Water theory, inadequacy

The simplest supposition, to make is that the increased concentration in the condensed film brings about increased velocity of reaction in virtue of a purely mass action effect. This theory, however, has been shown in many ways to be untenable. The clearest proof of its inadequacy is afforded by the study of those reactions in which the same substance can undergo transformation in alternative ways. Thus alcohol vapour can suffer decomposition into ethylene and water or into aldehyde and hydrogen according to the equations ... 

Having recognized the theoretical inadequacy of the dielectric theory for polar solvents, I started to reconsider the entire problem of solvation models. Because the good performance of dielectric continuum solvation models for water cannot be a result of pure chance, in some way there must be an internal relationship between these models and the physical reality. Therefore I decided to reconsider the problem from the north pole of the globe, i.e., from the state of molecules swimming in a virtual perfect conductor. I was probably the first to enjoy this really novel perspective, and this led me to a perfectly novel, efficient, and accurate solvation model based upon, but going far beyond, the dielectric continuum solvation models such as COSMO. This COSMO for realistic solvation (COSMO-RS) model will be described in the remainder of this book. 

Later, Pople concluded that A satisfactory theory must be based on the distortion of the bonds .Pople also noted the inadequacy of the Stockmayer potential for condensed water and said It is necessary to allow for the finite separation of the charges. A simple model containing a distribution of point charges was briefly discussed and discarded as not adequately representing the elastic bend coefficient of a bond. The possibility of a tetrahedrally distributed charge was mentioned, but not pursued. 

This inadequacy of the theory, irrespectively of whether a binding or a partitioning electrostatic model is used, goes far beyond the observations of Petrache et al. that the Hamaker constant should be modified in the presence of salts,or those ofMandu and Ruckenstein, that the hydration or the undulation force may also depend on the salt. Our results imply that the electrolytes are affecting the actual water-lipid interface, in a way that cannot be accommodated by the existing theory. 

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