Interfacial Chemical Reactivity Enhancement

<p>This publication reports self-consistent solutions of reaction and adsorption equilibria indicate that interfacial reactivity enhancement is driven primarily by the adsorption free energy of the product (or activated complex). The results indicate that reactant surface activity has a smaller indirect influence on reactivity due to compensating reactant interfacial concentration and adsorption free energy changes, as well as adsorption-induced depletion of the droplet core. Experimental adsorption free energies and critical micelle concentration correlations provide quantitative surface activity estimates as a function of molecular structure, predicting an increase in interfacial reactivity with increasing product size and decreasing product polarity, aromaticity and charge (but less so for anions than cations). Reactions with small, neutral or charged products are predicted to have little reactivity enhancement, unless the product is rendered sufficiently surface active by, for example, interactions with interfacial water dangling OH groups, charge transfer, or voltage fluctuations.</p>