Experiment No.

8
Heat of Solution: Vant Hoff Isochore Method
Reyza Kathleen Dimaculangan, Neil Anthony L. Florin
Alex Carl L. Ng, Ferguie B. Solis *
3-Chem, Department of Chemistry
College of Science, University of Santo Tomas
Abstract
In this experiment, the heat of the solution of naphthalene in toluene was determined using the Vant Hoff
equation. In obtaining the values, the temperature as well as the mole fraction of the mixture was used in
graphing the plot. A negative slope was obtained when the values were plotted, the chemical reaction is
said to be an endothermic reaction given the slope. Using the slope, the heat of the solution was
calculated to be 13.6 kJ/mol.

1.

Introduction
Thermodynamics incurs the systematic discussion as energy is being transferred or

transformed in bulk matter. Thermochemistry involves the study of energy in a chemical reaction
manifested as heat. For a chemical reaction to occur, the force needed is known as Gibbs free
energy. Which is comprised of enthalpy and entropy, as summarized on Equation 1.[1]
Equation 1.

Go= -RT ln K

Using Equation 1, further derivations of the said equation yield the Vant Hoff equation
as seen on Equation 2. Equation 2 expresses the slope of the plot of the equilibrium constant (ln
K) as the function of temperature. Enthalpy of the system varies with temperature, however H
does not depend on pressure.[1]
Equation 2.

d ln k p H o
=
dT
RT 2

Using the Vant Hoff equation the values of 1/T vs. ln X can be plotted in order to
complete the objective, with the slope equal equal to -H/R. The plot is effective in estimating
the change in enthalpy of a chemical reaction. The equation can also be used to determine the
change of the equilibrium constant of a chemical equilibrium to the change in temperature, given
the change of enthalpy in the process by integrating Equation 2 to yield Equation 3.[1]

Equation 3.

ln

k 2 H o 1
1
=

k1
R
T2 T1

In this experiment, two compounds, naphthalene and toluene are used in determining the
heat of the solution. Physical properties of these compounds can be seen on Table 1.
Table 1. Physical Properties of naphthalene and toluene

Compound

Naphthalene

Toluene

Molecular Formula

C10H8

C7H8

Molecular Weight

128.17 g/mol

92.14 g/mol

Melting point

80.3oC

-95oC

Boiling point

218.0oC

111oC

Structure

The objectives of the experiment are to determine the heat of the solution of naphthalene
in toluene through the Vant Hoff Isochore method. Assuming the solution to behave ideally. The
solubility of the solute will be measured at varying temperatures, in order to calculate the heat of
the solution.
2.

Experimental
In this experiment, the reagents used were toluene and naphthalene. Some materials that

were used in the experiment were; 250 mL beaker, 10mL pipette, digital thermometer, two-holed
stopper, stainless steel wire stirrer, hot plate and an aspirator.
An approximate 15 grams of naphthalene was weighed on an analytical balance and
added into a large test tube. Using a pipette, 5mL of toluene was added. The stopper,
thermometer and stirrer were also added to the set-up. The test tube was allowed to warm in the
water bath until all of the solute was dissolved. The solution was then allowed to cool in air and

was stirred continuously. When a solid started to form, the temperature was noted. Five more
determinations were made, each with an addition of 1 mL portions of toluene per succeeding
trial.
3.

Results and Discussion

A substances behavior changes in increasing temperatures per se, its solubility behavior

depends on the strength the intermolecular forces of attraction. In this experiment, the
compounds are found to be non-polar. However, van der waals forces is said to exist in
naphthalene, whereas induced dipole-induced dipole is said to be present in toluene. When
mixed, the substances are said to exhibit a zero amount of Gibbs Free Energy between the
naphthalene- naphthalene, naphthalene-toluene and toluene-toluene caused by the coherence of
its properties. Despite this fact with regards to the intermolecular forces of attraction between the
solute-solute, solute-solvent and solvent-solvent, the strengths of the forces are not of the same
strength. Which can be used to treat the system as ideal, however not completely. [2]
Table 2. Values in determining the heat of the solution.

Volume of

Temperature (K)

1/T

Mole fraction of

Ln X2

Toluene
5
6
7
8
9
10

340.25
332.25
328.95
326.85
323.35
321.95

0.002939
0.003010
0.003040
0.003060
0.003094
0.003106

Naphthalene
0.686
0.648
0.615
0.585
0.558
0.534

-0.380
-0.442
-0.499
-0.554
-0.605
-0.655

The data obtained in this experiment as summarized in table 2 is used to plot the graph of
1/T against ln X2. Plotting the values, allows the heat of the solution of naphthalene in toluene to
be determined, by equating the slope to the Vant Hoff equation.

-0.3
-0.35
-0.4

f(x) = - 1633.17x + 4.44

R = 0.95

-0.45

ln X2 of Naphthalene

-0.5
-0.55
-0.6
-0.65
-0.7

Figure
1. Plot of 1/T vs. ln X2

In using the Vant Hoff Equation (Equation 2), it shows that d ln K/dt < 0 for a reaction is
considered to be an exothermic reaction provided that the slope determined is positive. In the
case of a negative slope, the ln K or the value of K itself decreases as the temperature rises.
Therefore, according to the Le Chateliers principle, this stress in the system causes it to shift
towards the endothermic reaction. On the other hand, decreasing the temperature will disfavor
the formation of products. As such energy release causes the temperature to decrease.[1]
Based on Figure 1, the graph shows that the mole fraction of naphthalene is inversely
related to temperature. Given that the observed plot is sloping downwards (negative slope), this
shows the reaction observed was an endothermic reaction. Thus, heat was absorbed inducing a
positive change in enthalpy. The slope of the graph as indicated is -1633.2, further calculations
suggest that the heat of the solution is 13.6 kJ/mol. Calculations done in obtaining the heat of the
solution can be seen on the Appendix section of this paper.

4.

Conclusion
Using the Vant Hoff Isochore method, the heat of the solution of naphthalene in toluene

was determined. The plot of 1/t vs. ln X2 showed a negative slope since it favors the endothermic
reaction. The heat of the solution was determined to be 13.6 kJ/mol.
5.

References

[1] Atkins, P. & de Paula, J. (2006). Physical Chemistry. 8th Edition.

USA: W. H. Freeman and Company
[2] Chemguide. Raoults law and non-volatile solutes. Article retrieved on 15 Feb 2016:
<http://www.chemguide.co.uk/physical/phaseeqia/raoultnonvol.html>
Appendix
Calculating the number of moles and mole fraction
Moles of Naphthalene=15.0128

Moles of Toluene=x mL

( 1128moleg )=0.117

g 1mole
=x moles of toluene
( 0.87
1 mL )( 92.14 g )

Mole fraction of Naphthalene=

0.117 moles naphthalene

Total moles of mixture

Determining the heat of the solution

y=1633.2 x +4.4448
slope=1633.2=

H
R

sol' n H =1633.2(8.314 J mol1 K1)

sol' n H =13.6 kJ mol