By J Burgess
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Extra info for Ions in Solution: Basic Principles of Chemical Interactions
3 THERMOCHEMISTRY OF ION SOLVATION The importance of ion hydration enthalpies in determining solubilities of salts was emphasised at the very beginning of this text (Introduction and Fig. 1 ). There it was shown, using the specific example of sodium chloride, that enthalpies of solution generally represent small differences between large lattice enthalpies and large ion hydration enthalpies. The main topics of this section are the dependence of ion hydration enthalpies on the nature of ions and the indications of strengths of ion-solvent interactions given by ion solvation enthalpies (cf.
Here the number of nearest neighbour vertices is again always three, but the geometric consequence of packing three types of polygon together is that all sides can no longer be quite equal. So the first peak in the radial distribution function is no longer sharp but somewhat broadened, to include the actual range of nearest-vertex distances. The range of next-nearest vertex distances will obviously be greater, giving a second broader peak. Very soon the peaks blur together, as shown in the middle plot of Fig.
9 compares hydration enthalpies for some pairs of cations of identical charge and approximately equal radii. Values for B-Group and transition metal cations are markedly more negative than for A-Group ions of similar radii. 2), with the extra hydration enthalpy ascribed to polarisation or covalent interaction contributions. 10). For anions such asp-, there is a Sec. 10- The reflection of Crystal Field stabilisation on ion hydration enthalpies for the first row d-block 2+ cations Cation cr2+ Mn2+ Fe2+ eo2+ Ni2+ Cu2+ Zn 2+ "' ds d6 d1 d8 tP dlO 0 4Dq 8Dq 12Dq 6Dq 0 6Dq CFSE llHhydr(kJ mol- 1) -1850 -1845 -1920 -2054 -2106 -2100 -2044 t possibility of increased ion-solvent interaction through hydrogen-bonding in protic solvents such as water.