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Experiment 2

Heat of Solution: Solubility Method



*Christian Paolo Asequia, **Ercille Mae Pacamo,
***Rene Susette Ann Pontillas, **** Mariza Silagan
Department of Chemical Engineering
Xavier University-Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro, Philippines
Juliet Dalagan, PhD
Department of Chemistry
Xavier University-Ateneo de Cagayan
Corrales Avenue, Cagayan de Oro, Philippines


Abstract: The experiment aims to determine the heat of
solution of Oxalic acid through the Solubility Method. The
experiment was carried through different temperatures
namely, 25, 30 and 35
o
C. A saturated solution of Oxalic acid
was prepared and heated to 40
o
C. It was then immersed into
three constant temperature water baths with samples of 5 ml
every temperature extracted and was titrated to Sodium
Hydroxide. The data for normality, weight of the sample and
equivalent weight of Oxalic acid was obtained for the
measurement of the solubility of Oxalic Acid. The use of the
Vant Hoff equation was done to measure the solubility which
has units expressed in terms of grams of solute per 100 grams
solvent. At a temperature of 35
o
C, the solubility of oxalic acid
was 6.45x10
-4
. For 30 and 25
o
C, the solubility was 5.85x10
-4

and 5.60x10
-4
, respectively. The logarithm of the solubility at
different temperatures was then plotted against the reciprocal
of the temperature in terms of Kelvins and was best-fitted with
an equation of the line, y= -562.62x 1.3688 . The given
slope of the line was -562.62 and was substituted to the Vant
Hoff equation, from this value, the heat of solution of
Oxalic Acid was calculated and it resulted to 10772.57 J/K-
mol with a percent error of 12.38%.


Keywords: Heat of Solution, Solubility Method, Solubility,
Vant Hoff Equation
I. INTRODUCTION

Solubility is a measure of the ability of a substance to
dissolve in a specific amount of another substance at standard
temperature and pressure. It is expressed in grams solute per
100 grams solvent. It is a special case of the equilibrium
constant and it is where the Vant Hoff equation is applicable.

The state of equilibrium, where the undissolved
solute is in equilibrium with the dissolved solute, is called
saturation. Therefore, in a saturated solution, the chemical
potential of the pure solid solute,
B
*(s, and the chemical
potential of B in solution,
B
, are equal.

[Equation 1]

Can be rearranged to:

[Equation 2]

Given that , the equation can now be written
as:

[Equation 3]

Neglecting the change in entropy, it can be expressed as:

[Equation 4]

The Vant Hoff equation relates the change in
temperature, T, to the change in the equilibrium constant, K,
given the standard enthalpy change, , for the process. Given
the equation:
[Equation 4]

Relating solubility derives the equation to:

[Equation 5]


Solubility can now be expressed to:

[Equation 6]

The heat of solution is the change in enthalpy
associated with the dissolution of a solvent at constant
pressure resulting in infinite dilution. In the process, energy
can be either absorbed or released.
[1]

The experiment aims to determine the heat of
solution of Oxalic Acid by measuring its solubility at three
different temperatures and at the same time apply the Vant
Hoff Equation to the data obtained.

II. EXPERIMENTAL SECTION
A 50 ml saturated solution of saturated solution of
Oxalic acid was prepared and was heated to 40
o
C and was
immersed in a constant temperature bath at 35
o
C. After 10
minutes of shaking, a 5 ml sample was withdrawn using a
pipet with its tip wrapped with cotton to prevent solid crystals
from drawing out. The 5 ml sample was placed in a pre-
weighed Erlenmeyer flask and was added with 10 ml of Water.
It was then titrated with an already standardized 0.25 N
Sodium Hydroxide and using Phenolphthalein as the indicator.
On the other hand, the remaining solution of saturated
Oxalic Acid solution was immersed again on a constant
temperature bath at 30
o
C. A 5 ml sample was withdrawn again
and was titrated with 0.25 N Sodium Hydroxide. The
remaining solution again was immersed in a constant
temperature water bath at 25
o
C. A 5ml sample was withdrawn
again and titrated with 0.25 N Sodium Hydroxide.
III. RESULTS AND DISCUSSION

The experiment involves the determination of the
heat of solution of Oxalic Acid in water via measuring its
solubility at three different temperatures. With the knowledge
of the Normality and weight of the sample, The Solubility in
terms of g Oxalic acid per 100 g water can be determined and
will carry out the whole calculation process.

