A characterization of the bulk-phase diagram from literature data and new NMR and DSC measurements provided us with valuable elements that are helpful for gaining, from aqueous solution, better insight into the surface behavior of polyethylene glycol on Aerosil 200. Adsorption isotherms built further to measurements by a depletion method showed a strong and temperature-dependent variation of the isotherm shape in agreement with the variations of interactions already evidenced in the bulk. In temperature-concentration areas, where water is behaving as a helix-promoting solvent, the finding of positive PEG adsorptions and stairlike isotherms agrees with observations reported in the literature. We identified some of the vertical parts as corresponding to the formation of monolayers of helix-shaped PEG molecules. In poor-solvent zones, adsorptions were null or negative, and the isotherms exhibited oscillations suggesting very different surface behavior. Our data analysis evidenced the presence of a much greater amount of water than in the previous surface states; however, the similar analysis of PEG behavior remains relevant. Indeed, the occurrence of first-order transitions in the surface layer implies some water reorganization, permitting the PEG molecules to move closer to the surface and become helix-shaped to rearrange in a monolayer. The surface phase diagram confirmed this analysis in a very satisfying way.
This paper reports on investigations about the adsorption at the air-water surface, and for the sake of comparison at the silica-solution interface, of two 1-2 electrolytes, Pb(NO(3))(2) and PbCl(2), at first alone and then from a mixture with carbofuran or with benzene; all of them were at concentrations below 10(-2) M. The limited domain, where the Debye and Hückel formalism for solutions and the Wagner-Onsager-Samaras (WOS) model for surfaces are correct, is then respected. This study was aimed at trying to identify the part played in the surface by the different particles of the system components and in particular the role of water. When aqueous solutions of nonorganic salts are dilute enough, their surface tensions are known to be salt concentration-independent; however, the zero value of the resulting relative adsorption has never been the subject of analysis about water behavior. By combining experimental relative adsorptions and Gibbs excesses calculated from the WOS theory, we will show that, in well-known solutions such as KCl ones, where the negative excess in salt can be very precisely modeled by the WOS theory, the resulting water excess Gamma(W) is negative. The same result can be obtained by taking into account the Ray-Jones effect. This observation drove us to wonder about the results of a similar analysis done on solutions of unsymmetrical electrolytes and on mixtures of salt and organic molecules. Experiments showed that, for all of the systems, Gamma(W) was negative. For a given salt, Gamma(W) was more negative in the presence of organic molecules, and carbofuran was a more efficient water repellent than benzene; water repulsion was greater with nitrates than with chlorides. From these data, it seems that water was repelled toward the solution bulk, whereas ions probably took place between the bulk and a layer of organic molecules. These observations called for a more detailed modeling.
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