In
fact, the heats of solution are the experimentally measured quantities,
and it is only with their help that we can get reasonable estimates
of heats of hydration. The lattice energies are on somewhat firmer
theoretical grounds. These "small" heats of solution are large enough
to have obvious physical consequences. The cooling when ordinary
table salt is dissolved in water is small, but can be felt if one
makes a concentrated solution and uses an aluminum tumbler. Ammonium
chloride absorbs so much heat when it dissolves that hoar frost
may form on the outside of the beaker. In contrast, sodium hydroxide
generates so much heat that the mixing beaker may become too hot
to touch.
To a certain extent, we can account for the trends in heats that
we see in the table. Ammonium chloride has a weaker lattice energy
than NaCl, because the NH4+ ion
is larger than Na+ and the binding
attractions in the crystal are weaker. Unfortunately, the hydration
energy also decreases with increasing ionic size, and it is difficult
to predict whether lattice energy or hydration energy will show
the greater change with larger ions.
The heats of hydration of Cl- and
OH- ions are similar, so in the
comparison of NaOH with NaCl, the dominant effect comes from weaker
crystal forces of NaOH in comparison with NaCl. The crystal structure
of NaOH is in fact a badly distorted NaCl structure, with the distortion
probably arising from the fact that the OH-
ions are nonspherical. It is possible that this distortion makes
the NaOH lattice easier to pull apart.
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