Adsorbate-adsorbent interaction spreading pressure

Thus, contributions include accounting for adsorbent heterogeneity [Valenzuela et al., AIChE J., 34, 397 (1988)] and excluded pore-volume effects [Myers, in Rodrigues et al., gen. refs.]. Several activity coefficient models have been developed to account for nonideal adsorbate-adsorbate interactions including a spreading pressure-dependent activity coefficient model [e.g., Talu and Zwiebel, AIChE h 32> 1263 (1986)] and a vacancy solution theory [Suwanayuen and Danner, AIChE J., 26, 68, 76 (1980)]. 

Comparison of Equations (2.61) and (2.67) shows that the second term of the right-hand side of Equation (2.67) is due to the spreading pressure, which is related to the interactions between adsorbed molecules, often referred to as the lateral interactions . It is only at very low coverages, where the spreading pressure is negligible, that the integral molar entropy of adsorption is simply dependent on the adsorbate-adsorbent interaction. 

The Gibbs adsorption isotherm shows the dependence of the extent of adsorption of an adsorbent on its bulk concentration or pressure. However, we also need to know the state of the adsorbate at the surface. These are interrelated because the extent of material adsorb-tion on a surface depends on the state of the surface. The behavior of the molecules in the surface film is expressed by a surface equation of state which relates the spreading pressure, n, which is the difference between the solvent and solution surface tensions, %= % - y to the surface concentration of the adsorbent. This equation is concerned with the lateral motions and interactions of the molecules present in an adsorbed film. In general, the surface equation of state is a two-dimensional analogue of the three-dimensional equation of state of fluids, and since this is related to monomolecular films, it will be described in Sections 5.5 and 5.6. It should be remembered that on liquid surfaces, usually monolayers form, but with adsorption on solid surfaces, usually multilayers form (see Section 8.3). 

Similarly, in the case of mercury, the spreading pressure of hydrocarbons on mercury is 0.8 to 0.9 of S [20, 21]. These results in liquid systems in which the adsorbed materials have only dispersion forces and can interact with the solids only by dispersion forces show that the value of 7T g is always less than S. Consequently, whenever liquid 2 does not spread over liquid 1, we may expect to be zero. Another way of... 

If there are no significant nonideal interactions in a mixed adsorbed phase then a comparison of the equilibrium pressures for the two pure sorbates at the same temperature and spreading pressure (or the same value of 0 provides... 

Cationic amphiphiles 2Ci8-glu-N spread on pure water, in the solution of 10 xM DNA containing 10 xM intercalating dyes (proflavine). The dye-intercalated DNA anions were expected to adsorb to the cationic lipid mono-layer due to electrostatic interactions and was transferred to a hydrophobized glass plate at a surface pressure of 35 mN m at 20 °C. From a moving area of a barrier, two layers of the monolayer were confirmed to be transferred in each one cycle (Y-type deposition). When the QCM plate was employed as a transfer plate, the transferred mass could be calculated from frequency decreases (mass increase on the QCM) [29-31]. It was confirmed that 203 10 ng of two lipid monolayers and 74 5 ng of DNA strands were transferred on to the substrate per dipping cycle, which means ca. 95% of the monolayer area was covered by DNA molecules. 

More complex with respect to molecular interaction is the case of formation of non-aqueous films on the surface of aqueous solutions from non-ionic surfactants [528], Films from octane were obtained by adsorption from drops of octane/non-adsorbing diluent (squalane) mixture. Occasionally the spreading of alkanes on aqueous surfactant solution gives stable thin oil films (e.g. on solutions of the anionic surfactants Aerosol OT) [529,530], Some evidence about the stability of asymmetric films can be derived from the data about the surface pressure and spreading coefficients of liquids on water surface. These data are known for many organic liquids [531,532], It should be also noted that the techniques for determination of the spreading coefficients have improved considerably [533,534]. Most precise values were obtained by measuring the surface pressure of a monolayer with a special substance introduced as an indicator [533]. 

Partly soluble triblock copolymers are also sometimes used for monolayer studies. Such investigations could provide data on desorption kinetics, and allow for comparison of the film structure, whether spread or adsorbed. However, attention should be paid to data interpretation in such cases because intricate equilibriums take place in such systems. A somewhat confusing study has been presented concerning the monolayer miscibility between PLA and PEO-PPO-PEO (also known as Pluronic) in monolayers [53]. The authors attempted to discuss interactions between the triblock copolymer and a homopolymer (PLA) on the basis of Langmuir monolayer experiments however, the results show unrealistic values for molecular areas, and therefore conclusions from those measurements cannot be quantitative. In particular, surface pressure-area isotherms for pure polymers and their mixtures reveal, in the compressed state, areas per monomer unit of the order of 3 h and below. Such low values cannot be real and most probably result either from material dissolution in the subphase or poor spreading at the air-water interface. Indeed, the isotherms do not appear smooth, which suggests low film stability and difficulties in forming a true monolayer. 

Dubinin has proven that the constant B reflects the lateral interaction energies existing between the adsorbed molecules. Because in Eqs. (307) and (308), Pq is the saturation pressure (i.e., the temperature is below the critical temperature of the absorptive), nj, may lose its physical meaning. Thus, it is more convenient to define a hypothetical or equivalent monolayer capacity (also denoted by wj,) which would result if the amount of adsorbate required to fill the pores were spread in a close-packed monolayer of molecules. To avoid this hypothetical monolayer... 

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