Energy hydration

The SPC/E model approximates many-body effects m liquid water and corresponds to a molecular dipole moment of 2.35 Debye (D) compared to the actual dipole moment of 1.85 D for an isolated water molecule. The model reproduces the diflfiision coefficient and themiodynamics properties at ambient temperatures to within a few per cent, and the critical parameters (see below) are predicted to within 15%. The same model potential has been extended to include the interactions between ions and water by fitting the parameters to the hydration energies of small ion-water clusters. The parameters for the ion-water and water-water interactions in the SPC/E model are given in table A2.3.2. 

Obviously sufficient energy is available to break the A1—Cl covalent bonds and to remove three electrons from the aluminium atom. Most of this energy comes from the very high hydration enthalpy of the AP (g) ion (p. 78). Indeed it is the very high hydration energy of the highly charged cation which is responsible for the reaction of other essentially covalent chlorides with water (for example. SnCl ). 

Element Ionisation energy (kj mof ) Metallic radius (nm) Ionic radius (nm) Heal oj laporibation at 298 K (kJ mol ) Hydration energy oj gaseous ion (kJ moI ) (V)... 

The magnesium ion having a high hydration energy (Table 6.2) also shows hydrolysis but to a lesser extent (than either Be or AF ). The chloride forms several hydrates which decompose on heating to give a basic salt, a reaction most simply represented as (cf. p. 45) ... 

The small lithium Li" and beryllium Be ions have high charge-radius ratios and consequently exert particularly strong attractions on other ions and on polar molecules. These attractions result in both high lattice and hydration energies and it is these high energies which account for many of the abnormal properties of the ionic compounds of lithium and beryllium. 

In this discussion, entropy factors have been ignored and in certain cases where the difference between lattice energy and hydration energy is small it is the entropy changes which determine whether a substance will or will not dissolve. Each case must be considered individually and the relevant data obtained (see Chapter 3), when irregular behaviour will often be found to have a logical explanation. 

The enthalpies for the reactions of chlorine and fluorine are shown graphically in Figure 11.2 as the relevant parts of a Born-Haber cycle. Also included on the graph are the hydration energies of the two halogen ions and hence the enthalpy changes involved in the reactions... 

Electron affinity and hydration energy decrease with increasing atomic number of the halogen and in spite of the slight fall in bond dissociation enthalpy from chlorine to iodine the enthalpy changes in the reactions... 

In the presence of appropriate ligands, the values may be affected sufficiently to make Cu(l) stable but since the likely aquo-complex which Cu(I) would form is [Cu(H20)2], with only two water ligands, the (hypothetical) hydration energy of Cu is therefore much less than that of the higher charged, more strongly aquated [Cu(H20)e]. ... 

Another possible explanation is that 2-methyl-2-propyl cation allows better access to solvent than adamantyl cation. Examine hydrates of 2-methyl-2-propyl and adamantyl cations. How many water molecules does each accomodate Calculate hydration energies for the two cations. (The energy of water is provided at left.)... 

The surface behavior of Na is similar to that of Cs, except that inner sphere complexes are not observed. Although Na has the same charge as Cs, it has a smaller ionic radius and thus a larger hydration energy. Conseguently, Na retains its shell of hydration waters. For illite (Figure 6), outer sphere complexes resonate between -7.7 and -1.1 ppm and NaCl... 

In wet corrosion the metal ions are hydrated—the hydration energy of most metal ions is very large and thus facilitates ionisation (see Section... 

A. Hydration energy profile, using the Bom formalism (Eqn. 1), shows the drop of ion self energy as a function of the radius of a hydration sphere. Note that even with a hydration shell of 10 A radius not all of the hydration energy is obtained. 

We have already mentioned that the stability of the metallic crystal and the ionization energies of the atom tend to increase in the series sodium, magnesium, and aluminum. In spite of this, aluminum is still an excellent reducing agent because the hydration energy of the Al+1 ion is very large (Table 20-III). 

HYDRATION ENERGIES OF SOME THIRD-ROW IONS (kcal/mole)... 

Alpha carbon atoms, 348 Alpha decay, 417, 443 Alpha particle, 417 scattering, 245 Aluminum boiling point, 365 compounds, 102 heat of vaporization, 365 hydration energy, 368 hydroxide, 371 ionization energies, 269, 374 metallic solid, 365 occurrence, 373 properties, 101 preparation, 238. 373 reducing agent, 367 Alums, 403 Americium... 

Figure 8-8. Hydration energies for divalent transition metal ions.

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