Kinetics of contracting geometry-type reactions in the solid state: implications from the thermally induced transformation processes of α-oxalic acid dihydrate

Kodani, Satoki; Koga, Nobuyoshi

doi:10.1039/d0cp03176c

Cited by 14 publications

(13 citation statements)

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“…By contrast, a systematic decrease in m value as the p (CO 2 ) values increased was evident using JMA( m ). In both curve fitting results, the calculated A value increased with the p (CO 2 ) value, exhibiting evidence of a mutual dependence between E a and A values, known as the kinetic compensation effect (KCE). − …”

Section: Resultsmentioning

confidence: 86%

“…In addition, a statistically significant linear correlation between the apparent E a and ln A values ( i.e ., ln A = a + bE a ), was observed to exist, as in the manner of the KCE (Figure S33). − This implies that conventional kinetic approaches whereby the effect of p (H 2 O) is not considered do not provide a universal kinetic description of the thermal decomposition of ZnCO 3 under various p (H 2 O) values.…”

Section: Resultsmentioning

confidence: 99%

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Universal Kinetics of the Thermal Decomposition of Synthetic Smithsonite over Different Atmospheric Conditions

et al. 2021

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The thermal decomposition of smithsonite (ZnCO 3 ) was studied to obtain a universal kinetic description of the process applicable to a range of reaction conditions. A synthesized ZnCO 3 was subjected to thermoanalytical measurements under various heating and atmospheric conditions in a flow of dry N 2 gas, or N 2 −CO 2 or N 2 −H 2 O mixed gases. Systematic shifts of the reaction temperature to higher or lower values by the effects of CO 2 or H 2 O, respectively, were identified as specific characteristics of the system. With reference to the physicogeometrical kinetic behavior of the reaction in a flow of dry N 2 gas, the retardation effect of CO 2 was demonstrated in the scheme of the physicogeometrical consecutive surface reaction (SR) and phase boundary-controlled reaction (PBR). The individual kinetics of SR and PBR were universally described over different CO 2 partial pressures using an accommodation function (AF) obtained by considering the consecutive elementary steps of SR and PBR. The catalytic effect of water vapor was assumed to result from contributions of water molecules to the consecutive elementary steps of SR and to the crystal growth of the solid product of the reaction (ZnO). An alternative AF derived considering the adsorption of water molecules on solid surfaces allowed us to obtain the universal kinetic description of the thermal decomposition over different water vapor pressures.

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Section: Resultsmentioning

confidence: 86%

Section: Resultsmentioning

confidence: 99%

Universal Kinetics of the Thermal Decomposition of Synthetic Smithsonite over Different Atmospheric Conditions

et al. 2021

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“…5,6 The steady energy supply to the reaction interface via thermal conduction through the surface product layer is disturbed by the enthalpy change resulting from the reaction at the reaction interface, which causes a self-heating or self-cooling effect on the interfacial reaction kinetics. 7,8 Therefore, the apparent kinetics of the thermal decomposition in a welldefined single reactant body vary with the sample shape and size, 9,10 as well as the reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Physico-geometrical kinetics of the thermal dehydration of sodium carbonate monohydrate as a compacted composite of inorganic hydrate comprising crystalline particles and matrix

Zushi

Iwasaki

Koga

2022

Phys. Chem. Chem. Phys.

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“…Therefore, carefully controlled reaction conditions might lead us to the discovery of exciting kinetic polymorphs with unexpected structures and properties. Several comparison studies on the reactivity and stability for a number of phase transition reactions for polymorphs have been reported to date. − However, efforts to elucidate the underlying reaction mechanisms related to symmetry have rarely been put in to design functional materials more efficiently.…”

Section: Introductionmentioning

confidence: 99%

Order and Disorder: Toward the Thermodynamically Stable α-BaMoO₂F₄ from the Metastable Polymorph

Lee

2021

Chem. Mater.

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A fully ordered noncentrosymmetric barium molybdenum oxyfluoride, α-BaMoO2F4, has been synthesized by a hydrothermal reaction at 200 °C in a concentrated hydrofluoric acid solution. A centrosymmetric polymorph with O/F disorder, β-BaMoO2F4, has been obtained in several minutes when the reaction mixture was stirred at room temperature in the same medium. Interestingly, we found that the metastable β-BaMoO2F4 transforms into the thermodynamically stable α-BaMoO2F4 in an ambient condition. More detailed kinetic studies using powder X-ray diffraction indicate that the MoO2F4 octahedra in the kinetic phase, β-BaMoO2F4, rearrange through the constant dissolution/precipitation process to find a more stable orientation and form the fully ordered α-BaMoO2F4. Density functional theory (DFT) calculations suggest that the formation of the thermodynamically stable α-BaMoO2F4 is driven by the strong Mo–O π-interactions induced by Ba2+ cations. The new finding on the understanding of the kinetics of solid-state reactions suggests a novel way toward an effective discovery of functional materials with asymmetric structures.

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Kinetics of contracting geometry-type reactions in the solid state: implications from the thermally induced transformation processes of α-oxalic acid dihydrate

Abstract: This study focuses on the physico-geometrical constraints of the kinetics of the thermal decomposition of solids as exemplified by the thermal dehydration of α-oxalic acid dihydrate and the subsequent thermally...

Cited by 14 publications

References 83 publications

Universal Kinetics of the Thermal Decomposition of Synthetic Smithsonite over Different Atmospheric Conditions

Universal Kinetics of the Thermal Decomposition of Synthetic Smithsonite over Different Atmospheric Conditions

Physico-geometrical kinetics of the thermal dehydration of sodium carbonate monohydrate as a compacted composite of inorganic hydrate comprising crystalline particles and matrix

Order and Disorder: Toward the Thermodynamically Stable α-BaMoO₂F₄ from the Metastable Polymorph

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Kinetics of contracting geometry-type reactions in the solid state: implications from the thermally induced transformation processes of α-oxalic acid dihydrate

Abstract: This study focuses on the physico-geometrical constraints of the kinetics of the thermal decomposition of solids as exemplified by the thermal dehydration of α-oxalic acid dihydrate and the subsequent thermally...

Cited by 14 publications

References 83 publications

Universal Kinetics of the Thermal Decomposition of Synthetic Smithsonite over Different Atmospheric Conditions

Universal Kinetics of the Thermal Decomposition of Synthetic Smithsonite over Different Atmospheric Conditions

Physico-geometrical kinetics of the thermal dehydration of sodium carbonate monohydrate as a compacted composite of inorganic hydrate comprising crystalline particles and matrix

Order and Disorder: Toward the Thermodynamically Stable α-BaMoO2F4 from the Metastable Polymorph

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Product

Resources

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Order and Disorder: Toward the Thermodynamically Stable α-BaMoO₂F₄ from the Metastable Polymorph