Enthalpy of Solution part 1

In this topic you will be looking at the energetics behind dissolving an ionic compound in water.

Dissolving ionic compounds

There are only two stages involved with this process:

1. breaking the ionic lattice gaseous ions e.g. NaCl(s) Na+(g) + Cl-(g)

2. hydrating the ions (forming bonds with water molecules) e.g. Na+(g) + Cl-(g) Na+(aq) + Cl-(aq)

Breaking the lattice

You will have looked at forming an ionic lattice when you did ionic bonding in Topic 2 at AS. This would be
called the lattice enthalpy and is exothermic as bonds are formed. Here, we are looking at the opposite
reaction, breaking the strong ionic bonds (lattice dissociation), which is endothermic.

The diagram on the left shows a lattice of positive and negative ions held together by strong electrostatic
forces. When it is broken we have free ions:

-
- + - + - + +
+ - + - + - + -
- + - + -
- + - - +
+ - +
+ -
+
After breaking the lattice, the ions are in the gaseous state. For example:

NaCl(s) Na+(g) + Cl-(g)

Hydration
The interaction between water molecules and the ions results in the ions being hydrated i.e. the are
surrounded by water molecules.
The + on the H is attracted to the negative ion, and the and - on the O is attracted to the positive ion.

As bonds between the water molecules and the ions are being made, this is an exothermic process called
hydration enthalpy.

= H2O
+
-
For example:

Na+(g) + Cl-(g) Na+(aq) + Cl-(aq)

Enthalpy of solution
The enthalpy of solution is the overall result of the lattice breaking up and the ions being hydrated. This
value tells you whether an ionic compound will dissolve or not.

NaCl(s) Na+(aq) + Cl-(aq)

a negative enthalpy of solution value means that it should dissolve

The point of all this is to see whether an ionic compound will dissolve or not. If Hsol is negative then it
will dissolve and if its positive it wont. Well thats the general rule.

But sometimes a compound with a positive Hsol value will still dissolve. This is due to entropy.

When dissolving a solid, there is a change of state (solid aqueous) so there must be an increase in
entropy.

If the entropy change is big enough it can overcome a positive H sol value and the compound will dissolve,
which is actually the case with NaCl. However, a very large positive value will be difficult to overcome and
it probably wont dissolve.

Hesss Law
Here is an example of using Hesss cycle for dissolving an ionic compound:
From the cycle you can say that:

-Hlatt + Hhyd = Hsol

or

Hsol = Hhyd - Hlatt

it is worth remembering this equation and then just rearrange for any other value that they ask you
to calculate.

Alternatively you could have drawn the cycle as shown below to get it in terms of H latt rather than -Hlatt:

Born-Haber Cycles
Another way is to represent this information is in a Born-Haber cycle.

The starting point at the top is the ions in their gaseous states. The structure of this cycle will be the same
no matter what ionic compound you are looking at.

Using the same theory as for Hesss Law, you would say:

Hhyd = Hlatt. + Hsol rearranges to give Hsol = Hhyd - Hlatt

 Na+(g) + Cl-
(g)

Hlatt

Hhyd
NaCl(s)

Hsol
Na+(aq) + Cl-
(aq)

be careful with the arrow for Hsol. Like a normal Born-Haber cycle a downward arrows =
exothermic and an upward arrow = endothermic. As Hsol can be positive or negative you may
have to draw the arrow going upwards, which should actually be the case for NaCl.

Also be careful with the hydration enthalpies. Remember that there are two values; one for each
ion.