I.

Introduction

Solubility is a property of a solution that is dependent on the strength of the attractions between
solute and solvent particles relative to the strengths of the attractions within the pure
substances (McMurry and Castellion 1998). A solution, in this case, describes a clear,
homogenous liquid composed of a mixture of two or more substances. The two parts of a
solution are the solute, which is the portion dissolved, and the solvent, which is the main liquid
component of the solution.

The two main factors that control solubility are polarity and molecular or ionic size. The process
of dissolution occurs as the solute particles "take the place" of the solvent particles in the
solution, which is dependent on the relative forces of attraction of all the particles in the
solution with themselves and each other (solute-solute, solvent-solvent, and solute-solvent).
Two liquids are called miscible, or mutually soluble in all proportions, when the intermolecular
forces in and between them are similar (Petrucci et al. 2006).

Between the dissolution of a molecular compound versus an ionic compound in water, the ions
of the latter that are adjacent to one another separate and become surrounded by water
molecules (an ion is said to be "solvated" at this point), while the molecular compound can only
dissolve if a sufficient amount of hydrophilic bonds are present, as any solute-solvent attraction
would be too weak to interfere with the hydrogen bonds existing in water.

In contrast to water, organic solvents are capable of dissolution in a broader range of organic
compounds due to their greater molecular size and a large amount of nonpolar bonds. Many
polar organic substances, such as sugars, amino acids, and even some proteins, are soluble in
water; however, as the number of carbon atoms in organic molecules increases, water solubility
decreases (McMurry and Castellion 1998). Substances with similar intermolecular forces of
attraction are capable of forming solutions ("like dissolves like"), and this explains that the
solvent power of a certain organic liquid is strongest with substances with properties similar to
its own.

VI. Discussion

Based on the data in Table 1.1., the results showed that agitating a mixture, such as KMnO4
crystals and water, causes the formation of a solution, which is homogenous and only has one
phase; "phase" here meaning a distinctive form of matter, such as a solid, liquid, gas or plasma.
The solvation, or dissolution process, explains how this solution forms due to a larger amount of
association between the attracted solute and solvent particles due to vigorous movement.

The nature of the solvent-solute interaction describes the intermolecular forces of attraction
(IMFA) as well as the polarity of the molecules in both the solute and solvent. In the exercise,
several different substances were made to interact with petroleum ether and water and their
solubility in the solvent was observed. Petroleum ether is a nonpolar solvent and therefore has
London Dispersion Forces (LDF) as its primary IMFA, while water is a polar solvent with LDF,
dipole-dipole interaction (DDI), and hydrogen bonding as its IMFA. Based on the data in Table
1.4., Petroleum ether is most able to dissolve nonpolar solutes while water is able to dissolve
polar solutes. Substances with similar IMFA are able to form solutions, though it is possible to
have slight solubility that may be mistaken as complete solubility due to a certain substance
having partial polarity or nonpolarity within its structure, which may have occurred in some of
the observations in Table 1.4. However, there is the exception of cellulose, which is a hydrogen
bond cross-link polymer and therefore cannot be dissolved in petroleum ether nor water
(Chaplin 2002).

Measures of solubility (in grams of solute per 100mL solvent) are always accompanied by a
comment on the temperature at which it was measured due to the varying results in solubility
at different ranges of temperature. Table 1.6. shows what is observed as a benzoic acid-water
solution is heated and then cooled. Benzoic acid is slightly soluble in cold water, but as
temperature increases in an exothermic reaction its solubility increases due to the breaking of
hydrogen bonds and the other IMFA present in water (LDF and DDI) are able to fully interact with
the nonpolar portion of benzoic acid that originally remained undissolved in a lower
temperature -- addition of more heat facilitates the dissolving reaction by providing more kinetic
energy to break bonds in the solid (Ophardt 2003).

The pH scale represents the concentration of hydrogen ions or [H+] in a solution, which is often
low in solutions like water; this scale distinguishes between acids (<7 on the pH scale), neutral
solutions (=7 on the pH scale), and basic/alkaline solutions (>7 on the pH scale) (Bylikin et al.
2014). The pH of a solution can affect the solubility of a solute, as the charge state of the solute
shifts with pH change; if the pH of the solution is such that a particular molecule carries no net
electric charge, the solute often has minimal solubility and precipitates out of the solution
(Boundless 2016). It is also possible to determine the functional groups present in each organic
compound based on their reaction to solvents of differing pH alone (Carpio 2015). For example,
based on Table 1.3.1. and 1.3.2., aniline was seen to be immiscible in all except 10% HCl, which
means that an amine is present in its structure.

