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On approaching to a distance equal to their diameters (0.276 nm), water molecules (jU = 6.23 x 10~28 C cm) form a quite stable entity with potential energy Udd= 3.32X 10~20J = 0.2eV. If a comparably large univalent ion approaches a dipolar water molecule (\q'\ = 1.6 x 10~19C), the absolute energy value is almost four times larger, that is Uid= -1.18 x 10"19 J = 0.7 eV. If one water molecule in liquid water is replaced in the tetrahedral lattice by an uncharged particle of the same dimensions, then the four closest water molecules suffice to retain the original arrangement. If the new particle has a sufficiently large charge, e.g. positive, then the arrangement must change. Two water molecules are bonded more strongly than previously and the other two must rotate their negative 'end' towards the cation (Fig. 1.4). Thus, depending on the size and charge of the ion, the original arrangement can either be retained or a new, strong structure can be formed, or some state between these two extremes emerges. The

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Strain (%)

Fig. 1.4 Disturbing effect of a cation (void circle) on water structure. Molecules 1 and 2 show reversed orientation

308W

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ordering of the liquid can be completely destroyed if the ion disturbs the original arrangement without forming a new one Negative hydration numbers are then obtained for some ions, as if these salts produced 'depolymerization' of the water structure This phenomenon is termed structure breaking The destructive effect increases with increasing ionic radius, eg in the order Li+<Na+<Rb+<Cs+, Cl", NO 3 " < Br" < r < C1O3and with increasing charge, eg in the order Li+<Be2+<Al3+ Figure 15 schematically depicts a partially distorted water structure A region is formed in the immediate vicinity of the ion where the water molecules are electrostatically bonded so strongly to the ion that they lose the ability to rotate The value of the permittivity thus decreases sharply (to 6-7 compared to a value of 7854 at 25 C in pure water) This region is termed the primary hydration sphere.

0.025

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Depending on conditions, regions further from the centre of the ion contain a more or less distorted water structure and regions even further away retain the original structure It should be realized that the structure breaking results in an increase in the entropy of the system and thus in a decrease in its Gibbs energy (according to the well-known relationship at constant temperature, AG = AH TAS) If a more complex dissolved particle contains both charged (polar) and uncharged (non-polar) groups, then this entropy factor becomes important The structure of the solvent remains intact at the 'non-polar surface' of the particle In order to increase the entropy of the system this 'surface' must be as small as possible to decrease the region where the solvent structure is unbroken.

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This is achieved by a close approach of two particles with their non-polar regions or by a conformation change resulting in a contact of non-polar regions in the molecule These, mainly entropic, effects termed hydrophobic (in general solvophobic).

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Fig. 1.5 A scheme of hydration: (1) cation, (2) primary hydration sheath (water molecules form a tetrahedron), (3) secondary hydration shell, (4) disorganized water, (5) normal water

26 0 1 2 Time (min) (c) 3 4

interactions are, for example, the important factors affecting the conformational stability of proteins in aqueous solutions. O. J. Samoilov proposed a statistical approach to hydration. Ions in solution affect the thermal, particularly translational, motion of the solvent molecules in the immediate vicinity of the ion. This translational motion can be identified with the exchange of the solvent molecules in the neighbourhood of the ion. Retardation of this exchange is thus a measure of the ion solvation. If the water molecule remains in the vicinity of other water molecules for a time r and in the vicinity of the ion for a time rh then the ratio XJT is a measure of the solvation. If T , / T 1 , the water molecule is bonded very strongly to the ion. On the other hand, r / / r < l indicates negative solvation the ion breaks the solvent structure and the solvent molecules in its vicinity can more readily be exchanged with other molecules than those in the solvent alone, where a certain degree of ordering remains. Experimental values of the ratio T//T for aqueous solutions using H218O molecules lie in the range from tenths to unities. Some molecular solvents (such as ammonia, aliphatic amines, hexamethylphosphortriamide) dissolve alkali metals; solutions with molalities of more than lOmol-kg" 1 are obtained. Ammonia complexes M(NH3)6 analogous

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