Theme 9.

CHEMISTRY OF SOLUTIONS

Contents:

Introduction. Solutes and Solvents. Concentration

Types of Solutions
Ideal Solutions
Definition and Properties
Binary Ideal Solutions
Raoults Law
P-x and T-x Diagrams. Distillation
Diluted Ideal Solutions. Henrys Law
Colligative Properties

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction.

A Solution is defined as an Homogeneous Mixture of two or more

Components and composed of one single Phase.

A Phase is a System (portion of universe) in which Physical Properties are

essentially Uniform. A Component is one or more Substances with Uniform
Composition.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Solute and Solvent.

A Solution is formed when a Substance (or more) disperses uniformly

throughout another.

Examples of solutions are Liquid Solutions (e.g. a dye in water) or Gaseous

(e.g. atmosphere) or Solids (e.g. 18 carat gold, made with gold and 25%
copper).

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Solute and Solvent.

A Solution is formed when a Substance (or more) disperses uniformly

throughout another.
Solutions are composed of one Solute (or more) and a Solvent.
The Solvent is the component in major Proportion, which determines the
Phase of the Solution (e.g. NaCl in water). Solutes are the rest of the
Components in the solution.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction.

Solutions are formed depending on:

- The Natural Tendency of Substances (solvent and solute) to mix and
spread into larger volumes, when not impeded somehow.

- The type of Intermolecular Interactions involved in the dissolution

process, and the accompanying Energy Changes.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Why Solutions are Formed.

Molecules of Gases (e.g. O2 and Ar), when not physically separated, mix
together (both gases occupying the overall volume) spontaneously
(without any kind of energy input from outside the system).
This (gas molecules randomly distributed throughout the system) results in
an increase of Entropy.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Why Solutions are Formed.

Mixing of Gases is always spontaneous, as intermolecular forces are too

weak.
With Solids and/or Liquids, as intermolecular forces are important, there
will be Mixing assuming that Energetic Changes are Favourable.

Sodium Chloride dissolves in water

because intermolecular interactions
between ions and water molecules
(ion-dipole) compensate for the
attractions between ions in the solid
cristal.
For the same reason, NaCl does not
dissolve in gasoline.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Why Solutions are Formed.

Three kinds of Intermolecular Interactions play in important role in Solution

Formation:
- Solute-Solute (e.g. Na+ and Cl- ions in solid NaCl). Those must be
overcome so that solute particles are dispersed throughout the solvent,
in order that solute dissolves.
- Solvent-Solvent (e.g. water molecules in the liquid state). Those
interactions must be overcome to make room for the solute molecules
(or ions).
- Solute-Solvent (e.g. ion-dipole interactions between Na+ and Cl- ions and
water molecules), that occur when the components mix. The Energy gain
in this stage must compensate for the energy requirements in the
previous steps. Otherwise there will not be dissolution (e.g. insoluble
salts, like AgCl in water).

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Why Solutions are Formed. Energetics of the
Process of Dissolution.

The Dissolution Process requires firstly to overcome Solute-Solute and

Solvent-Solvent Intermolecular Interactions. In other words, to separate
solute and solvent particles (ions or molecules).
These two steps are endothermic (require energy input).

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Why Solutions are Formed. Energetics of the
Process of Dissolution.

If the Energy Change associated to the buildup of solute-solvent

interactions is even greater than the two combined endothermic processes
mentioned before, then heat (enthalpy) is released in the overall dissolution
process (exothermic).

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Types of Solutions.

Regarding the Solvent:

Aqueous
Non aqueous
Regarding Solutes Phase:
Gas in Gas
Air (O2, N2, Ar and other gases)
Gas in Liquid
Carbonated water, soda (CO2 in water)
Gas in Solid
H2 in palladium metal (catalyst for hydrogenation)
Liquid in Liquid
gasoline (mixture of hydrocarbons)
Liquid in Solid
Mercury in Silver (dental amalgam)
Solid in Liquid
Sea Water (NaCl in water)
Solid in Solid
Metal Alloys (sterling silver, Ag + 7.5% Cu)
Regarding Solutes Nature:
Electrolytes
conduct electricity
Non electrolytes
do not conduct electricity

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Concentration.