Table 1 Solubility of Oxalic Acid per 100g Water at different Temperature

Table 1 shows the amount of Sodium Hydroxide that
was dispensed during the titration. Also, the Normality which
was calculated through the standardization of NaOH was also
determined. As observed in Table 1, the solubility of Oxalic
Acid per 100 g of water is decreasing as the temperature is
also decreasing from 35 to 25
o
C. This describes the
relationship between its solubility and temperature which is
Linear.

Table 2. Logarithm of Solubility with corresponding 1/T
T (
o
C) T in (K) Ave. S (1/T) Log S
35.0 308.15 6.45x10
-4
3.299x10
-3
-3.190
30.0 303.15 5.85x10
-4
3.245x10
-3
-3.233
25.0 298.15 5.60x10
-4
3.345x10
-3
-3.125

Table 2 shows the data for the reciprocal of the
temperature and the logarithm of the average solubility. These
data are essential values for the graph to be able to determine
the equation of the line and obtaining the slope for the
determination of the Heat of Solution.
Figure 1 . Graph of Log S as a function of Temperature

Figure 1 is the graphical representation of the values
in Table 2. As observed in the graph, as the temperature
increases, the solubility of the oxalic acid also increases. The
equation of the line was also obtained and was found out to be
y = -562.62x - 1.3688. The graph has a negative slope which
indicates that the reaction is an endothermic reaction or heat
absorbing reaction. The heat of solution was determined by
using the equation,

m (slope of the line) = - (H
soln
) / 2.303R

This then resulted to a heat of solution of 10772.60
J/K-mol. The error also was calculated and turned out to have
an error of 12.38%.

With the results obtained, it can be concluded that
solubility greatly varies with temperature and because it is an
endothermic reaction, the solubility and temperature have a
direct relationship. As the temperature of the solution
increases, the average kinetic energy of the molecules that
make up a solution also increases. The increase in the kinetic
energy allows the solvent molecules to more effectively
break apart the solute molecules that are held together by
intermolecular attractions. Furthermore, with the increase of
the average kinetic energy they destabilize the solid state of
the solute. The increased vibration of the molecule causes
them to be less able to hold together therefore, they dissolve
readily.
[2]

IV. ERROR ANALYSIS
Several errors were committed and surfaced during
the execution of the experiment. These errors might be the
cause of the deviation of the outcome of the experiment
from its true values. One of the errors would be the personal
errors. Since the experiment involves titration, the readings
may have differed since it varies from one person to
Temperature
(
o
C)
Volume
NaOH
used
(ml)
Normality
(N)
Solubility
(gC
2
H
2
O /
100g
H
2
O)
Average
Solubility
35.0 3.1

0.236
6.6x
10-4
6.45x10
-4

2.95 6.3x10
-4

30.0 3.90 8.3x10
-4
5.85x10
-4

1.60 3.4x10
-4

25.0 2.65 5.6x10
-4
5.60x10
-4

another. Instrumental errors may also have contributed to
the error since impurities present in the equipment may
have mixed during the saturation of the oxalic acid solution.
V. CONCLUSION

The heat of solution of the Oxalic acid Water
reaction was determined through the use of Vant Hoff
equation. It resulted to 10772.60 J/K-mol and was compared
to its actual value. The percent error of the value was found
out to 12.38%. Also , the reaction was found out to be
endothermic which indicates a direct relationship between the
solubility and the temperature of the reaction.

REFERENCES
[1]HTTP://WWW.SCRIBD.COM/DOC/86320208/HEAT-OF-
SOLUTION-THEORY (DATE ACCESED: 12/17/2013)

[2]https://www.boundless.com/chemistry/solutions/factors-
affecting-solubility/solid-solubility-and-temperature/ (date
accesed: 01/13/2014)

APPENDICES
I. CALCULATIONS
(a) Standardization




N = M = 0.236 M
(b) Mass of Oxalic Acid

m
OxalicAcid
= 0.083 g
(c) Solubility

(d) Equation of the Line:
y = -562.62x 1.3688
m = -0.562
(e) Heat of Solution



(f) Percent Error



% Error = 12.38%


Figure1. Logarithm of Solubility as a function of temperature