Exercise 1

SOLUBILITY AS A PHYSICAL PROPERTY

A solution is a clear homogeneous mixture of two or more substances; the term is most commonly
applied to those in liquid form, for which the test for homogeneity is a uniform appearance and total lack
of cloudiness. The solvent is the main liquid component of a solution, while the other present substances
are said to be dissolved and are collectively referred to as the solute. Solubility then, is the comparative
ability of the substances to dissolve in a given solvent and is usually measured as grams solute per 100 mL
solvent at a specific temperature.

Polarity and molecular (or ionic) size are the main factors that govern solubility. When one
substance dissolves in another, particles of the solute (either molecules or ions) must be distributed
throughout the solvent and in a sense, the solute particles in the mixture occupy positions that are
normally taken by solvent molecules. Thus, ease with which a solute particle may replace a solvent particle
depends on the relative forces of attraction of solvent particles for each other, solute particles for each
other, and the strength of solute-solvent interactions.

When an ionic substance dissolves in water, the ions that are adjacent to one another in the solid
become separated and are surrounded by water molecules. In the immediate vicinity of the positive ion,
the surrounding water molecules are oriented so that the negative ends of their dipole points in the
direction of the positive charge. The water molecules surrounding a negative ion have their positive ends
directed at the ion. An ion, enclosed within this cage of water molecules is said to be hydrated and
generally, when a solute particle becomes surrounded by molecules of solvent we say that it is solvated. In
a sense, the solvent insulates the ions from each other.

On the other hand, molecular compounds dissolve in water only if they contain sufficient portion of
hydrophilic or water loving bonds polar bonds involving oxygen or nitrogen atoms bearing a partial
negative charge whereby hydrogen bonding to water molecules is possible. Otherwise, any attraction
between solute and solvent molecules is too weak to disrupt the hydrogen bonding that holds the water
molecules together, and mixing is not possible.

The solvent power of organic liquids is very different from that of water because of the greater
molecular size and the presence of a number of nonpolar bonds in their molecules. Compared to water,
organic solvents are capable of dissolving a much wider range of organic compounds. Like dissolves like is
a general rule which emphasizes the fact that the solvent power of a given organic liquid is greatest for
substances of polarity similar to its own.

In this experiment, the exact solubility values of the different solutes will not be measured, but it is
important to note whether the indicated amounts of solute and solvent mix to give a solution or not. At
the end of the experiment, the students should be able to:

1. Observe and describe the dissolution process;

2. Establish that solubility is a physical property which is dependent on some factors like the
nature of the solute and solvent, pH and temperature; and

3. Perform and observe the salting-out process.

EXPERIMENTAL PROCEDURE

(Caution: Organic solvents are flammable and generally toxic. Stay away from an open flame when
working with them, and avoid breathing their vapors.)
A. PRELIMINARY OBSERVATIONS ON THE DISSOLUTION PROCESS

Drop a small crystal of potassium permanganate into about 50 mL of water contained in a 250-mL
Erlenmeyer flask that is placed on a white background. Observe what happens.

B. SOLUBILITY IN ORGANIC SOLVENT AT ROOM TEMPERATURE

(Before doing this part, record the descriptions of the pure organic compounds in your data table.)

Place 2.0 mL of petroleum ether in a small, clean, dry test tube. Add the organic compound (3
drops of a liquid or a spatula tip of solid), and mix by thorough agitation. Examine the mixture and
record its description.

Using the above procedure, test the solubility of each of the following organic compounds.

Set A: acetic acid, benzoic acid, sodium benzoate

Set B: cyclohexanol, dextrose, cellulose (cotton fiber)

C. SOLUBILITY IN WATER AT ROOM TEMPERATURE

Adapt the procedure given in the preceding section using water in place of the organic solvent.
Test the same set of compounds for their solubility in water at room temperature. (Save the test
tube containing benzoic acid-water mixture for part D).

D. EFFECT OF TEMPERATURE ON SOLUBILITY

Carefully without any spillage, pour the contents of the test tube containing the benzoic acid-water
mixture into a large test tube. Use 1.5 mL extra water to rinse out any solids adhering to the walls
of the small test tube into the larger one. The resulting mixture now contains a larger portion of
water. Is it enough to dissolve all the benzoic acid? If not, heat the tube over a small flame or in a
water bath. Observe what happens to the mixture. When all the solids have disappeared, remove
the tube from the heat and allow it to cool slowly. Observe what happens.

E. EFFECT OF PH ON SOLUBILITY

Using the procedure in part B, determine the solubility of the following compounds in the following
solvents: water, 10% HCl, 10% NaOH, and 10% NaHCO3.

Set C: aniline, diethylamine, naphthalene

Set D: benzoic acid, phenol, toluene

F. SALTING OUT AND ITS EFFECTS

Add 10 drops of 1-butanol to 4 mL water in a large clean test tube, and mix thoroughly. If any
butanol remains undissolved, add a few drops of water and agitate the mixture until finally a true
solution is observed. Record its appearance. Now, add a spatula of sodium chloride and agitate
the contents of the tube until the solids are completely dissolved. Is there any difference between
this mixture and the original solution? If no difference is observed, add more sodium chloride and
 shake as before. Allow the mixture to stand for a while and repeat the examination. Record the
appearance of the new mixture.

