Rate Constants Of Chemical Reactions Research Articles

Suppressed atmospheric chemical aging of cooking organic aerosol particles in wintertime conditions

Abstract. Cooking organic aerosol (COA) is one of the major constituents of particulate matter in urban areas. COA is oxidized by atmospheric oxidants such as ozone, changing its physical, chemical and toxicological properties. However, atmospheric chemical lifetimes of COA and its tracers such as oleic acid are typically longer than those that have been estimated by laboratory studies. We tackled the issue by considering temperature. Namely, we hypothesize that increased viscosity of COA at ambient temperature accounts for its prolonged atmospheric chemical lifetimes in wintertime. Laboratory-generated COA particles from cooking oil were exposed to ozone in an aerosol flow tube reactor for the temperature range of −20 to 35 °C. The pseudo-second-order chemical reaction rate constants (k2) were estimated from the experimental data by assuming a constant ozone concentration in the flow tube. The estimated values of k2 decreased by orders of magnitude for lower temperatures. The temperature dependence in k2 was fit well by considering the diffusion-limited chemical reaction mechanism. The result suggested that increased viscosity was likely the key factor to account for the decrease in chemical reactivity at the reduced temperature range, though the idea will still need to be verified by temperature-dependent viscosity data in the future. In combination with the observed global surface temperature, the atmospheric chemical lifetimes of COA were estimated to be much longer in wintertime (> 1 h) than in summertime (a few minutes) for temperate and boreal regions. Our present study demonstrates that the oxidation lifetimes of COA particles will need to be parameterized as a function of temperature in the future for estimating environmental impacts and fates of this category of particulate matter.

Activation volume and quantum tunneling in the hydrogen transfer reaction between methyl radical and methane: A first computational study.

We present a theory of the effect of quantum tunneling on the basic parameter that characterizes the effect of pressure on the rate constant of chemical reactions in a dense phase, the activation volume. This theory results in combining, on the one hand, the extreme pressure polarizable continuum model, a quantum chemical method to describe the effect of pressure on the reaction energy profile in a dense medium, and, on the other hand, the semiclassical version of the transition state theory, which includes the effect of quantum tunneling through a transmission coefficient. The theory has been applied to the study of the activation volume of the model reaction of hydrogen transfer between methyl radical and methane, including the primary isotope substitution of hydrogen with deuterium (H/D). The analysis of the numerical results offers, for the first time, a clear insight into the effect of quantum tunneling on the activation volume for this hydrogen transfer reaction: this effect results from the different influences that pressure has on the competing thermal and tunneling reaction mechanisms. Furthermore, the computed kinetic isotope effect (H/D) on the activation volume for this model hydrogen transfer correlates well with the experimental data for more complex hydrogen transfer reactions.

Non-Equilibrium Wigner Function and Application to Model of Catalyzed Polymerization.

The quantum Wigner function and non-equilibrium equation for a microscopic particle in one spatial dimension (1D) subject to a potential and a heat bath at thermal equilibrium are considered by non-trivially extending a previous analysis. The non-equilibrium equation yields a general hierarchy for suitable non-equilibrium moments. A new non-trivial solution of the hierarchy combining the continued fractions and infinite series thereof is obtained and analyzed. In a short thermal wavelength regime (keeping quantum features adequate for chemical reactions), the hierarchy is approximated by a three-term one. For long times, in turn, the three-term hierarchy is replaced by a Smoluchovski equation. By extending that 1D analysis, a new model of the growth (polymerization) of a molecular chain (template or te) by binding an individual unit (an atom) and activation by a catalyst is developed in three spatial dimensions (3D). The atom, te, and catalyst move randomly as solutions in a fluid at rest in thermal equilibrium. Classical statistical mechanics describe the te and catalyst approximately. Atoms and bindings are treated quantum-mechanically. A mixed non-equilibrium quantum-classical Wigner-Liouville function and dynamical equations for the atom and for the te and catalyst, respectively, are employed. By integrating over the degrees of freedom of te and with the catalyst assumed to be near equilibrium, an approximate Smoluchowski equation is obtained for the unit. The mean first passage time (MFPT) for the atom to become bound to the te, facilitated by the catalyst, is considered. The resulting MFPT is consistent with the Arrhenius formula for rate constants in chemical reactions.

