Polarization of water

Zhao X L, Ong S W and Eisenthal K B 1993 Polarization of water-molecules at a charged interface. Second harmonic studies of charged monolayers at the air/water interface Chem. Phys. Lett. 202 513-20... 

The beneficial effect of water in the arene - arene interaction can be explained by the fact that this solvent is characterised by a low polarisability so that interactions of the aromatic rings with water are less efficient than with most organic solvents. Also the high polarity of water might lead to a polarisation of the aromatic rings, thereby enhancing electrostatic interactions. Finally, hydrophobic interactions may be expected to play a modest role. 

Water as the solvent is essential for the acid-base setting reaction to occur. Indeed, as was shown in Chapter 2, our very understanding of the terms acid and base at least as established by the Bronsted-Lowry definition, requires that water be the medium of reaction. Water is needed so that the acids may dissociate, in principle to yield protons, thereby enabling the property of acidity to be manifested. The polarity of water enables the various metal ions to enter the liquid phase and thus react. The solubility and extent of hydration of the various species change as the reaction proceeds, and these changes contribute to the setting of the cement. 

Figure 5.3 Polarization of water molecules by (a) a cation and (b) an anion 5.1.2 Near-Critical Water...

In the first model, the mnneling electron mainly interacts with the electronic polarization of water ( = 1.88) since tunneling was assumed to be fast in comparison with the orientational response of the dipolar molecules of the liquid. Considering water as a dielectric continuum between a jellium spherical tip and planar substrate yields an effective barrier for tunneling that is about 1 eV lower than that for the vacuum case [95]. This result is consistent with photoemission studies of metal/aqueous interfaces, which reveal electron emission into water at 1 eV below the vacuum level [95-97]. Similar models have been employed to examine the effect of thermal fluctuations on the tunneling current [98-100]. Likewise, a related model assessing the noise associated with the reorientation of adsorbed molecules has been presented [101]. 

The polar reactant ethylene glycol is consumed and as a consequence the catalyst phase becomes smaller and more polar, because of the higher polarity of water compared to ethylene glycol. At the same time a very non-polar reactant is consumed with butadiene and a large amount of semi-polar products are formed, which can also act as a mediator. As a result, more of the semi-polar solvent s3 is required at the beginning than after the reaction and the reaction mixture may no longer spht up into two phases. 

Cosolvents and salts mix completely with water to form homogeneous solutions, but with different effects. Cosolvents decrease the polarity of water and reduce the ability of an aqueous system to squeeze out nonpolar solutes, resulting in an increase in the solubility of nonelectrolytes. On the other hand, salts decrease the solubility on nonelectrolytes by increasing the polarity of water, thereby increasing the ability of the aqueous system to squeeze out the nonpolar solutes. 

Table 3.6 shows the dipole moments of some common solvent molecules. While dipole moments for HMPA and DMSO are different, the values for water, HF, and THF are similar. Water and HF, which both readily dissolve ionic compounds, are more polar solvents than THF. The use of dipole moments as a polarity indicator, seriously underestimates the polarities of water and HF as solvents. 

Water is an ideal candidate as a replacement solvent. It is nontoxic, nonflammable, readily available, inexpensive, and easy to handle. Unfortunately, switching from organic to aqueous solvents is not a simple task. As with coating applications, the high polarity of water offers many difficulties in its implementation as a reaction medium... 

Multidimensional coordinate characterizing the polarization of water molecules... 

To take into account the charge-solvent interaction, we introduce a multidimensional coordinate Xk that characterizes the polarization of water molecules around the k-th base pair. Then a standard linear response expansion enables one to express the interaction with the water environment as a function of Xk as... 

Because the kinetic energy dissipation of an excess electron by surrounding water molecules plays an essential role during the formation of electron-radical pairs, the influence of the quantum polarization of water molecules and OH radical must be investigated in detail. Further experimental studies on the short-time dependence of vibronic couplings in aqueous environment would permit to understand the contribution of Jahn-Teller effects on the crossing of an elementary redox reaction with OH radical. 

Polarization of water molecules and surface acidity, in relation to the nature of interlamellar cations. 

The problem of polarization of solvent molecules, as well as solutes in a solution, is a serious one when MD simulations are applied to electrolyte solutions. Attempts have been made to combine ab initio calculations with the usual MD simulation process in which the polarization of water molecules caused by ion-water interactions is estimated at each step of the MD calculations, and thus, we can expect that... 

An important aspect that deserves attention is the extreme polarity of water. Its solubility parameter is around 25, while all other compounds in table 2.2, polar or non-polar, are found between about 5 and 16. 

M. Manciu, E. Ruckenstein Polarization of Water near Dipolar Sutfaces A Simple Model for Anomalous Dielectric Behavior, LANGMUIR 21(2005) 11749-11756. 

One can therefore conclude that there is no commonly accepted explanation for the microscopic origin of the hydration repulsion. The main purpose of this paper is to show that a suitable model for the polarization of water layers, based on the earlier work of Schiby and Ruckenstein,10 is compatible with both simulations and experiments on hydration repulsion. 

The first physical models for the hydration force related the interactions to the polarization of water near a surface,... 

The Gruen—Marcelja model could relate the hydration force to the physical properties of the surfaces by assuming that the polarization of water near the interface is proportional to the surface dipole density.9 This assumption led to the conclusion that the hydration force is proportional to the square of the surface dipolar potential of membranes (in agreement with the Schiby—Ruckenstein model),6 a result that was confirmed by experiment.10 However, subsequent molecular dynamics simulations revealed that the polarization of water oscillated in the vicinity of an interface, instead of being monotonic.11 Because the Gruen—Marcelja model was particularly built to explain the exponential decay of the polarization, it was clearly invalidated by the latter simulations. Other conceptual difficulties of this model have been also reported.12 13... 

---