G. SEPARATION OF A SIMPLE TERNARY (1:1:1 BY WEIGHT) MIXTURE OF BENZOIC ACID, NAPHTHALENE AND M-
NITROANILINE

Dissolve 3.0 g of the mixture in 20 mL of dichloromethane. Transfer the mixture quantitatively into
a separatory funnel using dichloromethane for washing so that the total volume of
dichloromethane used is 30 mL. Extract the dichloromethane mixture with 20 mL of 10% HCl twice.
Perform water test to determine which layer is organic or aqueous. Separate the layers and
reserve the organic layer. Neutralize the combined aqueous layers with 20% NaOH while using an
ice bath for cooling the mixture. Collect the solids obtained and wash with cold water.

Extract the organic layer with 20 mL of 10% NaHCO3 twice. Combine the aqueous layer and
neutralize with concentrated HCl while using an ice bath for cooling the mixture. Collect the
crystals and wash with cold water.

Evaporate dichloromethane from the remaining organic extract using a steam bath (Do this under
the fumehood!). Determine the mass of the three components of the mixture and obtain the
percentage recovery. Transfer the recovered solids into their designated containers (Consult your
instructor!).

H. WASTE DISPOSAL

PART WASTE GENERATED DISPOSAL

A KMnO4 mixture
B Solutions
Heterogenous mixtures
C Solutions
Heterogenous mixtures
D Final Mixture
E Final Mixtures
F Final Mixture
G Aqueous layers
KMnO4 wastes
Part B soluble waste bottle
Part B insoluble waste bottle
Water-soluble organic compounds waste bottle
Part C insoluble waste bottle
Decant the liquid into the sink and transfer solids into the solid
wastes bottle
Non-halogenated organic waste bottle
Water-soluble organic compounds waste bottle
Neutralize then pour into the sink

For your record

Before you leave the laboratory, make sure your notebook contains a clear presentation of all your
observations, including the description of all organic compounds you used. Then you can study your data
later to prepare the latter part of your report. Specific questions to consider are the following:

1. What happens to the unit particles of a solute when it dissolves in a liquid?

2. A true solution is homogeneous and said to have only one phase. What is a phase?
3. How do you explain the difference in the solubility of the Set A compounds in the organic solvent?
How about the Set B compounds?
4. How do you explain the difference in the solubility of the Set A compounds in water? How about
the Set B compounds?
5. How do you explain the difference in the solvent power of water and the organic solvent?
6. What is meant by the salting-out effect? Illustrate.
7. Reports of exact solubility figures in g solute per 100 mL solvent are accompanied by a notation on
the temperature of measurement. Why is this necessary? How would you explain the effect of
temperature on solubility?
 MODEL REPORT FORM
(Prepared for this exercise only)

Table 1.1 Preliminary observations on the dissolution process

Reagents/Actions Taken Observations
KMnO4 crystals
KMnO4 crystals + 50 mL water
Mixture after swirling

Table 1.2 Description of organic compounds

Compounds Description (color, odor, appearance, etc.)
Petroleum Ether
Acetic Acid
Benzoic Acid
Sodium Benzoate
Cyclohexanol
Dextrose
Cellulose (cotton fiber)

Table 1.3 Solubilities at room temperature: pet ether vs. water

In petroleum ether In water
Sample Solution Solution
Mixture Description Mixture Description
(+/-) (+/-)
Acetic Acid
Benzoic Acid
Sodium Benzoate
Cyclohexanol
Dextrose
Cellulose
(Cotton Fiber)
Legend: + means soluble
- means insoluble
+/- means slightly soluble

Table 1.4 Effect of pH on solubility.

In water In 10% HCl In 10% NaOH In 10% NaHCO3
Sample Soln Soln Soln Soln
Description Description Description Description
(+/-) (+/-) (+/-) (+/-)
Aniline
Diethylamine
Naphthalene
Toluene
Benzoic acid
Phenol
Table 1.5. Salting-out and its effects on solubility
10 drops 1-butanol + 4 mL
1-butanol-water solution treated with sodium chloride
H2O
freshly shaken after standing

Table 1.6 Effect of temperature on solubility: Benzoic acid + 4 mL H2O mixture

Action Observations

Freshly shaken

Hot mixture

Cooled after heating

Table 1.7 Separation and purification of a ternary mixture.

Action Observations
Ternary mixture
Addition of dichloromethane
Addition of 20% HCl
- organic layer
- aqueous layer
- aqueous layer + 20% NaOH
- recovered crystals
Addition of 20% NaHCO3
- organic layer
- aqueous layer
- aqueous layer + conc HCl
- recovered crystals
Evaporation of CH2Cl2
- residue

Table 1.8 Data on percentage recovery.

Mass (g) Percent recovery (%)
Mixture 1, 2 and 3
- container + sample -
- empty container -
- sample -
Component 1
- container + sample -
- empty container -
- sample
Component 2
- container + sample -
- empty container -
- sample
 Component 3
- container + sample -
- empty container -
- sample

REFERENCES:

BRADY, JK AND GE HUMISTON. 1982. General Chemistry Principles and Structure. New York: John Wiley
and Sons, Inc.
RENFROW, WB AND PJ HAWKINS. 1962. Organic Chemistry Laboratory Operations. New York: The
McMillan Company.