Physical pharmacy

100

FINAL
30

MID-TERM
15

Quiz /H.W/Assig. 15

PRACTICAL
30

Oral
10

Determination of vapor pressure of solution

Definitions
Solution Solvent Solute Solubility

Matter

Concentration expression

Vapor pressure Vapor pressure of solution

Escaping tendency Ideal solution Real solution
Rauolts law

Solid, liquid, gas

Solution Mixture of two components that or more

form a single phase, homogeneous down molecular level

to

the

 Solvent

Component that determines the phase of the solution constitutes the largest proportion of the system

 Solute

dispersed as throughout the solvent; i.e. dissolved in the solvent

molecules or Ions

Solubility
Is the maximum amount of solute that passes into solution when an equilibrium is established between the solution and excess, i.e. undissolved substance

Methods of Expressing Concentration of solutions

Quantity per quantity Percentage (%) Molarity Molality Mole Fraction

Methods of Expressing Concentration

1.Quantity per quantity: Concentrations are often expressed simply as the weight or volume of solute that is contained in a given weight or volume of the solution. w/v (majority), w/w, v/v

Methods of Expressing Concentration

2.Percentage (%)
% w/v = weight of solute/volume of solution x 100 % w/w = weight of solute/weight of solution x 100

% v/v = volume of solute/volume of solution x 100

Methods of Expressing Concentration

the number of moles (gram molecular weights) of solute in 1 liter of solution. unit of molarity is mol/l. Molar concentration and its symbol M describe the molarity of a solution Number of moles = weight(gram)/ mol.wt 1 Molar = gram mol wt / liter Molarity: no. of moles/ liters of solution

3.Molarity M:

Methods of Expressing Concentration 4.Molality m: the number of moles (gram molecular weights) of solute in 1 kg of solvent. i.e. mol/kg. Molality: no. of moles/ kg of solvent

Methods of Expressing Concentration

5.Mole Fraction: number of moles of solute divided by the total number of moles of solute and solvent, i.e mole fraction of solute= n1/n1+n2 n1 and n2: numbers of moles of solute and solvent, respectively.

Solution properties
Definitions
Solution Solvent Solute Solubility

Matter Vapor pressure Vapor pressure of solution

Ideal solution

Concentration expression

Real solution

rauolts law

Kinetic theory of matter

Solid state

Liquid state

Gas state

Kinetic theory of matter

gaseous state: The thermal motions of molecules of a substance can overcome the attractive forces that exist between the molecules,
molecules undergo a completely random movement within the container

Kinetic theory of matter

liquid state: Van der Waals forces of attraction, lead to some degree of coherence between the molecules of liquids.
Consequently, liquids occupy definite volume. a

Kinetic theory of matter solid state: The intermolecular forces are so strong that a high of order,
hardly influenced by thermal motions

Vapor pressure All condensed systems have the inherent ability to give rise to a vapor pressure.

Vapor pressure

Vapor pressure
Although solids and liquids are condensed systems with cohering molecules some of the surface molecules in these systems will occasionally acquire sufficient energy to overcome the attractive forces exerted by adjacent molecules and so escape from the surface to form a vaporous phase.

Vapor pressure Definition The pressure exerted by the vapor at equilibrium is referred to as the vapor pressure of the substance.

Vapor pressure surface loss of vapor from liquids by the process of evaporation is more common than surface loss of vapor from solids via sublimation.

Vapor pressure
However, the vapor pressures exerted by solids are usually much lower than those exerted by liquids, why?
because the intermolecular forces in solids are stronger than those in liquids so that the escaping tendency for surface molecules is higher in liquids.

Solution properties
Definitions
Solution Solvent Solute Solubility Saturated solution

Matter

Vapor pressure
definition

Solid, liquid, gas

Concentration expression

Vapor pressure solution

rauolts law

of

Tendency of escaping Ideal solution Real solution

Vapor pressure of solution

In the case of a liquid solvent containing a dissolved solute (solution):
molecules of both solvent and solute may show a tendency to escape from the surface and so contribute to the vapor pressure.