"Salting out" is known to be a purification method that utilizes the reduced solubility of certain
molecules in a solution of very high ionic strength. This method is achieved as all of the
hydrophobic parts of a molecule are collected together and the hydrophillic portions are left to
interact with the water; at a certain ionic strength, the water molecules are no longer able to
support the charges of both the ions and the organic substance, which results in the
precipitation of the least soluble solute (Chemistry LibreTexts 2016). Table 1.5. shows the
occurrence of this upon addition with sodium chloride (NaCl) to a water and 1-butanol solution,
and standing for several minutes, wherein a precipitation of small crystal-like solids (NaCl) was
observed. NaCl was the least soluble solute in the solution, and therefore it precipitated out
upon an excess addition due to the inability of the water molecules to support both the NaCl
and 1-butanol ion charges, as mentioned above.

Liquid-liquid extraction, or solvent extraction, is a batch-type phase-distribution technique used

in the separation of mixtures (Cantwell and Losier 2002). This is done in the exercise by making
the solid mixture into a liquid mixture through addition of dichloromethane (DCM) and
separating them into organic and aqueous layers using both polar and nonpolar solvents.
According to the data in Table 1.7., the ternary mixture was made of three separate components
that were extracted from one another by use of immiscible layers through addition of other
solutions (such as HCl, NaOH, and NaHCO3) and a separatory funnel. As shown in the data in
Table 1.8., the percentage recoveries of both component 1 and 2 yielded around 73-76%
recovery, while component 3 yielded a negative result due to personal error as a result of
improper handling and contamination of the sample.

VII. Summary and Conclusion

As shown by this exercise, solubility is affected by: (1) the nature of the solute-solvent
interaction, (2) the temperature of the solution, and (3) the pH of the solvent. The exercise also
shows that the solvation process may be completed through agitation of the mixture, and that
salting out may be used in the purification of a solution. Also, a mixture with more than two
components may still be separated by means of liquid-liquid extraction.

The solvation process relies on the interaction and attraction of solute and solvent particles with
one another, therefore this process may be "sped up" so to say through agitation of the mixture;
observation of this can be seen in Table 1.1. "Salting out", on the other hand, is a purification
method that releases the least soluble solute in the solution upon excess addition of a certain
substance; in the exercise, this substance is NaCl, as seen in Table 1.5.

Solutes are most likely to dissolve in solvents that share similar IMFA and polarity, or "like
dissolves like", which is mostly exhibited by the data in Table 1.4.; it is possible, however, for
cases of slight solubility due to the substance not being completely polar or nonpolar. The
solubility of a solute in a solvent increases as temperature increases in an exothermic reaction,
exhibited by the data in Table 1.6., due to more heat facilitating the breaking of bonds in the
solute for complete dissolution. pH, as exhibited by Tables 1.3.1. and 1.3.2., is able to affect
solubility through shifting the charge state of the solute, and it may also serve as a means for
determining the functional groups present in a certain organic substance.

VIII. References

A. Books

BYLIKIN, S., HORNER, G., MURPHY, B., TARCY, D. 2014. Chemistry: Course Companion. Oxford,
UK: Oxford University Press. 197-200.

MCMURRY J., CASTELLION M.E. 1998. Fundamentals of General, Organic, and Biological
Chemistry. 2nd Edition. Upper Saddle River, NJ: Prentice Hall. 233-237.
O'NEIL, M.J., ed. 2001. The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals.
13th Edition. New Jersey, USA: John Wiley & Sons. 2708.

PETRUCCI, R.H., HARWOOD, W.S., HERRING, F.G.,MADURA, J.D. 2006. General Chemistry:
Principles and Modern Applications. 9th Edition. Lebanon, IN: Prentice Hall.

B. Journals

CANTWELL, F.F., LOSIER, M. 2002. Comprehensive Analytical Chemistry 37 (1): 297-340.

C. Web Resources

BOUNDLESS. 2016. The Effect of pH on Solubility. Retrieved August 20, 2017 from
https://www.boundless.com/chemistry/textbooks/boundless-chemistry-textbook/acid-base-
equilibria-16/solubility-equilibria-120/the-effect-of-ph-on-solubility-490-6881/

CARPIO, P.T. 2015. Solubility of Organic Compounds. Retrieved August 20, 2017 from
https://www.scribd.com/doc/51216508/Solubility-of-Organic-Compounds

CHAPLIN, M. 2002. Cellulose. Retrieved August 20, 2017 from

http://www1.lsbu.ac.uk/water/cellulose.html

CHEMISTRY LIBRETEXTS. 2016. Salting out. Retrieved August 20, 2017 from
https://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Thermodynamics/Non-
Ideal_Systems/Salting_Out

OPHARDT, C.E. 2003. Temperature/Pressure on Solubility. Retrieved August 20, 2017 from
http://chemistry.elmhurst.edu/vchembook/174temppres.html

IX. Remarks

Other than the sample of cellulose used being changed from cotton fiber to tissue paper, there
were no other changes or modifications to the procedure.

In regards to improvement of the exercise, it would be better performed if the laboratory

equipment were updated and complete, as some systematic error may have occurred due to old
and contaminated instruments. Also, the portion with the separation of a ternary mixture would
benefit from at least two trials for better accuracy with the percentage recovery, and it should be
performed separately from the solubility tests to avoid error and lack of time.