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LIST OF FIGURES AND TABLES

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3
ABSTRACT

This experiment was done in order to determine the solubility of the benzoic
acid over a range of temperatures and consequently calculate its heat of
solution. The experiment was conducted by using a solution of saturated
benzoic acid together with the titration method using 0.1M NaOH solution and
phenolphthalein indicator. This operation was performed at 300C and 600C;
and was done by heating the solution contained in the 250ml conical flask and
conducting the titration upon equilibrium. Variables such as temperatures,
initial and final mass as well as the initial and final volumes of the solution
before and after titration, giving rise to the calculation of the solubility of the
benzoic acid as well as the enthalpy of dissolution.

4
INTRODUCTION

The heat of solution, also called enthalpy of dissolution, or enthalpy of solution

is the enthalpy change associated with the dissolution of a substance in a
solvent at constant pressure resulting in infinite dilution. The enthalpy of
solution is one of the three dimensions of solubility analysis. Solubility is the
amount of a particular substance that can dissolve in a particular solvent; it is
usually given in mol/L. A solvent is a species capable of dissolving other
substances (solutes), while a solute is the dissolved matter in a solution, or the
component of a solution that changes its state.
For a given solute, the heat of solution is the change in energy that occurs as
one mole of the solute dissolves in a solvent. During the dissolving process,
solutes either absorb or release energy.
If solutes absorb energy from the solvent as they dissolve, the solution gets
colder and the reaction is endothermic. If solutes release energy to the solvent
as they dissolve, the solution gets warmer and the reaction is exothermic. By
using a titration method to determine the solubility and measuring the change
in the temperature of the solution during the dissolving process, the heat of
solution can be calculated.
Solutions are very common in nature. In order for any reaction to occur there
must be a change in energy. The ease of dissolution is dependent on the
temperature of the system and type of solution, being endothermic or
exothermic. Generally, when dissolution occurs, the entropy of the system
increases. It is important to determine the heat of solution (enthalpy change);
this is because a change in enthalpy takes account of energy transferred to the
environment through the expansion of the system under study.
The total enthalpy, H, of a system cannot be measured directly. Thus, change
in enthalpy (∆ H ), is a more useful quantity than its absolute value. The change,
∆ H , is positive in endothermic reactions, and negative in exothermic
processes. Enthalpy is a thermodynamic potential. It is a state function and an
extensive quantity. The enthalpy is the preferred expression of system energy
changes in many chemical, biological, and physical measurements, because it
simplifies certain descriptions of energy transfer.

5
ABSTRACT

This experiment was done in order to determine the solubility of the benzoic
acid over a range of temperatures and consequently calculate its heat of
solution. The experiment was conducted by using a solution of saturated
benzoic acid together with the titration method using 0.1M NaOH solution and
phenolphthalein indicator. This operation was performed at 300C and 600C;
and was done by heating the solution contained in the 250ml conical flask and
conducting the titration upon equilibrium. Variables such as temperatures,
initial and final mass as well as the initial and final volumes of the solution
before and after titration, giving rise to the calculation of the solubility of the
benzoic acid as well as the enthalpy of dissolution.