Roles of temperature and ventilation in oxygen consumption: A chemical kinetics view from the van't Hoff-based formulation

In this study, we successfully estimated the apparent activation energy of a microbially driven oxygen-consuming reaction (microbial-driven) based on tracer data. The concept of the apparent chemical reaction rate constant was employed to estimate various thermodynamic parameters associated with the oxygen consumption rate in conjunction with Arrhenius/Eyring equations. Normal Ea values of 80–90 kJ mol−1 were found in the upper layers of the South China Sea and Sulu Sea, while higher Ea values (300–1000 kJ mol−1) were observed in the rapidly ventilated Mediterranean Sea, the Sea of Japan, and the Bering Sea with lower temperatures. We classified the characteristics of typical sea basins into four categories. The temperature-dependent oxygen consumption rate relationship in each marine region was systematically calculated to derive the respective thermodynamic characteristic values. This allowed us to parameterize the rate-temperature relationship into thermodynamic quantities, enabling more effective integration of distinct basin characteristics within different sea areas into the marine biochemical model. Parameterization facilitates relatively accurate prediction of changes such as temperature, oxygen consumption rate.

Detailed kinetic mechanism for nitrocellulose low temperature decomposition

In the current investigation a detailed kinetic scheme of nitrocellulose (NC) is developed. Despite being studied for decades, NC did not have a detailed model yet. Thanks to Reaction Mechanism Generator open-source software a NC decomposition scheme has been generated. Optimizations of that model have been performed including intermediates thermodynamic properties calculations with Gaussian 16 at the B3LYP 6-31G(d,p) level of theory. Model reduction and decomposition computations were achieved with Chemkin-Pro. NC detailed mechanism has been optimized thanks to experimental data available in the literature, by slightly adjusting some rate constants of relevant chemical reactions. For instance, mean deviation of NO molar fraction is about 5.64% showing that the model follows the general trend of measured results. The final NC model consists in 62 species and 803 gas phase reactions. Eventually, NC and hexogen (RDX) models have been merged to predict overpressures obtained experimentally on a RDX-NC propellant. Numerical and experimental results have been confronted regarding the ignition temperature, initial pressure and surrounding gas nature. Computed results have been congruent when compared to experimental data, especially under argon atmosphere with an ignition temperature of 1173 K. Evidences from global trends indicate that the developed model can provide encouraging computations results for future research and investigations.

A Theoretical and Experimental Square-Wave Voltammetric Study of Ascorbic Acid in Light of Multi-Step Electron Transfer Mechanism

A detailed theoretical and experimental study of the complex redox mechanism of ascorbic acid in aqueous phosphate buffer solution (pH = 7.3) by square-wave voltammetry is presented. Experimental square-wave voltammograms at edge plane pyrolytic graphite electrode consist of a typical irreversible peak for a direct two-step electrode oxidation of the ascorbic acid. The complex mechanism of oxidation of the ascorbic acid was represented by a theoretical model for E1C’E2C mechanism. Morphology of theoretical square-wave voltammograms greatly depended on different specific parameters of the model. This feature was used to make the best fit between experimental and theoretical voltammograms for 2 different step potentials, which resulted in revelation of all specific parameters (standard electrochemical rate constant, diffusion coefficient, electron transfer coefficient and rate constants for both chemical reactions) of the model. Therefore, we showed that using only square-wave voltammetry, both experimentally and theoretically, it is possible to make a detailed study of the complex oxidation of ascorbic acid and further enlighten its redox mechanism.

Novel 3D analysis of reduction behavior of single iron-oxide particle in CO-CO2 gas atmosphere

The production of steel, which is achieved by the reduction of iron ores mainly through indirect reduction reactions in a blast furnace, is gradually increasing worldwide. Because the reducing gas diffuses three-dimensionally, irregular particle shapes influence the reduction through differences in the diffusion length. The analysis of actual irregularly shaped iron-ore particles using existing models is difficult because they are primarily effective for 1D systems. Therefore, a novel reduction model based on the 3D diffusion equation that accommodates irregular particle shapes and 3D systems was developed in this study. The established model was validated by reproducing experimental conditions and comparing the quantified effective diffusivity and chemical reaction rate constant using the shrinking core model. In addition, the model was used to investigate the reducing behavior of an actual sintered-ore particle and the effects of particle sphericity and macro pore content. The sintered-ore particle had a higher reduction rate than that of a spherical equivalent with the same volume because sections of the surface with shorter diffusion lengths facilitated the gas diffusion. Additionally, the particle sphericity was determined to be inversely proportional to the reduction rate because the rate of gas diffusion into the particle depended on the diffusion length. With respect to porous particles, the gas was found to readily diffuse into the particles through pores, leading to a higher reduction rate for higher pore numbers. Overall, the gas diffusion was confirmed to drive the reduction reaction.

