Theory Of Van Der Waals-Platteeuw Model

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Theory of van der Waals-Platteeuw model
Modifications to the well-known van der Waals-Platteeuw (VDW-P) model (van der Waals and Platteeuw, 1959) led to several thermodynamic models for predicting hydrate formation and/or dissociation conditions. The VDW-P model was derived which was based on the similarity between the hydrate formation and Langmuir adsorption. However, both the mechanisms are different, even if the adsorption mechanism is able to explain the nonstoichiometric feature of hydrates.
A brief discussion on the VDW-P hydrate model
Following were the assumptions based on which VDW-P model was developed. A cavity can have at most one guest gas molecule. Applicability of the ideal gas partition function is for the guest molecules. A pair of potential function is used to describe the interaction between guest and water molecules and cavity is considered as …show more content…

The first step is a quasi-chemical reaction for the formation of a stoichiometric basic hydrate and the second step is the physical adsorption for filling the empty linked cavities by gas molecules by applying Langmuir adsorption theory, resulting into the non-stoichiometric property of hydrate.
In the first step, following Sloan (1990), we assume that clusters formed when the gas molecules are dissolved in water and each guest molecule is surrounded by several water molecules. These clusters come together resulting into a basic hydrate, which is a combination of a basic cavities and linked cavities. Here, the basic cavities are fully occupied by the gas molecules, leaving linked cavities unfilled (empty cavity) and hydrate becomes stoichiometric. Following complex reaction descries the above process H2O + λ2G → Gλ2 .H2O
Where G stands for the gas species and λ2 is the number of basic cavities (large cavities) per water molecules. During this step basic hydrate encases the linked cavities in

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