6
7
THEORY

The heat of solution or enthalpy of solution is one of the three dimensions of

solubility analysis. It is the change in enthalpy associated with the dissolution
of a solvent at constant pressure resulting in infinite dilution, thus as one mole
of the solute dissolves in the solvent. In the process, energy can either be
absorbed or released; it is expressed in kJ/mol at constant temperature, with
positive values indicating endothermic values and negative values indicating
energy released or exothermic energy. Dissolving a gas in liquid solvent
releases energy, as heat, into the surroundings in an exothermic reaction. The
temperature of the solution decreases as energy leaves the system; therefore,
solubility of a gas increases with a decrease in temperature of solution. On the
other hand, when the solution is heated, the reverse reaction occurs and gas
evolves. Enthalpy of hydration is one of the most common types of heat of
solution. A substance, commonly a salt is dissolved in water. When completely
dissolved, the heat of solution is at its maximum. Dissolution of a solute can
occur in three steps:
a. Breaking of solute-solute attraction (endothermic)
b. Breaking of solvent-solvent attractions (endothermic)
c. Forming solvent-solute bonds (exothermic)
The sum of the individual enthalpy changes of each step is the overall value of
the enthalpy change. Stronger bonds are formed in solutions with negative
enthalpy changes and these solutions tend to have a lower vapor pressure. A
positive enthalpy indicates that the solute is not easily dissolved in the solvent;
while a negative enthalpy indicates that a solute is easily dissolved in the
solvent.
Three conditions are fulfilled in the process, as mentioned before, the pressure
remains constant, the temperature remains constant (indicating standard
conditions of temperature and pressure), and there is expansion against the
atmosphere and work is done. The enthalpy of solution is only valid for
dissolution of a pure substance into another pure substance. Enthalpies of
solution of most substances can be measured directly when the resulting
solution is liquid. A constant temperature can be maintained if the solute is
dissolved slowly.

8
When a solid is dissolved in a solvent in which it is soluble, it dissolves until
saturation is reached at a certain temperature. It is necessary to determine the
amount of solute dissolved and the nature of solid phase in equilibrium with
the solution when performing solubility measurements. Solubility depends on
temperature; it increases with temperature in an endothermic reaction and
decreasing with increase in temperature in exothermic reactions. The well-
known van't Hoff equation relates the solubility of a reaction, K, to the
enthalpy change of that reaction, ∆ H :
d lnx −∆ H
=
dT RT2

Integrating the equation gives:

x 2 −∆ H 1 1
ln ⁡( )= ( − )
x1 R T2 T1

Where x1 is solubility at T1 and x2 is solubility at T2.

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DESCRIPTION OF APPARATUS

The apparatus used during the experimental work were:

 Measuring cylinder
 Retort stand
 Separating funnel
 Beakers
 Conical Flask
 Burette
 25ml Pipette
 Thermostat
 Heater
 Thermometer
The chemicals used to for the experimental work were: solid benzoic acid,
sodium hydroxide pellets, phenolphthalein indicator and water.

PROCEDURE

200ml of distilled water was heated with 2g benzoic acid to obtain a

saturated solution.
The solution was placed in a thermostat to bring it to a constant
temperature.
25ml of the heated solution of benzoic acid was withdrawn twice and each
titrated with 0.1M sodium hydroxide with phenolphthalein indicator.
A pipette was used to withdraw 25ml of the benzoic acid solution and drain
it into a 100ml conical flask. Three drops of the phenolphthalein indicator
were added to the solution
The benzoic acid solution was titrated using the sodium hydroxide solution.
Once the colour of the solution changed to light pink, the volume of sodium
hydroxide used was recorded, 28.5ml.
The experiment was done at 300C and repeated at 600

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11
RESULT

Average value of NaOH used: At 310C, V́ = 11.75ml

At 500C, V́ = 13.85ml

The dissolution of benzoic acid is given by the following chemical equation:

−¿¿
H 5 CO 2 ¿
C 6 H 5 C O 2 H ⇋ H +¿+C 6

And the reaction of benzoic acid and sodium hydroxide is given by the
following chemical equation:
C 6 H 5 C O2 H + NaOH ⇋ C6 H 5 C O2 Na+ H 2 O

During the titration process, when equilibrium is reached the number of moles
of benzoic acid and sodium hydroxide are equal. Thus:
nbenzoic acid = nNaOH
At 310C, with average volume of NaOH used being 11.75ml
The number of moles of sodium hydroxide is found to be:
n b=C b x V b

Where b is NaOH
Cb = 0.1M
Vb = 11.75xI0-3L
nb = 0.1M x 11.75xI0-3L
nb = 11.75x10¯4moles of NaOH
Recall nbenzoic acid = nNaOH
Therefore, naT1 = 11.75x10¯4moles of benzoic acid

