introduction

A solute dissolves in a solvent to form a solution. In general, the solvent is the most abundant component. In an
solution, the solvent dissolves the solute by breaking the bonds between solute particles and forming bonds with it.
However, this is only possible when the intermolecular forces of the solute and solvent are similar in nature. In such
way, some substances may, may not dissolve or may partially dissolve depending on the nature of the solvent.

The solubility (S) of a solute is the maximum amount that dissolves in a fixed quantity of a given solvent at a given
temperature.[1] Quantitatively, it is usually measured in molality (mol solute/kg solvent) or as ratio between the mass
of the solute and the solvent (mass solute/mass solvent). [1] When the amount of solute in the solvent approaches its
maximum solubility, a solubility equilibrium is establishedthe solute establishes a dissolutionprecipitation
equilibrium between the solid substance and its dissolved form. This solution is called a saturated solution. [2]

For dissolution to occur, solute-solute interactions are broken and are replaced with solvent-solute interactions
process which involves absorption and release of heat, respectively. There are three stages that occur before a solution
is formed. Firstly, the solute particles separate from each othera process which requires overcoming the
intermolecular attractions between solute particles and is thus, endothermic and requires heat. Secondly, solvent
particles separate from each otherlike the first one, a process which requires heat. Lastly, the solute and solvent
particles mix and form a solutiondifferent particles attract each othera process which releases heat and is thus,
exothermic. The overall process is called a thermochemical solution cycle, and in yet another application of Hesss
law, combining the three individual enthalpy changes to find the heat (or enthalpy) of solution (DHsoln), which is the
total enthalpy change that occurs when solute and solvent form a solution:

[heat equation]

The heat of solution can be mathematically related to its solubility using the vant hoff equation:

= +

!@#$%^&*()

The objective of the experiment is to determine the heat of solution of oxalic acid in water by measuring its solubility
in various temperatures. The measured solubilities was subjected to linear regression to fit the vant hoff equation to
determine the slope which is related to the heat of solution.
Experimental Section

A. Preparation of Standard Solutions

Standard KHP solution. Solid KHP of mass _____ was weighed and analytically transferred to a 250 mL volumetric
flask, and was filled to mark with distilled water.

Standardized 0.25 M NaOH Solution. A 250 mL 0.5 M NaOH solution was delivered into a 500 mL volumetric flask
and diluted to mark with distilled water. The solution prepared was standardized against 40 mL Standard KHP solution
using phenolphthalein as an indicator. Two trials of the titration was performed.

B. Determination of Solubility of Oxalic Acid at Different Temperatures

A 50 mL saturated solution of oxalic acid was prepared in a 100 mL beaker at a temperature of about 40OC. The
beaker containing the solution was immersed in a constant temperature water bath at the following temperatures: 35,
30 and 25. The solution was shaken until constant temperature was achieved. From each temperature, two 5 mL
samples of the saturated solution were withdrawn using a pipet whose tip was wrapped with a cotton to filter solid
crystals, and were delivered to a pre-weighed flask. The flask was reweighed with the sample.

The sample was diluted with 100 mL distilled water, and was titrated with the standardized 0.25 M NaOH solution
using phenolphthalein as an indicator.

Results and discussion

Aqueous Solubility of Oxalic Acid

The solubility of the oxalic acid in water was determined at the following temperatures: !@##$$%^&. The measured
solubility S (expressed in various units) at different temperatures were listed in Table 1, and plotted in Figures 1 and
2. The solubility of oxalic acid increases exponentially with absolute temperature as shown in Figure 1. The natural
logarithm of the solubility has a negative linear relationship with the reciprocal of the absolute temperature as shown
in Figure 2. Nevertheless, both models show that as temperature increases, the solubility of oxalic acid also increases.

The measured solubilities are shown to be in agreement with other studies, as shown in Figure 3. They follow the
same trend with slight numerical deviation, which is within the expected error.

Heat of Solution of Oxalic Acid

The heat (enthalpy) of solution of oxalic acid in water was determined using the vant hoff equation. The natural
logarithm of the oxalic acid solubility and the reciprocal of the absolute temperature was analyzed using linear
regression, as shown in Figure 2. The measured heat of solution of oxalic acid was !@#$%^&, showing that the
solution of oxalic acid is an endothermic process which requires heat. The value obtained was in agreement with other
works with acceptable deviations, as shown in the Table 2.