Vapor pressure of liquid

The relative tendencies to escape will depend:
on the numbers of the different molecules in the surface of the solution on the strengths of the attractive forces between adjacent solvent molecules on the strengths of the attractive forces between solute and solvent molecules

If solute is non-volatile or solid

The intermolecular forces between solid and liquid molecules are relatively strong
such solute molecules do not generally escape from the surface of a solution and contribute to the vapor pressure.

If solute is non-volatile or solid The solute is non-volatile so the vapor pressure is due to
the dynamic equilibrium between the rates of evaporation and condensation of solvent molecules in the solution.

If solute is volatile or liquid In a mixture of miscible liquids, i.e. a liquid in liquid solution,
the molecules of both components are likely to evaporate and contribute to the overall vapor pressure exerted by the solution.

Ideal solutions; Raoult's Law:

Francois Marie Raoult (1830 - 1901)

Ideal solutions; Raoult's Law:

In the model it is assumed that the strengths of all intermolecular forces are identical, i.e. solvent-solvent, solutesolvent and solute-solute interactions are the same and are equal to the strength of the intermolecular interactions in the pure solvent or pure solute.

Ideal solutions; Raoult's Law:

Because of this equality the tendencies of solute and solvent molecules to escape from the surface of the solution will be determined only by their relative numbers in the surface. Since a solution is homogeneous by definition then the relative numbers of these surface molecules will be reflected by the relative numbers in the whole of the solution which can be expressed by the mole fractions of the components

Binary solution (with two components)

The total vapour pressure P exerted by such a binary solution P = P1 + P2 = Po1X1+ Po2X2 X1 & X2 : mole fractions of the solute and solvent, respectively. P1 & P2 : partial vapour pressures exerted above the solution by solute and solvent, respectively, Po1 & Po2: vapour pressures exerted by pure solute and pure solvent respectively

Definition of ideal solution:

The solution which obeys Raoult's law. Ideal behaviour should only be expected from systems having chemically similar components, why?
because it is only in such systems that the condition of equal intermolecular forces between components, that is assumed in the ideal model, is likely to be satisfied.

Example of Ideal solution

Raoult's law is obeyed over an appreciable concentration range by relatively few systems in reality e.g.
Mixtures of benzene + toluene, n-hexane + n-heptane ethyl bromide + ethyl iodide

2-Real or Non-Ideal Solutions

The majority of real solutions do not exhibit ideal behaviour, why?
because solute-solute, solute-solvent and solvent-solvent forces of interaction are unequal.

The effective concentration of each component cannot be represented by normal expression of concentration, e.g. the mole fraction x but by the so-called activity or thermodynamic activity

Real or Non-Ideal Solutions

P1 = P1oa1 This equation is applicable to all systems whether they are ideal or non-ideal. In ideal solution a = x, in real solutions a
The ratio of activity/concentration is termed the activity coefficient (f) and it provides a measure of the deviation from ideality.

Positive deviation from Raoult`s law

If the attractive forces between solute - solvent molecules are weaker than solute- solute or solvent solvent
then the components will have little affinity for each other.

Positive deviation from Raoult`s law cont.

The escaping tendency of the surface molecules in such a system is increased when compared with an ideal solution. i.e. P1, P2 and P are greater than expected from Raoult's law thermodynamic activities of the components are greater than their mole fractions, i.e. a1 > X1 and a2 > X2.

e.g. alcohol + benzene water + diethyl ether benzene + water

small deviation

less miscible (greater + D) immiscible (very large +D)

Negative deviation from Raoult`s law

If the solute and solvent have a strong affinity for each other that results in the formation of a complex or compound P1, P2 and P are lower than expected and a1< X1 and a2< X2. e.g. chloroform + acetone, pyridine + acetic acid and water + nitric acid.
negative deviation from Raoult's law occurs.