At 500C, with average volume of NaOH used being 13.85ml

The number of moles of sodium hydroxide was:
n b=C b x V b

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Cb = 0.1M
Vb = 13.85xI0-3L
nb = 0.1M x 13.85xI0-3L
nb = 13.85x10¯4moles of NaOH
And nbenzoic acid = nNaOH
Therefore, naT2 = 13.85x10¯4moles of benzoic acid
n at 1
x 1=
nat 1 +nat 2

11.75 x 10−4
x 1=
11.75 x 10−4 +13.85 x 10− 4
x 1=0.4590

at 2n
And x 2= n +n
at 1 at 2

13.85 x 10−4
x 2=
11.75 x 10−4 +13.85 x 10− 4
x 2=0.5410

Solubility (mole fraction) Temperature (K)

0.459 304
0.541 323

Putting the values of mole fraction and temperature into the van’t Hoff
equation, with R being the universal gas constant = 8.314Jmol-1k-1:
x 2 −∆ H 1 1
ln ⁡( )= ( − )
x1 R T2 T1

0.541 −∆ H 1 1
ln ⁡( )= ( − )
0.459 8.314 323 304

−∆ H −4
0.1644= (−1.935 x 10 )
8.314

13
0.1644 x 8.314
=−∆ H
−1.935 x 10− 4
−7062.3485=−∆ H
J
∆ H =7062.3485
mol
kJ
∆ H =7.06
mol

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15
CONCLUSION

The heat of solution, ΔH, was found to be 7.06kJ/mol.

16
RECOMMENDATIONS

17
REFERENCES

1. Bookrags. (2006). Heat of Solution. Retrieved August 16, 2011, from

BookRags: http://www.bookrags.com/research/heat-of-solution-woc
2. Department of Chemical Engineering. (2011). Practical Manual S4.
Durban, KZN, South
3. Africa: Durban University of Technology. M, S. J., Ness, H. V., & Abbott,
M. (2003). Introduction to Chemical Engineering
4. Thermodynamics. In J. Smith, H. V. Ness, & M. Abbott, Introduction to
Chemical Engineering Thermodynamics (pp. 426 - 432). New York:
McGraw - Hill.
5. University, A. (2005). heat of solution. Retrieved August 14, 2011, from
http://www.pulse.pharmacy.arizona.edu/resources/heatofsolution.pdf
6. Zumdahl, S. A., & Zumdahl, S. S. (2006). Chemistry. In S. A. Zumdahl, & S.
S. Zumdahl, Chemistry (pp. 489 - 492). Urbana: Houghton Mifflin.
7. Haase, R. In Physical Chemistry: An Advanced Treatise; Jost, W., Ed.;
Academic: New York, 1971; p 29.
8. Laidler, K. The World of Physical Chemistry; Oxford University Press:
Oxford, 1995; p 110.
9. C.Kittel, H.Kroemer In Thermal Physics; S.R Furphy and Company, New
York, 1980; p246
10.DeHoff, R. Thermodynamics in Materials Science: 2 ed.; Taylor and
Francis Group, New York, 2006.

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APPENDIX:

a. Solubility (S) is the property of a solid, liquid or gaseous chemical

substance called solute to dissolve in a solid, liquid or gaseous solvent.
Solubility is measured in mol/L, mg/L, mol/kg
b. The equilibrium constant (K) of a chemical reaction is the value of its
reaction quotient at chemical equilibrium, a state approached by a
dynamic chemical system after sufficient time has elapsed at which its
composition has no measurable tendency towards further change.
K - Equilibrium constant
x - Solubility
x1 - Solubility at temperature, T1
x2 - Solubility at temperature, T2
∆H - Standard enthalpy of solution; kJ/mol
T - Temperature; K
R - Universal gas constant, 8.314Jmol-1k-1
Cb - Concentration of base
Vb - Volume of base
nb - Number of moles of base
nNaOH - Number of moles of NaOH
nbenzoic acid - Number of moles of benzoic acid

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