Solutions:
A solution is a chemically and physically homogeneous mixture of two
or more substances. The term solution generally denotes a
homogeneous mixture that is liquid, even though it is possible to have
homogeneous mixtures that are solid or gaseous.
Thus, it is possible to have solutions of solids in liquids, liquids in
liquids, gases in liquids, gases in gases, and solids in solids. The first
three of these are most important in pharmacy.
Formation of Solution
Types of Solutions based on Particle Size:
Depending on the size of the dispersed particle, they are classified as true
solutions, colloidal solutions, and coarse dispersions.
True solutions: Particle size is less than 1 nm. If sugar is dissolved in water, it is
supposed that the ultimate sugar particle is of molecular dimensions and that a
true solution is formed.
Colloidal dispersions/colloidal solutions/Colloids: From 1 nm to 0.5 μm.
Colloidal silver sols are colloidal dispersions of silver nanoparticles (Ag) in a
liquid medium, usually water.
Coarse dispersions/Dispersed systems: Particle size is greater than 0.5 μm. If
very fine sand is mixed with water, a suspension of comparatively large
particles, each consisting of many molecules, is obtained.
Solubility
By
Dr. Imran
Solubility is defined in quantitative terms as the concentration of solute
in a saturated solution at a certain temperature, and in a qualitative
way, it can be defined as the spontaneous interaction of two or more
substances to form a homogeneous molecular dispersion.
Solubility is an intrinsic material property that can be altered only by
chemical modification of the molecule.
Generally speaking, the solubility of a compound depends on the
physical and chemical properties of the solute and the solvent as well
as on such factors as temperature, pressure, the pH of the solution,
and, to a lesser extent, the state of subdivision of the solute.
The thermodynamic solubility of a drug in a solvent is the maximum
amount of the most stable crystalline form that remains in solution in a
given volume of the solvent at a given temperature and pressure under
equilibrium conditions.
A saturated solution is one in which the solute in solution is in
equilibrium with the solid phase.
An unsaturated or subsaturated solution is one containing the
dissolved solute in a concentration below that necessary for complete
saturation at a definite temperature.
Solute-solvent interactions
Water is a good solvent for salts, sugars, and similar compounds,
whereas mineral oil is often a solvent for substances that are normally
only slightly soluble in water. These empirical findings are summarized
in the statement, “like dissolves like.”
Solubility Expressions:
The solubility of a drug may be expressed in a number of ways. The
United States Pharmacopeia (USP) describes the solubility of drugs as
parts of solvent required for one part solute.
Types of Solvents:
Polar Solvents: The solubility of a drug is due in large measure to the
polarity of the solvent, that is, to its dipole moment. Polar solvents
dissolve ionic solutes and other polar substances. Accordingly, water
mixes in all proportions with alcohol and dissolves sugars and other
polyhydroxy compounds.
Nonpolar Solvents: The solvent action of nonpolar liquids, such as the
hydrocarbons, differs from that of polar substances. Nonpolar solvents
are unable to reduce the attraction between the ions of strong and
weak electrolytes because of the solvents' low dielectric constants.
Nonpolar compounds, however, can dissolve nonpolar solutes with
similar internal pressures through induced dipole interactions. The
solute molecules are kept in solution by the weak van der Waals–
London type of forces. Thus, oils and fats dissolve in carbon
tetrachloride, benzene, and mineral oil. Alkaloidal bases and fatty acids
also dissolve in nonpolar solvents.
Semipolar Solvents:
Semipolar solvents, such as ketones and alcohols, can induce a certain
degree of polarity in nonpolar solvent molecules, so that, for example,
benzene, which is readily polarizable, becomes soluble in alcohol. In
fact, semipolar compounds can act as intermediate solvents to bring
about miscibility of polar and nonpolar liquids. Accordingly, acetone
increases the solubility of ether in water.
Alcohol exerts intermediate solvent action on water–castor oil
mixtures.
Solubility of Liquids in Liquids:
Frequently two or more liquids are mixed together in the preparation
of pharmaceutical solutions. For example, alcohol is added to water to
form hydroalcoholic solutions of various concentrations; volatile oils are
mixed with water to form dilute solutions known as aromatic waters;
volatile oils are added to alcohol to yield spirits and elixirs; ether and
alcohol are combined in collodions ; and various fixed oils are blended
into lotions, sprays, and medicated oils.
Liquid–liquid systems can be divided into two categories according to
the solubility of the substances in one another:
(a) complete miscibility
(b) partial miscibility
The term miscibility refers to the mutual solubilities of the components
in liquid–liquid systems.
Complete miscibility: Polar and semipolar solvents, such as water and
alcohol, glycerin and alcohol, and alcohol and acetone, are said to be
completely miscible because they mix in all proportions. Nonpolar
solvents such as benzene and carbon tetrachloride are also completely
miscible. Completely miscible liquid mixtures in general create no
solubility problems for the pharmacist and need not be considered
further.
Partial miscibility: When certain amounts of water and ether or water
and phenol are mixed, two liquid layers are formed, each containing
some of the other liquid in the dissolved state.
Immiscibility:
Immiscibility is phenomenon in which two liquids can not be dissolved
into one another but they form distinct layers.
Factors affecting solubility:
Following factors affect solubility of solids in liquids:
(i) Temperature
(ii) Effect of salts
The solubility of a solid in a liquid depends on the temperature. In the
process of solution, if heat is absorbed (as evidenced by a reduction in
temperature), Δ is by convention positive, and the solubility of the
solute will increase with increasing temperature. Such is the case for
most salts, as is shown in Figure 13-2, in which the solubility of the
solute is plotted as the dependent variable and the temperature as the
independent variable, and the line joining the experimental points
represents the solubility curve for that solute.
Exothermic reaction: If a solute gives off heat during the process of
solution (as evidenced by an increase in temperature), by convention Δ
is negative, and solubility decreases with an increase in temperature.
This is the case with calcium hydroxide and, at higher temperatures,
with calcium sulfate. (Because of the slight solubility of these
substances, their solubility curves are not included.)
When heat is neither absorbed nor given off, the solubility is not
affected by variation of temperature, as is nearly the case with
sodium chloride.
Solubility curves usually are continuous as long as the
chemical composition of the solid phase in contact with
the solution remains unchanged, but if there is a
transition of the solid phase from one form to another, a
break will be found in the curve. Such is the case with
Na2SO4.10H2O, which dissolves with absorption of heat
up to a temperature of 32.4°C, at which point there is a
transition of the solid phase to anhydrous sodium
sulfate, Na2SO4, which dissolves with evolution of heat.
This change is evidenced by increased solubility of the
hydrated salt up to 32.4°C, but above this temperature
the solubility decreases.