Thermodynamics, adsorption excess properties

Fischer et al, [122] proposed a model to predict the adsorption isotherm of krypton in porous material at supercritical temperature. In their study, a model pore of infinite length is formed by concentric cylindrical surfaces on which the centers of solid atoms are located. The interaction between an adsorbate and an individual center on the pore wall is described by the LJ 12-6 theory, and the overall potential is the integral of this interaction over the entire pore surface. With thermodynamic relations, Fischer et al. obtained the functional dependence of the saturation adsorption excess and the Henry s law constant on the pore structure. The isotherm was then produced by the interpolation between Henry s law range and saturation range. They tested their theory with the adsorption of krypton on activated carbon. It was shown that, with information on the surface area of the adsorbent and thermodynamic properties of the adso bate, their model gives more than quantitative agreement with experimental data. If a few experimental data such as the Henry s law constant at one temperature are available, the isotherms for all temperatures and pressures can be predicted with good quality. 

Adsorption. Some substances tend to adsorb onto an interface, thereby lowering the interfacial tension the amount by which it is lowered is called the surface pressure. The Gibbs equation gives the relation between three variables surface pressure, surface excess (i.e., the excess amount of surfactant in the interface per unit area), and concentration—or, more precisely, thermodynamic activity—of the surfactant in solution. This relation only holds for thermodynamic equilibrium, and the interfacial tension in the Gibbs equation is thus an equilibrium property. Nevertheless, also under nonequilibrium conditions, a tension can be measured at a liquid interface. 

A curious example is that of the distribution of benzene in water benzene will initially spread on water, then as the water becomes saturated with benzene, it will round up into lenses. Virtually all of the thermodynamics of a system will be affected by the presence of the surface. A system containing a surface may be considered as being made up of three parts two bulk phases and the interface separating them. Any extensive thermodynamic property will be apportioned among these parts. For example, in a two-phase multicomponent system, the extra amount of an i component that can be accom-mondated in the system due to the presence of the interface ( ) may be expressed as Qi Qii where is the total number of molecules of i in the whole system, Vj and Vjj are the volumes of phases I and II, respectively, and Q and Qn are the concentrations of i in phases I and II, respectively. The surface (excess) concentration of i is defined as Fj = A, where A is the surface area. At equilibrium, the chemical potential of any component is the same in each bulk phase and at the surface. The Gibbs adsorption equation, which is one of the most widely used expression in surface and colloid science is shown in Eq. (2) ... 

Equations (22j-(2dJshow that the unsteady-state mass and energy balances within the adiabatic adsorber can be written using the surface excess of each component of the gas mixture as the primary variables to define the extent of adsorption. The isosteric heat of adsorption of component i (q,) and the heat capacity of the adsorption system (C ), defined using the GSE framework, become the appropriate thermodynamic properties to describe the energy balance. 

The major property of surfactants is their ability to adsorb at interfaces and thus to decrease the surface excess energy and to modify the interface. Various adsorption and surface tension isotherms are used in the thermodynamic description of this phenomenon see Sec. II. 

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