A chemical credit framework to predict the removal performance of organic chemicals of concern from water through an ozonation process

Ozonation is an effective barrier for removing a wide spectrum of organic Chemicals of Concern (CoC) in a water treatment process. In this study, bench- and full-scale tests were conducted on a secondary treated effluent at the Eastern Treatment Plant (ETP) of Melbourne Water to probe the performance of ozonation in removing CoC in a wastewater discharge. From the secondary treated effluent as the feed to the ozone process, 58 organic chemicals were measured out of a possible 949 compounds by using the AIQS-DB analytical method. A chemical credit framework for the ozonation process has been established according to the bench-scale results. Chemical classifications based on the chemical structures (aromatics, aliphatic and halogenated aliphatic compounds) and reaction rate constants with O3 (KO3) and the ∙OH radical (K∙OH) and a combined O3/TOC ratio and O3 CT value as operating parameters were confirmed to be useful and important in determining whether a chemical would be removed by ozone. It is shown that an O3/TOC ratio of >0.404 was shown to be necessary to overcome the instantaneous ozone demand (IOD) to guarantee enough ozone to oxidise CoC. For CoC with KO3 >105M − 1s − 1 and K∙OH >109M − 1s − 1, an O3/TOC ratio of ≥0.461 or a measurable O3 CT of ≥0.063 mg min/L can achieve log reduction values (LRVs) of ≥1, these are chemicals with aromatic structures; For CoC with low KO3 and high KOH, a combined O3/TOC ratio and O3 CT value inclusive of a chemical structure classification is indicated as necessary criteria to evaluate the removal. UV254 and TOC were demonstrated to be good online surrogates of ozone barrier performance in the absence of continuous O3/TOC ratio and O3 CT value measurements. Full-scale operational results confirm the effective predictions of the chemical credit framework, which highlights the necessity and importance of monitoring both the O3/TOC ratio and O3 CT values to predict the removal efficiency of a given chemical with a known response to O3 or a known chemical structure.

Heat-constrained modelling of calcium sulphate reduction

A two-dimensional finite difference model has been developed to describe the reduction of kilogram quantities of dehydrated phosphogypsum. The model's scope has been limited to focus on the heat transfer and reactions that occur within a mass of material contained in a vessel inside a furnace rather than also including the effects of heat transfer to the vessel. Changes in the heat transfer properties (k, p, and Cp) are incorporated as the composition of the mass changes as the chemical reactions progress. The model is validated against experimental data, with samples heated to iooo°C at 3°C min-1 while purging with nitrogen gas. A sensitivity analysis of model predictions to the pre-exponential factor of the reaction rate constant of the main chemical reaction and the thermal conductivity of the powder bed indicated that, at the envisaged process conditions, the behaviour of the system depends much more on the rate of heat transfer than on the rate of the chemical reaction. The model demonstrated a significant increase in accuracy when the thermal conductivity was modelled to increase linearly with temperature compared to assuming a constant value.

Quantized Constrained Molecular Chains: Vibrations, Internal Rotations and Polymerization

The present work has a twofold purpose. a) It proposes a quantum-mechanical approach to constrained molecular chains and their small vibrations and rotations, by employing in a compact way vector variables and operators associated to the constituent units of the chain. The methods here differ from standard approaches based upon cartesian coordinates and normal modes and generalize previous quantum Hamiltonians describing only rotational degrees of freedom. Several models in D = 2, 3 spatial dimensions, with new Hermitean Hamiltonians, are formulated and analyzed. The chains studied successively display an increasing number of constraints: freely-jointed, freely-rotating and with constrained torsions. Conservation of total orbital angular momentum is analyzed. As a partial test, by using the present approach, the vibrational frequencies of certain triatomic molecules (water vapour, hydrogen sulfide, heavy water and sulfur dioxide) are computed and shown to be consistent with experimental data. b) A new (quantum-mechanical) analysis of polymerization, namely, the growth of a freely-jointed molecular chain (of the kind considered above) by binding an additional unit 1 to the chain, is presented. They move in a very dilute solution in a fluid at rest in thermal equilibrium about room temperature. The analysis is based upon a mixed (quantum-classical) distribution function in phase-space: a quantum Wigner-like one for unit 1 and a classical Liouville one for the chain. That leads to an approximate Schmolukowski equation for unit 1 alone and, through it, to compute the mean first passage time (MFPT) for unit 1 to become bound by the chain. The resulting MFPT displays a temperature dependence consistent with the Arrhenius formula for rate constants in chemical reactions.