The solution of oxalic acid is an endothermic processheat is absorbed and the temperature is expected to decrease.
This also implies that the solvent-solvent and solute-solute bonding is stronger than that of the solute-solvent bonding.
Before a solution is formed, solvent-solvent and solute-solute bonding are broken, a process that is endothermic, and
solute-solvent bonding are formed, a process which is exothermic. By applying the Hesss law, the total heat of
solution simply the sum of the heat of these three processes, as shown before by Scheme 1. An endothermic solution
means that more heat is required to break the solvent-solvent and solute-solute bonding. Though the forming of
solvent-solute bonding releases heat, the magnitude is lesser that what was absorbed to break the bonding between
like molecules.

Water molecules are bonded by strong hydrogen bonding forces. Oxalic acid molecules are bonded by two moieties
capable of donating hydrogen bonding forces (-OH), four moieties capable of accepting hydrogen bonding forces (=O,
-OH), and van der waals forces. These makes water-water and oxalic acid-oxalic acid bonding very strong and thus,
requires high amount of heat to break. Though water and oxalic acid can also form strong hydrogen bonding, the heat
it will release will be lower in magnitude compared to the breaking of bond of like molecules.

Relation of Solubility and Temperature

As shown by the vant hoff eqation, the solubility increases with temperature when the slope of the line is negative,
that is when the heat of solution is positive (endothermic), and decrease with temperature when the slope of the line
is positive, that is when the heat of solution is negative (exothermic). In oxalic acid, the solubility increase with
temperature because the process is endothermic.

Systems in equilibrium follow the Le Chteliers principle which that if a stressor is added to the system, the system
will adjust to a new equilibrium. Since solubility is also a form of equilibria, it also follows the Le Chteliers principle.
In the experiment, the changes in temperature, which is the addition of heat, can be viewed as a stressor. In such way,
since the process is endothermic, the system adjusts by consuming the excess heat in favor of the formation of
dissolved oxalic acid.

Error Analysis

Sources of error in the experiment are the uncontrolled variations of temperature, the premature precipitation of oxalic
acid during sampling process, the measurement uncertainties of the measuring devices used (analytical balance and
buret) and the purity of oxalic acid and distilled water used.

The temperature variation upon transferring the sample using the pipet was uncontrolled and causes premature
crystallization. Though the tip of the pipet is covered with cotton, the amount of oxalic acid dissolved may have
already been reduced. A warm cotton could have been wrapped around the pipet maintain the temperature, at least
during the delivery of the sample.

Conclusion

The process of dissolving oxalic acid is endothermic and absorbs heat. The solubility of oxalic acid increases
exponentially with absolute temperature. For the temperature range of !@#$$% the integral heat of solution of oxalic
acid was measured !@#$%^&*( !@#$$ with a solubility given by the model !@#$%^, valid at temperature between
!@#$$.

References

[1] Silberberg

[2] david

[3] Katz, E. W.; Hoyer, F. E. Purification of Organic Acids by

Recrystallization. In Proceedings of the International Symposium on
Industrial Crystallization ISIC 98, Tianjin, China, September 21-
25, 1998; pp 277-281.

Abstract

The integral heat of solution of oxalic acid in water was determined using its solubility measurements at different
temperatures. Water baths of different temperature were prepared. Saturated solutions of oxalic acid were immersed
in each water bath and samples were withdrawn. Analysis of samples were done by titration with NaOH. Results show
that solubility increase exponentially with absolute temperature and that the solution process is endothermic, having
a value of !#$$%%. The solubility S of oxalic acid was correlated to the absolute temperature T by the equation:
!@#$%%.

The heat required to dissolve

When the amount of solute present in the solution is equal to its solubility, the solution is referred as a saturated
solution, where no more solute can be dissolved.

In a solution, there are two main components: the solvent and the solute. The solvent is the dominant specie in the
solution, dissolving the minority, which is the solute. In an ideal solution, solvent molecules surround the solute
molecules and bind them with intermolecular forces. For this to happen, solvent-solvent and solute-solute interactions
must be broken to allow solvent-solute interactions to form.