EXPERIMENT 2: SOLUBILITY AND THERMODYNAMICS

Introduction
This experiment allows you to examine an equilibrium reaction, a solubility curve, and the
thermodynamics associated with equilibrium concepts in a simple, quick, safe and cheap
way.
There are two simplifying assumptions made in the calculations:
• the activities of the ions and the ionic strength of the solutions are not considered, and
• the temperature at which crystals become visible is probably lower than equilibrium
temperature
In this experiment several thermodynamic variables (∆H, ∆S and ∆G) will be calculated
for the simple dissolution reaction of potassium nitrate (KNO3) (strong electrolyte) shown
below.

KNO3 (s) + H2O ⇌ K+ (aq) + NO ̄3 (aq)

The solubility in mole/liter of the compound will be measured for six or seven
temperatures over a range of 40 – 60 ℃. These values will then be used to calculate the
thermodynamic variables using the method outlined in the calculations section below.

Procedure
Caution: Potassium nitrate is a strong oxidiser and skin irritant. Avoid contact with skin,
eyes, and mucous membranes. Avoid shock, heat and contact with combustible materials.

1. Weigh 20 g KNO3 and transfer it to a large test tube (25 x 200 mm). Note: Technical
grade KNO3 does not seem to work well.
2. Add 15 mL water and heat the test tube in a boiling water bath, with stirring, until all
the KNO3 has been dissolved.
3. Determine and record the volume of the KNO3 solution. This can be done by filling
another large test tube (25 x 200 mm) with water until the volumes in both tubes are
the same, then measuring the volume in the test tube filled with water in a graduated
cylinder.
4. Remove the test tube with KNO3 solution from the water bath and allow it to cool
while slowly stirring the solution. Insert a thermometer into the solution.
5. Record the temperature when the crystals first appear. It is assumed at this
temperature the system is at equilibrium and it is possible to calculate the equilibrium
concentrations of the ions.
6. Add 5 mL water to the test tube and warm the mixture until the solid has all dissolved.
Determine the solution volume as before and record.
7. Cool slowly and record the temperature at which crystals first appear.
8. Repeat the cycle (steps 6 and 7) adding 5 mL until a crystallisation point temperature
near room temperature is reached. This should take 6 – 7 determinations.
9. When you have obtained all data, record it on the whiteboard for the class to use in
their laboratory reports i.e. use the averaged data for the whole class to carry out the
calculations that follow.

Calculations
The dissolution reaction may be considered to be at equilibrium when the solid is in
contact with a saturated solution – just the condition you have when crystallisation
begins. The solubility, s, of the salt in moles per liter may be calculated from the amount
of salt weighed out and the volume of the solution.

The equilibrium constant K for the reaction will be:

K = [K+][ NO3̄ ] = (s)(s) = s2 (1)

The equilibrium constant K may be used to calculate ∆G for the reaction at each
temperature using the following relationship:
∆G = −RT ln K (2)
where T is the Kelvin temperature and R is the gas constant (8.314 JK ̄ 1mol ̄ 1). Using
eqn. (1), calculate K for each temperature, and eqn. (2) calculate ∆G for each
temperature. The variation of K with temperature is such that if a plot of ln K (y-axis)
versus 1/T is made, the result is straight line with the slope -∆H/R (Clausius-Claperyon
relationship). Construct this graph and determine the slope and hence the value of ∆H for
the reaction. (∆H is nearly a constant over a small range of temperature).
Use the values of ∆G and ∆H to calculate ∆S at each temperature from the relationship,
∆G = ∆H - T∆S.
Is the reaction exothermic? Does crystallisation increase or decrease the entropy?