Resilience of parity-violation-induced chiral selectivity to nonequilibrium temperature fluctuations in open systems

We consider the sensitivity of chemical reactions, able to undergo spontaneous mirror symmetry breaking, to chiral bias in the presence of nonequilibrium temperature fluctuations and derive a selectivity criterion. For this, we estimate the magnitude of fluctuations $\ensuremath{\delta}k$ in chemical reaction rate constants $k$ arising from the nonequilibrium temperature fluctuations $\ensuremath{\delta}T$ about a mean value $T$. To leading order, the relative rate constant fluctuations $\ensuremath{\delta}{k}_{i}/{k}_{i}$ for each reaction $i$ are given by the product of the activation enthalpy $\mathrm{\ensuremath{\Delta}}{H}_{i}^{\ifmmode\ddagger\else\textdaggerdbl\fi{}}/RT$ for the $i\mathrm{th}$ reaction multiplied by the relative rms temperature fluctuations $\ensuremath{\delta}{T}_{\mathrm{rms}}/T$. The latter are determined by the system's specific heat at constant volume: ${C}_{V}$. We test this criterion with simulations carried out for an open-flow fully reversible Frank model, and for a range of parity-violating energy differences (PVED) within the theoretically estimated upper and lower bounds. Depending on the relative magnitudes of the deterministic PVED bias and the temperature fluctuations, the PVED bias can either (i) select the final stable chiral outcome deterministically or (ii) select one of two possible stable chiral outcomes with an asymmetric statistical weighting. For larger temperature fluctuations, the PVED bias loses its selectivity, and the final stable chiral outcomes are stochastic and equally probable. This paper points towards the possible design of small volume chemical flow reactors capable of detecting the elusive PVED bias in bulk systems, provided other sources of fluctuations can be sufficiently controlled and attenuated.

Investigation of the combustion process of activated fuel in an automotive diesel engine

BACKGROUND: Intensive development of the transport sphere and the extension of the fleet of tractors and cars, as well as the tightening of standards and requirements in the field of exhaust gas emissions have resulted in increased requirements for the combustion process. This problem can be solved by improving the working process in the engine by preheating the fuel to 300 C in the high pressure fuel supply system. Under external thermal influence, the conditions of mixture formation are improved, an increase in the rate of preflame reactions and a positive change in the dynamics of the combustion process are observed. When potential energy of hydrocarbon molecules increases in the activated complex system, energy is redistributed among active molecules. Along with this, the rate coefficient of a chemical reaction increases due to the concentration of foci of hydrocarbon molecules that have reached the energy barrier.
 The object of research is the process of diesel fuel combustion at preliminary external influence on it.
 AIMS: The aim is to study the combustion process of a motor-tractor diesel engine upon fuel activation. Development of a scheme of individual phases of the activated diesel fuel combustion of depending on the temperature at heating.
 METHODS: Theoretical study and analysis of the combustion process of thermally preprepared fuel for an automotive diesel engine. Theoretical determination of the dependence of the rate of formation and concentration of toxic components and dispersed particles on the rate constant of direct and reverse chemical reactions, as well as on the activation temperature of fuel at emission in exhaust gases.
 RESULTS: The actual coefficient of molecular change of the working mixture increases when diesel fuel is activated. The rate of formation of total nitrogen oxides and hydrocarbons increases by 1.79% and 3.66%. The proportion of unburned carbon in the combustion process on activated fuel varies within (24) %.
 CONCLUSIONS: Theoretically, a scheme for changing individual phases of the activated fuel combustion process by time and temperature has been developed. Fuel heating accelerates the pre-flame preparation in the liquid phase, shortens the duration of the rapid gorenje phase. The concentration of toxic indicators depends on the constant of the chemical reaction rate and the activation temperature of the fuel.

