Water polarisability

Solvent suppression. General formalism to describe the evolution of the water polarisation in the course of an NMR experiment was presented by Hiller et al The model calculations were used to optimise the efficiency of water suppression. These have demonstrated that the performance of flip-back methods improve with the increase of the longitudinal relaxation rate of water protons. To this aim relaxation agents that selectively enhance water relaxation can be successfully used. 

The three-body contribution may also be modelled using a term of the form i ( AB,tAc,J Bc) = i A,B,c exp(-Q AB)exp(-/i Ac)exp(-7 Bc) where K, a, j3 and 7 are constants describing the interaction between the atoms A, B and C. Such a functional form has been used in simulations of ion-water systems, where polarisation alone does not exactly model configurations when there are two water molecules close to an ion [Lybrand and Kollman 1985]. The three-body exchange repulsion term is thus only calculated for ion-water-water trimers when the species are close together. 

Corongiu G 1992. Molecular Dynamics Simulation for Liquid Water Using a Polarisable and Flexible Potential. International Journal of Quantum Chemistry 42 1209-1235. 

Dang L X, J E Rice, J Caldwell and P A Kollman 1991. Ion Solvation in Polarisable Water Molecular Dynamics Simulations. Journal of the American Chemical Society 113 2481-2486. 

Sprik M and M L Klein 1988. A Polarisable Model for Water Using Distributed Charge Sites. Journal of Chemical Physics 89 7556-7560. 

This perturbation method is claimed to be more efficient than the fluctuating dipole method, at least for certain water models [Alper and Levy 1989], but it is important to ensure that the polarisation (P) is linear in the electric field strength to avoid problems with dielectric saturation. 

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. 

If three oxygens of each tetrahedron are shared, sheet struetures form (Fig. 16.4d). This is the basis of clays and micas. The additional M attaches itself preferentially to one side of the sheet - the side with the spare oxygens on it. Then the sheet is polarised it has a net positive charge on one surface and a negative charge on the other. This interacts strongly with water, attracting a layer of water between the sheets. This is what makes clays plastic the sheets of silicate slide over each other readily, lubricated... 

It should be emphasised that potential-pH diagrams can also be constructed from experimental E -I curves, where E is the polarised potential and / the current. These diagrams, which are of more direct practical significance than the equilibrium potential-pH equilibrium diagrams constructed from thermodynamic data, show how a metal in a natural environment (e.g. iron in water of given chloride ion concentration) may give rise... 

Horvith, J. and HackI, L., Check of the Potential/pH Equilibrium Diagrams of Different Metal-Sulphur-Water Ternary Systems by Intermittent Galvanostatic Polarisation Method , Corros. Sci., 5, 525 (1965)... 

Sulphates, silicates, carbonates, colloids and certain organic compounds act as inhibitors if evenly distributed, and sodium silicate has been used as such in certain media. Nitrates tend to promote corrosion, especially in acid soil waters, due to cathodic de-polarisation and to the formation of soluble nitrates. Alkaline soils can cause serious corrosion with the formation of alkali plumbites which decompose to give (red) lead monoxide. Organic acids and carbon dioxide from rotting vegetable matter or manure also have a strong corrosive action. This is probably the explanation of phenol corrosion , which is not caused by phenol, but thought to be caused by decomposition of jute or hessian in applied protective layers. ... 

The problem of the high resistance polarisation decreases with increasing water content and salinity, such as prevails during immersion in seawater, where these anodes are particularly useful. Since no problems of burial arise in that environment an endless variety of disused iron-ware has been utilised for anodes, e.g. pipes, piling, machinery, rails and even obsolete shipping which has not been economic to salvage. Consumption rates in excess of the theoretical value have been reported for steel in different waters . 

In electrolytes containing both sulphate and chloride ions, the sulphate ion favours the formation of lead sulphate which is rapidly transformed to lead dioxide. The continuing satisfactory operation of the anode depends upon the initial conditions of polarisation. The lead dioxide is of better quality and more adherent when formed below 108 Am in solutions containing higher sulphate concentrations or when the water is agitated" . 

Current density requirements depend on the environment, galvanic effects, velocities and other factors influencing polarisation. In the absence of galvanic influences or other secondary effects 30mA/m may be sufficient in sea-water to maintain adequate polarisation for protection once it has been achieved it is however normally necessary to apply 100-150 mA/m to achieve initial polarisation within a reasonable period and if rapid protection is required, current densities as high as 500 mA/m may be applied. 

From Fig. 10.40 it will be seen that contact between the electrolyte (soil or water) and the copper-rod electrode is by porous plug. The crystals of CUSO4 maintain the copper ion activity at a constant value should the halfcell become polarised during measurements. The temperature coefficient of such a cell is extremely low, being of the order of 1 x 10" V/°C and can thus be ignored for all practical purposes. To avoid errors due to polarisation effects, it is necessary to restrict the current density on the copper rod to a... 

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