Adsorption–desorption kinetics and chemical potential of adsorbed and gas-phase particles

Zhdanov, Vladimir P.

doi:10.1063/1.1349178

Cited by 15 publications

(15 citation statements)

References 44 publications

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“…For example, transition state theory``supposes'' (there is no derivation of the rate expression [28]) that the isothermal, unidirectional rate of gas desorption depends only on the conditions in the adsorbed phase. Whereas, the transition probability concept used in SRT indicates that the unidirectional gas desorption rate depends on properties in both the adsorbed phase and in the gas phase.…”

Section: Discussionmentioning

confidence: 99%

Liquid-Vapour Phase Change Rates and Interfacial Entropy Production

Ward¹

2002

Journal of Non-Equilibrium Thermodynamics

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Measurements have recently been made of the thermodynamic conditions at the interface during steady state, liquid-vapour phase transitions. In these stationary, nonequilibrium states discontinuities were recorded in the temperature and other intensive properties. Independently of whether evaporation or condensation was taking place, it was found that the interfacial temperature was higher in the vapour phase than that in the liquid. The expression for the interfacial entropy production during these phase change processes is formulated using statistical rate theory. The interfacial entropy production rate is not a minimum when there is a phase change process taking place, but if the system is required to be closed (no net phase change), the interfacial entropy production rate is a minimum. States of minimum entropy production rate can exist arbitrarily far from equilibrium, provided a certain relation exists between the properties of the substance undergoing the phase change. For water, it is found that states of minimum entropy production rate are only slightly displaced from the stationary, nonequilibrium states existing when a net phase change rate is present.

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Section: Discussionmentioning

confidence: 99%

Liquid-Vapour Phase Change Rates and Interfacial Entropy Production

Ward¹

2002

Journal of Non-Equilibrium Thermodynamics

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“…Right now, at the beginning of 21st century, there is not even general agreement concerning the theoretical fundamentals of adsorption kinetics [1]. However, our current understanding of adsorption kinetics is surprisingly poorer.…”

Section: Introductionmentioning

confidence: 99%

“…The obtained expressions for dadt were next generalized by Rudzinski In spite of the impressive success of the new SRT approach to quantitatively explain and describe the adsorption/desorption kinetics in so many real adsorption systems, this approach has recently been criticized by Zhdanov [1], defending the ART approach.…”

Section: Introductionmentioning

confidence: 99%

“…Some of the objections launched by Zhdanov in his previous dispute with Nagai in the series of papers published in the Surface Science Journal, [56±60] were defeated by Nagai, but the recent critical paper by Zhdanov [1] does not refer to them. In view of the existing controversy, it seems necessary to analyze and compare both the fundamentals of the ART and the SRT approaches, and their applications in describing the kinetics of adsorption/desorption on/from real, more or less energetically heterogeneous solid surfaces.…”

Section: Introductionmentioning

confidence: 99%

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Phenomenological Kinetics of Real Gas-Adsorption-Systems: Isothermal Adsorption

Rudziński¹,

Pańczyk²

2002

Journal of Non-Equilibrium Thermodynamics

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Since Langmuir published the derivation of his famous adsorption isotherm equation in 1918, hundreds of papers on the kinetics of gas adsorption on solid surfaces have appeared in the world literature. Until the early ®fties of the 20th century, these were mainly papers reporting on experimental studies of the kinetics of adsorption in various adsorption systems. Surprisingly, although the Langmuir isotherm described the adsorption equilibria fairly well, the related kinetic expressions generally failed to describe the adsorption kinetics. So, beginning in the early ®fties, vigorous attempts were made to improve that kinetic approach based on ideas of the Absolute Rate Theory (ART). Since then, one has been able to see more progress on the theoretical side than in the related experimental studies. However, the vast majority of these papers treated hypothetical adsorption kinetics in virtual adsorption systems with well-de®ned surfaces. This was especially true in the case of the theoretical studies of isothermal adsorption kinetics. Certain progress was made in theoretical studies of the kinetics of thermodesorption, where the energetic heterogeneity of the real solid surfaces was demonstrated in an impressive way. Here, almost all the attempts to take energetic surface heterogeneity into account were based on a further generalization of the ART approach.In the early eighties a new family of fundamental approaches appeared, linking the rate of adsorption/desorption processes to the chemical potentials of the bulk and the adsorbed molecules. Among them the so-called Statistical Rate Theory (SRT) has received the most advanced theoretical attention. The new SRT approach has been generalized during recent years for the case of energetically heterogeneous surfaces. This has been done for both the isothermal kinetics and the kinetics of thermodesorption. So we have only two fundamental approaches which have been Brought to you by | Purdue University Libraries Authenticated Download Date | 6/4/15 11:42 PM generalized for consideration of the kinetics of gas adsorption in the real systems, i.e. the ART and the SRT approaches.The purpose of the present review is to discuss the features of the adsorption kinetics in real adsorption systems, where the solid surface energetic heterogeneity is the main factor determining these features. For that purpose we will thoroughly analyze existing and possible future generalizations of both the ART and SRT approaches, taking this crucial physical factor into account. Next, we will apply the obtained theoretical expressions to quantitatively simulate the observed adsorption kinetics in real adsorption systems.Our study does not refer to the special case of the kinetics of sorption by porous media where the exchange of mass between the gas and the adsorbed phase may not be assumed as the only possible rate-controlling step. 150 W. Rudzinski, T. Panczyk

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“…IKL was recently extended to include lateral interactions according to regular solution theory and the Kiselev association model as well as energetic heterogeneity (mRSK and LF-mRSK models) (Marczewski 2011). This model was also compared to the classic SRT model, corresponding to the same equilibrium isotherms but developed in opposition to the classic Langmuir kinetics (Ward and Findlay 1982;Zhdanov 2001;Rudzinski and Panczyk 2002a, b;Panczyk 2006;Plazinski et al 2009). Moreover, a new ''fractal-like'' ''approach'' to MOE, IKL and SRT models provided other possible extensions to those equations (Haerifar and Azizian 2012).…”

Section: Introductionmentioning

confidence: 99%

Adsorption and desorption kinetics of benzene derivatives on mesoporous carbons

2013

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Adsorption and desorption of benzoic and salicylic acids and phenol from a series of synthesized mesoporous carbons is measured and analyzed. Equilibrium adsorption isotherms are best described by the LangmuirFreundlich isotherm. Intraparticle diffusion and McKay's pore diffusion models, as well as mixed 1,2-order (MOE), integrated Langmuir kinetic equation (IKL), LangmuirFreundlich kinetic equation and recently derived fractallike MOE (f-MOE) and IKL models were compared and used to analyze adsorption kinetic data. New generalization of Langmuir kinetics (gIKL), MOE and f-MOE were used to describe desorption kinetics. Analysis of adsorption and desorption half-times shows simple relation to the size of carbon pores.

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Adsorption–desorption kinetics and chemical potential of adsorbed and gas-phase particles

Cited by 15 publications

References 44 publications

Liquid-Vapour Phase Change Rates and Interfacial Entropy Production

Liquid-Vapour Phase Change Rates and Interfacial Entropy Production

Phenomenological Kinetics of Real Gas-Adsorption-Systems: Isothermal Adsorption

Adsorption and desorption kinetics of benzene derivatives on mesoporous carbons

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