Rotational thermodynamic parameters for asymmetric-top molecules: classical vs. quantum approaches and new analytical partition function

We investigated classical and quantum rotational partition functions, rotational energies and rotational entropies for asymmetric-top molecules in a canonical system within a wide range of temperatures under the rigid rotor approximation. We then derived the temperature, , below which classical approach is not valid, and the complex quantum approach is strongly recommended. This temperature certainly increases with the inertia moment of the molecule and follows a power function when rotational partition functions are considered. As for linear-, spherical- and symmetric-top molecules, quantum approach is not needed at all for energetic rotational parameters, whatever the temperature for asymmetric-top molecules. Therefore, there is no real frontier between the classical and quantum approaches when energetic rotational parameters are concerned, though the frontier is naturally a bounded decreasing sequence converging to zero when rotational partition functions are rather concerned. Particularly, classical approach fails describing rotational partition functions for light molecules or molecules at low temperatures. Moreover, all the closed-form expressions proposed in the whole literature fail drastically approaching quantum and exact results for light molecules or molecules at low temperatures. In regard to the importance of partition functions in the evaluation of rate constants for chemical reactions and accurate intensities lines in spectroscopy, we proposed new accurate and simple analytic expression of the rotational partition functions of asymmetric-top molecules, valid at all temperatures.

Mathematical modeling and kinetic behavior of Indian Umblachery cow butter and its nutritional degradation analysis under modified atmospheric packaging technique

AbstractMain objective of the study is to evaluate the effect of polyphenols enrichment, modified atmosphere packaging (CO2: 20%, N2: 75%, O2: 5%) and storage time on the shelf‐life solidity and nutritional degradation of butter from Indian native breed of Umblachery cow. The butter samples were incorporated and enriched with polyphenols and flavonoids from the seed coat extracts of Cajanus cajan (136.5 mg of gallic acid equivalents/g and 68.7 mg of quercetin equivalents/g) and butylated hydroxyl anisole (200 ppm) and the oxidative solidity and nutritional and flavor retention was evaluated without changing its organoleptic properties during 6 months of storage with and without MAP at 4, 15, and 25°C. SCECC significantly reduced the formation of oxidation products and the kinetics of shelf‐life of butter with predictive Arrhenius model was assessed in real time and accelerated according to temperature with the maximum activation energy of 5,309.2 J/mol for SCECC enriched and 3,191.4 J/mol for butylated hydroxyl anisole incorporated samples with modified atmosphere packaging at 4°C for peroxide value. The loss of polyphenols during storage was analyzed and it was 21–36% at 4°C and 31–55% at 25°C with and without modified atmosphere packaging at the end of sixth month. Organoleptic evaluations indicated that the samples treated with polyphenols combined with modified atmosphere packaging had lowermost lipid deterioration and exhibited high level of protective effects on nutritional degradation and recorded highest overall acceptability at 4°C and minimum level of sensorial behavior was observed at 25°C at the end of sixth month.Practical ApplicationsEnrichment of polyphenols with food emulsion can profitably influence their oxidative stability and the emulsions should sustain optimal quality and stability throughout the storage period. Lipid oxidation is the major deteriorative process with substantial commercial implications in terms of product cost. Due to the heavy demand for natural antioxidants, the polyphenols of seed coat extracts of Cajanus cajan have been used and correlated these results with enhancement of butter and increase its shelf life by modified atmospheric packaging. The activation energy and the rate constant of chemical reaction enabled the construction of kinetic models, which helped to estimate rate of changes in the butter sample. In order to estimate quality changes, we evaluated the polyphenolic loss, sensory features, and microbiological changes. The results of this study may deliver technical basis in the utilization of SCECC as a natural antioxidant with MAP to prevent lipid rancidification or nutritional loss in butter.

Theory of vibrational polariton chemistry in the collective coupling regime.

We theoretically demonstrate that the chemical reaction rate constant can be significantly suppressed by coupling molecular vibrations with an optical cavity, exhibiting both the collective coupling effect and the cavity frequency modification of the rate constant. When a reaction coordinate is strongly coupled to the solvent molecules, the reaction rate constant is reduced due to the dynamical caging effect. We demonstrate that collectively coupling the solvent to the cavity can further enhance this dynamical caging effect, leading to additional suppression of the chemical kinetics. This effect is further amplified when cavity loss is considered.

