Determination of the differential heat of solution

Determination of the Benzoic acid solubility in water

Summary
The aim of this experiment is to emphasize the relation between solubility and
temperature and to calculate the differential heat of solution for a solid at saturation.
Theoretical aspects
The equilibrium conditions between solid phase and liquid phase for a 2 components
system could be considered in 2 ways:
a) If the solution is in equilibrium with solid phase of the component in excess( the
solvent) one says that the solution is at freezing point and the curve which represents the
variation of this temperature depending on liquid composition is called the freezing point
curve.
b) If the solid phase of the component which is found in a smaller quantity( solute) is in
equilibrium with the solution ,one says that is the case of a saturated solution and the
temperature variation on composition is represented by the solubility curve.
As there are no thermodynamic differences between solvent sand solute, the distinction
among freezing curves and solubility curves is just a matter of convention. The solution
process consists essentially from two steps with opposite thermal effects:
-the breaking of crystalline network of the solid, which requires consumption of energy
-the solvation (hydration for solution in water) through which intermolecular links
between solvent and solute are established, the process being accompanied by release of
energy
The global effect is either endothermic or exothermic as one of the processes above
prevails.
One of the simplest cases of phase equilibrium is that of a saturated solution in contact
with excess solute; molecules leave the solid and pass into solution at the same rate at
which molecules from the solution are deposited on the solid. The term solubility refers
to a measure, on some arbitrarily selected scale, of the concentration of the solute in the
saturated solution.
Here the molal concentration scale will be used and the solubility then becomes equal to
the molality mi,s of the solute in the saturated solution.
An equilibrium constant relation may be written for the phase equilibrium considered:
a
K i *i
(eq.1)
ai
Here ai represents the activity of the solute in the saturated solution and a , the activity of
the pure solid solid ( conventionally equal to unity).The activity ai is related to the
molality mi of the solute by means of the activity coefficient i, a function of T , P and
composition which approaches unity as mi approaches zero. Then:
K a i , s (mi , s ) i , s mi , s
(eq.2)
,where the subscript s indicates that the relation applies to the saturated solution.

The change in K with temperature at constant pressure reflects a change in mi,s , and also
the change in i,s, which is affected by both the variation s in temperature and
concentration of the solution.
ln K
T

H
R T 2

(eq.3)
, where H= standard enthalpy change for solution process. This quantity should not be
confused with any actual experimentally measurable heat of solution: it can be
determined indirectly, however.
It is obtained:

ln

x 2(T2 )
x

(T1 )
2

d H sat

In the case of diluted solutions:

1 1

T
1 T2
x2(T2 ) c1(T2 )

x2(T1 ) c2(T1 )

(eq.4)
(eq.5)

From the (eq.4) and (eq.5) we get that:

c 2(T2 ) d H sat
ln (T1 )
R
c2

1 1

T
1 T2

which allows us to calculate the differential heat of solution:

c 2(T2 )
R ln (T )
c2 1
d
H sat
1 1

T
1 T2

(eq.6),

(eq.7)

Determination of the benzoic acid solubility in water

The determination of a solid solubility can be easily proceeded by mixing an excess of
solute with the solvent, till the equilibrium state is established. Then the saturated
solution is filtered and analyzed to estimate the solute concentration at saturation (mi,s).
The solubilities of benzoic acid (i) in water are determined at room temperature and at
45C. Having these data the differential heat of solution of benzoic acid at saturation
should be computed.
Laboratory equipment
A, thermostate,2 100-ml Erlenmeyer bottles, 2 pipettes( 50 and 100 ml), one short rubber
tube to be attached t the pipettes, glass wool, one burette, on 250 ml Erlenmeyer
flask,0.1N NaOH solution, distilled water, benzoic acid and phenolphthalein as indicator.
Working procedure
In one of the Erlenmayer bottles with caps introduce 1 g benzoic acid and 75 ml water.
Stirr at room temperature for about an hour. In the other Erlenmayer flask, introduce 2g
benzoic acid and 75ml water. Leave it in a thermostat at about 45C for about an hour
(this is enough time to reach the equilibrium). After this, the determination of solubilities
can begin. To prevent drawing small crystals into the pipette along with solution, a filter

from glass wool into a rubber tube is wrapped around the tip of the pipette. The filter is
removed before draining the pipette. In the first Erlenmayer flask introduce 50 ml of
benzoic acid solution at room temperature and in the other flask introduce 10 ml of the
solution of benzoic acid which was maintained in the thermostat. Each solution in titrated
with 0.1NaOH solution, in the presence of phenolphthalein as pH indicator.