate coefficients were obtained (in cm3/(molecule·sec)): k4(TFP + Cl) = (1.75 ± 0.21) × 10−10, k5(TFH + Cl) = (2.05 ± 0.23) × 10−10, k6(TFMH + Cl) = (2.71 ± 0.34) × 10−10. Reactivity trends of FDKs were discussed and Free Energy Relationships analysis was developed. The expression lgkOH = 1.68 lgkCl + 5.71 was obtained for the reactivity of the studied FDKs together with similar unsaturated VOCs with Cl and OH radicals Additionally, acetic acid (CH3C(O)OH) and trifluoroacetic acid (CF3C(O)OH) were positively identified and quantified as degradation products using in situ FTIR spectroscopy. According to the identified products, atmospheric chemical mechanisms were proposed. The atmospheric implications of the studied reactions were assessed by the estimation of the tropospheric lifetimes of TFP, TFH, and TFMH concerning their reaction with Cl atoms to be 48, 41, and 31 hours, respectively. The relatively short residence in the atmosphere of the fluorocarbons studied will have a local/regional impact with restricted transport. Global warming potential (GWP(20yr)) calculated for the studied fluoro diketones were 0.014, 0.003 and 0.001 for TFP, TFH and TFMH, respectively with a negligible contribution to the greenhouse effect.

Mechanism insights into low-temperature oxidation of n-heptane on CeO2 surface: A DFT study

The low-temperature oxidation (LTO) mechanism of n-heptane on CeO2 surfaces was investigated in this study employing density functional theory (DFT). Firstly, the adsorption conformations of relevant species were optimized, and the main reaction steps' energy barriers and reaction-rate coefficients were calculated. The results show that the hydroxyl groups of fuel radicals strengthen the adsorption of fuel radicals on CeO2 surfaces. Furthermore, the energy barriers associated with the low-temperature (LT) chain branching pathway of n-heptane on the CeO2 surface exhibit lower values compared to those observed in the gas phase. The presence of CeO2 is also observed to mitigate the detrimental impact of competing reactions on the low-temperature branching pathway of n-heptane. It should be noted that the energy barrier for the decomposition of H2O2 on the CeO2 surface is 32.575 kcal/mol, 33.2 % lower than that in the gas phase, which allows H2O2 to be decomposed much easier at low temperatures. The resultant OH radicals desorb to the intimated gas phase, accelerating the oxidation of fuel molecules in the gas phase. Therefore, n-heptane transitioned to high-temperature ignition more easily and rapidly in the presence of CeO2. The calculation's findings adequately explain the experimental finding that adding CeO2 improves diesel fuel combustion.

Can astronomical observations be used to constrain crucial chemical reactions? The methoxy case. SOLIS XVIII

ABSTRACT To understand the origin of interstellar molecules we rely on astrochemical models, the gas-phase networks of which contain ≥7000 reactions. However, just a tiny fraction of them have parameters derived in laboratory experiments. Theoretical quantum mechanical (QM) calculations can also provide this information. Unfortunately, sometimes theoretical predictions and experimental values disagree, as is the case for the paradigmatic reaction CH3OH + OH → CH3O + H2O. Both laboratory experiments and QM calculations found an unexpected increase in the rate coefficients with decreasing temperature. However, experimental and theoretical estimates of the rate coefficients diverge by up to two orders of magnitude at the low temperatures of interest in interstellar chemistry. This work aims to test whether astronomical observations can help untangle this confusing situation. To this end, we first carried out new QM calculations to derive the rate coefficients of the major destruction reaction of the methoxy radical, CH3O + H, and then we compared astronomical observations from the IRAM/NOEMA Large Programme SOLIS with astrochemical model predictions. Our new rate coefficient for the CH3O + H reaction is 5–10 times larger than that in the astrochemical data base KIDA in the 10–100 K range. When including the new methoxy destruction rate coefficients, the comparison between observations and model predictions favours the rate coefficients of the CH3OH + OH reaction from QM calculations. We conclude that QM calculations are an important alternative to laboratory experiments when it comes to the harsh conditions of interstellar objects and that astronomical observations can be used to constraint the rate coefficients of relevant reactions.

A model for the hydrogenation and charge states of fullerene C60. Implications for diffuse interstellar band research

The diffuse interstellar bands (DIBs) are a set of sim 600 absorption features at optical and near-infrared wavelengths that are found in the interstellar medium in the Milky Way and other galaxies. They remain mostly unidentified and represent the greatest unsolved mystery in astronomical spectroscopy of the past 100 years. Many studies indicate that the carrier molecules are likely carbonaceous molecules, such as polycyclic aromatic hydrocarbons (PAHs) or fullerenes, a theory that is supported by the identifications of five DIBs in the near-infrared attributed to C$_ This work aims to narrow down which compounds related to C$_ $ could be promising DIB carrier candidates.\ We did so by conducting a theoretical study of its hydrogenation and charge balance. We defined a system of relevant reactions, and for each reaction we computed or derived from the literature a reaction rate coefficient. Assuming a steady state, we then computed a distribution of relative abundances in each hydrogenation and charge state. From the model outcomes, we expect the most abundant hydrogenated buckminsterfullerene compound in the diffuse interstellar medium to be C$_ $H$^+$.

Numerical simulation of photocurrent transients generated from passive films and anodic films on pure Ti

A numerical simulation of photocurrent transient was proposed to estimate properties of passive films and anodic films formed on pure Ti. To simulate photocurrent transient, partial differential equations describing the change in the concentration and positions of photoexcited charge carriers with time were developed based on the generation, recombination, and transports of the carriers. Simulations were performed by screening several parameters. The electron mobility, donor density, recombination coefficient and interfacial reaction rate coefficient were estimated by fitting simulated photocurrent transients to experimentally obtained transients.

Decomposition mechanism of lumpy dolomite particles

Cylindrical cm-sized dolomite particles were decomposed using the two steps decomposition scheme. Several studies on dolomite decomposition have been done using µm- to mm-sized samples over the years. However, these sizes are too small for industrial kiln application and ignore the influence of important parameters, e.g. thermal conductivity, on the decomposition process. In this work, the decomposition behavior of lumpy dolomite particles in each step was investigated. Experimentally measured sample temperature and conversion profiles in steps 1 and 2 are respectively similar to those obtained for the decomposition of pure magnesite and limestone. To measure the core temperature and conversion is to essentially analyze the decomposition behavior. The thermophysical material properties of the decomposition product in each step as a function of temperature was estimated using the shrinking core model. Finite difference method was employed in solving the 1D heat equation describing the process. The reaction rate coefficient in step 1 is shown to have a weak temperature dependence, the thermal conductivity of the product, MgO∙CaCO3, slightly increases with temperature but the permeability is not dependent. In step 2, the reaction coefficient and MgO∙CaO thermal conductivity and pore diffusivity do not show a clear temperature dependence. Finally, the sensitivity of the material and transport properties on the decomposition process was studied under shaft kiln condition. Thermal conductivity is observed to have the highest influence on decomposition with a value of up to 60 % at 1400 °C and for 120 mm particles.