Simulation of two electrode reactions coupled by the chemical reaction.

A model of an ECE mechanism consisting of two reversible electrode reactions coupled by the kinetically controlled, second order, reversible chemical reaction is developed for the staircase cyclic voltammetry on the rotating disk electrode. The relationship between the limiting current of the second wave and the rate constant of chemical reaction is investigated. The concentration of electroinactive component of the forward reaction influences the half-wave potential of the first wave and the limiting current of the second wave. The responses of the mechanisms with reversible and irreversible chemical reactions are compared.

Progress towards machine learning reaction rate constants.

Quantum and classical reaction rate constant calculations come at the cost of exploring potential energy surfaces. Due to the "curse of dimensionality", their evaluation quickly becomes unfeasible as the system size grows. Machine learning algorithms can accelerate the calculation of reaction rate constants by predicting them using low cost input features. In this perspective, we briefly introduce supervised machine learning algorithms in the context of reaction rate constant prediction. We discuss existing and recently created kinetic datasets and input feature representations as well as the use and design of machine learning algorithms to predict reaction rate constants or quantities required for their computation. Amongst these, we first describe the use of machine learning to predict activation, reaction, solvation and dissociation energies. We then look at the use of machine learning to predict reactive force field parameters, reaction rate constants as well as to help accelerate the search for minimum energy paths. Lastly, we provide an outlook on areas which have yet to be explored so as to improve and evaluate the use of machine learning algorithms for chemical reaction rate constants.

Assessing and rationalizing the performance of Hessian update schemes for reaction path Hamiltonian rate calculations.

The reaction path Hamiltonian (RPH) can be used to calculate chemical reaction rate constants, going beyond transition-state theory in taking account of recrossing by providing an approximation to the dynamic transmission coefficient. However, the RPH necessitates the calculation of the Hessian matrix at a number of points along the minimum energy path; the associated computational cost stands as a bottleneck in RPH calculations, especially if one is interested in using high-accuracy electronic structure methods. In this work, four different Hessian update schemes (symmetric rank-1, Powell-symmetric Broyden, Bofill, and TS-BFGS updates) are assessed to see whether or not they reliably reproduce calculated transmission coefficients for three different chemical reactions. Based on the reactions investigated, the symmetric rank-1 Hessian update was the least appropriate for RPH construction, giving different transmission coefficients from the standard analytical Hessian approach, as well as inconsistent frequencies and coupling properties. The Bofill scheme, the Powell-symmetric Broyden scheme, and the TS-BFGS scheme were the most reliable Hessian update methods, with transmission coefficients that were in good agreement with those calculated by the standard RPH calculations. The relative accuracy of the different Hessian update schemes is further rationalized by investigating the approximated Coriolis and curvature coupling terms along the reaction-path, providing insight into when these schemes would be expected to work well. Furthermore, the associated computational cost associated with the RPH calculations was substantially reduced by the tested update schemes. Together, these results provide useful rules-of-thumb for using Hessian update schemes in RPH simulations.

The effects of gravitational potential on chemical reaction rates

This study aims to answer through a mathematical model and its numerical simulation the question whether the kinetic rate constants of chemical reactions are influenced by the strength of gravitational field. In order to calculate the effects of gravity on the kinetic rate constants, the model of kinetic rate constants derived from collision theory is amended by introducing the mass and length corrections provided by general relativity. Numerical simulations of the model show that the rate constant is higher where the gravitational field is more intense.

LAMMPS molecular dynamics simulation of methane decomposition on nickel thin films at high temperatures

The activation energy of methane decomposition by nickel was calculated using models of nickel thin films, a large-scale atomic/molecular massively parallel simulator (LAMMPS) and a ReaxFF potential. The rate constants of the first-order chemical reaction of methane decomposition were obtained by analyzing the number of undecomposed methane molecules in individual movie frames. The obtained activation energies of methane decomposition on the Ni (111) surfaces showed values close to those reported in the literature. The structural change of a Ni thin film with (111) surfaces was simulated to investigate how carbon and hydrogen atoms are deposited on the Ni thin film upon the decomposition of methane molecules at a high temperature. The catalytic activity of the (111) Ni thin film was found to decrease from the time point of critical supersaturation of carbon in the Ni thin film.