Compensation Effect in Heterogeneous Catalysis

Galwey, Andrew K.

doi:10.1016/s0360-0564(08)60072-3

Cited by 219 publications

(129 citation statements)

References 268 publications

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“…A value very close to that found in the oxidation reactions of propene and acetylene over various oxides (30). This observation suggests that the general form of the rate-limiting step is similar in these related reactions.…”

Section: Discussionsupporting

confidence: 80%

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Oxidation of 1-butene by nitrous oxide over manganese(III) and related transition metal oxides

Ross¹,

Fairbridge²

1984

Can. J. Chem.

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The oxidation of 1-butene by nitrous oxide over manganese(II1) oxide was studied in a continuous flow system from 573 to 673 K. Kinetic parameters were derived from the exponential relationship: r = ka P::~P:~;, over reactant partial pressure ranges, 0.30 < PN20 < 2.60 kPa and 0.43 < PC,,, < 8.27 kPa. The reaction mechanism proposed involves a complex sequence of steps which include surface radical reactions. On the basis of a comparison of specific reaction rates, the catalytic activity series for the reaction over a number of transition metal oxides was: Introduction The catalytic performance of manganese oxides in several redox reactions involving hydrocarbons with oxygen or nitrogen oxides has been reported recently. The work has included the oxidation of ethane by nitric oxide over unsupported manganese(II1) oxide (1) and the oxidation of 1-butene and ethane by oxygen over manganese(II1) oxide supported on carbon fibres (2). The results of these experiments pointed to complex surface mechanisms with rate-controlling steps most probably associated with the interactions of species within the adsorbed layer.In the present investigation an attempt has been made to evaluate the kinetics of the catalysis of 1-butene by nitrous oxide over manganese(II1) oxide. Measurements of reaction rates were supplemented by structural analysis. A general comparison of the catalytic activities in the reaction of metal oxides of the first transition series has also been carried out.

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Section: Discussionsupporting

confidence: 80%

“…A number of theoretical models have been proposed to explain this compensation effect, and these have been summarized recently (30).…”

Section: Discussionmentioning

confidence: 99%

Oxidation of 1-butene by nitrous oxide over manganese(III) and related transition metal oxides

Ross¹,

Fairbridge²

1984

Can. J. Chem.

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“…7. It can be seen that there is an obvious linear relation between ln(A) and E. The kinetic compensation effect was a widely phenomenon not only in the fields of science, notably heterogeneous catalysis 41,42) but also in chemistry. 43,44) Previous studies believed that kinetic compensation effect was resulted from pure mathematics treatment by the use of Arrhenius formula of free energy, 45) but many theories were developed to explain this effect in follow-up studies.…”

Section: Kinetic Parameters Analysismentioning

confidence: 99%

Experiments and Kinetic Modeling for Reduction of Ferric Oxide-biochar Composite Pellets

Wang

Zhang

et al. 2017

ISIJ Int.

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The reduction behavior, phase transformation and microstructure evolution of four ferric oxide-biochar composite pellets (RLC-pellet, PHC-pellet, MCC-pellet and PSC-pellet) were investigated by use of nonisothermal thermogravimetric, X-Ray diffraction (XRD) and Scanning electron microscopy (SEM) analysis. The apparent kinetic parameters of reduction process were estimated by fitting the experimental data to the three parallel nth order rate models. The results showed that ferric oxide-biochar composite pellet reduction process was divided into three stages of Fe 2 O 3 →Fe 3 O 4 , Fe 3 O 4 →FeO and FeO→Fe, where the first stage was independent to the next two stages. The sequence of reduction reactivity as to all samples was MCC-pellet > PHC-pellet > PSC-pellet > RLC-pellet. Meanwhile, increasing heating rate could efficiently improve the reduction reactivity. Through kinetic analysis, it was found that three parallel nth order rate models could well represent reduction process, and activation energies of three stages calculated by the model were 204.9-405.5 kJ/mol, 259.6-643.8 kJ/mol and 291.5-685.8 kJ/mol, respectively. The marked compensation effect was also presented between the activation energy and pre-exponential factor.

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“…This phenomenon is usually referred to as the compensation effect, but it has also been called the Constable law, the isokinetic relationship or the &rule (Exner 1964, Khait 1983. A thoroughly studied example is the compensation effect in heterogeneous catalysis which has been reviewed by Galwey (1977). The compensation effect has also been observed by e.g.…”

Section: A(o) = a E-ae/krmentioning

confidence: 99%

A phenomenological model for the Meyer-Neldel rule

Dyre

1986

J. Phys. C: Solid State Phys.

145

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Abstract. In this paper it is argued that the generality of the Meyer-Neldel rule compels one to adopt a phenomenological approach if a universally valid model is aimed at. It is shown that there exists only one possible phenomenological model. This model is based on an exponential probability distribution of energy barriers. The model predicts a power-law frequency dependence of the AC conductivity with the exponent s given by s = 1 -T/T, where T,, is the characteristic temperature of the Meyer-Neldel rule. It is conjectured that the exponential energy barrier distribution derives from a 'glass transition' at To. The generalisation of the model to account for the compensation effect in other contexts is briefly discussed, using the case of heterogeneous catalysis as an example.

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Compensation Effect in Heterogeneous Catalysis

Cited by 219 publications

References 268 publications

Oxidation of 1-butene by nitrous oxide over manganese(III) and related transition metal oxides

Oxidation of 1-butene by nitrous oxide over manganese(III) and related transition metal oxides

Experiments and Kinetic Modeling for Reduction of Ferric Oxide-biochar Composite Pellets

A phenomenological model for the Meyer-Neldel rule

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