The Concentration of a Solution quantitatively indicates the amount of

solute in a Solution:

It also means that the Components of the solution and the Relative
Abundances are known.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Concentration.

The Concentration of a Solution quantitatively indicates the amount of

solute in a Solution:
Molarity (M): it is the number of solute moles per volume (liters) of solution.

Molality (m): it is the number of solute moles divided per mass (kg) of
solvent

Mole Fraction (xA): it is the number of moles of a particular component

divided by the total number of moles

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Concentration.

The Concentration of a Solution quantitatively indicates the amount of

solute in a Solution:
Percentage (%): the amount of solute (in volume or mass) per amount (in
volume or mass) of solution referred to one hundred.

In case of very dilute solutions, the amount (mass) of solute is referred to

one million or one billion parts of solution (respectively parts per million,
ppm and parts per billion, ppb)

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Concentration.

The Concentration of a Solution quantitatively indicates the amount of

solute in a Solution:

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Concentration. Solubility.

Solubility is defined as the amount of solute (normally expressed in g) that

can be dissolved in a certain amount of a determined solvent (normally
expressed in liters or in 100 mL) at a given temperature.

e.g. solubility of NaCl in water is 35.7 g in 100 mL of water atr 25C

At this point, it is said that a Saturated Solution is obtained (no more NaCl
can be added to that amount of solvent at this temperature that resulted in
a stable solution).

Solubility is affected by the types of intermolecular interactions, by the

temperature, and, specially in gas solutions, also by the pressure.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Concentration. Solubility. Effect of Intermolecular
Interactions.

Solubility is affected by the types of intermolecular interactions, by the

temperature, and in gas solutions also by the pressure.
The strength of Intermolecular Interactions between solute and solvent will
influence solubility. The stronger the solute-solvent interactions are, the
higher the solubility is.

Hydrogen bond between

two ethanol molecules

Hydrogen bond between

ethanol and water molecules

For this reason, solutes are soluble in solvents with which they can build
intermolecular interactions similar to those existing in the pure form (likedissolves-like, or Similia similibus solvuntur).

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Concentration. Solubility. Effect of Temperature.

In most cases with solids dissolving in liquids, solubility increases with

temperature, as dissociation of solid into particles is favored at higher
temperatures.

There are few exceptions to this rule (e.g. cerium(III) sulphate, Ce2(SO4)3)

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Concentration. Solubility. Effect of Temperature.

But for Gases dissolving in Liquids (e.g. carbonated water), solubility

generally decreases with temperature increasing, as more dissolved gas
goes to the gas phase at higher temperatures.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Solubility. Effect of Pressure. Henrys Law.

Pressure does not greatly affect Solubility in Liquid and Solid Solutions.
But for Gases dissolving in Liquids (e.g. carbonated water), solubility
generally increases with Pressure, as the partial pressure of the gas above
the solvent (liquid) increases.
This is explained by Henrys Law, which states that the solubility of a gas in
a liquid solvent is directly proportional to the partial pressure of the gas
above the solvent.

Sg = k Pg

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Solubility. Effect of Pressure. Henrys Law.

The Henrys Law states that the solubility of a gas in a liquid solvent is
directly proportional to the partial pressure of the gas above the solvent.

Sg = k Pg

where Sg is normally expressed as molarity (M)

and k depends on the gas, solvent and temperature

At Equilibrium, the rate of gas molecules dissolved in the liquid that go back
to the gas phase equals that of gas molecules being incorporated into the
liquid (being dissolved).

If Pressure is increased, more gas molecules will be incorporated into the

liquid solvent (solubility increases), until a new equilibrium is reached, in
which solubility will have been increased.

Theme 9. CHEMISTRY OF SOLUTIONS

Solutions. Introduction. Solubility. Effect of Pressure. Henrys Law.

An Example of Henrys Law are the bubbles that appear when opening a
bottle of a carbonated soft drink.

This is because those drinks are bottled at a CO2 partial pressure higher
than 1 atm, and thus more CO2 is dissolved in the water.
When the container is opened to the air, CO2 pressure on the liquid is thus
reduced, so is solubility, and excess CO2 (non dissolved) escapes as
bubbles.