Solid-liquid interface surface entropy

The third paper in this subject that we were able to retrieve is due to Biswas et al. [145]. In their introduction to the paper they said that dynamic and mechanistic aspects of adsorption of surfactants at the solid-liquid interface, particularly silica surface, were rare and quoted six papers. The most recent among them was due to Tiberg [146] in 1996. Adsorption kinetics was studied by Biswas et al. [145] using classical batch experiments. They found that the adsorption follows a two-step first-order rate equation. From the calculated rate constants they obtained the activation energies and entropies concluding that both processes are entropy controlled. 

To p. 11. According to N. H. Fletcher, J. Crystal Growth 28, 375 (1975), the free energy of solid - melt interfaces in many systems (e.g., water - ice) is determined above all by the low entropy of the liquid layers adjacent to the solid surface. This loss of entropy occurs because the above layers are more ordered than the melt far from the solid. 

Perhaps the simplest type of a polymeric surfactant is a homopolymer, that is formed from the same repeating units, such as PEO or poly(vinyl pyrrolidone). These homopolymers have minimal surface activity at the O/W interface, as the homopolymer segments (e.g., ethylene oxide or vinylpyrroUdone) are highly water-soluble and have little affinity to the interface. However, such homopolymers may adsorb significantly at the solid/liquid (S/L) interface. Even if the adsorption energy per monomer segment to the surface is small (fraction of kT, where k is the Boltzmann constant and T is absolute temperature), the total adsorption energy per molecule may be sufficient to overcome the unfavourable entropy loss of the molecule at the S/L interface. 

When a gas comes in contact with a solid surface, under suitable conditions of temperature and pressure, the concentration of the gas (the adsorbate) is always found to be greater near the surface (the adsorbent) than in the bulk of the gas phase. This process is known as adsorption. In all solids, the surface atoms are influenced by unbalanced attractive forces normal to the surface plane adsorption of gas molecules at the interface partially restores the balance of forces. Adsorption is spontaneous and is accompanied by a decrease in the free energy of the system. In the gas phase the adsorbate has three degrees of freedom in the adsorbed phase it has only two. This decrease in entropy means that the adsorption process is always exothermic. Adsorption may be either physical or chemical in nature. In the former, the process is dominated by molecular interaction forces, e.g., van der Waals and dispersion forces. The formation of the physically adsorbed layer is analogous to the condensation of a vapor into a liquid in fret, the heat of adsorption for this process is similar to that of liquefoction. 

For liquids and solids, specific orientation and conformation of msymmetrical molecules (ions) in the interfacial regions result not only in the maximization of their interaction energy, but also yield entropy effects that cannot be neglected. For example, molecular dynamics calculations of the intermolecular potential function points to a predominant orientation of the water dipoles at the Liquid-Gas interface [45]. Other examples are an icelike structuring of water molecules in the vicinity of crystalline solid surfaces [46] and a specific orientation of the alcohol molecules in the interface between a liquid n-alkanol and water [47]. 

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