Vapours pressure and distillation of partially miscible & miscible liquids & Diffusion and Osmosis

By Engr. Asadullah Memon B.E (Petroleum and Natural Gas)

Immiscible and miscible liquids.

Partially miscible liquids are liquids that do not mix at all proportions at all temperatures.

THE BOILING POINT

The Boiling Point is the temperature at which internal vapor pressure of the liquid is equal to the pressure exerted by its surroundings If the liquid is open to the atmosphere, the boiling point is the temperature at which the internal vapor pressure of the liquid becomes equal to atmospheric pressure (~760 mm Hg). The internal vapor pressure of a pure liquid rises steadily as the temperature is increased until the boiling point is reached The temperature remains constant throughout the boiling process of a pure liquid. At the boiling point, the liquid and vapor are in equilibrium...if the composition of each phase remains constant, the temperature will remain constant

In a Distillation Process a liquid is heated to its boiling point, the vapors expand out of the container and are then cooled below the boiling point temperature, where they recondense as a liquid

Raoults Law
For a mixture of two miscible liquids (A and B), the total vapor pressure is the sum of the individual vapor pressures:

Ptotal = PA + PB
where

PA = NAliquid x PA And PB = NBliquid x PB

where PA is the vapor pressure of pure A and PB is the vapor pressure of pure B and NAliquid is the mole fraction of A and NBliquid is the mole fraction of B where

NAliquid = moles A/moles A + B and NBliquid = moles B/moles A +B

Vapor Enrichment
From Raoults Law we can obtain the following relationships:

NAvapor = PA/PT
And

NBvapor = PB/PT
If A is more volatile than B, BPA < BPB and PA > PB Then

NAvapor > NAliquid

The result of this process is that when a mixture of two miscible liquids with different boiling points is heated,the vapor will have a different composition than the liquid. THE VAPOR IS ENRICHED IN THE MORE VOLATILE (LOWER BOILING) COMPONENT.

Distillation Process

Liquid-Vapor Composition Diagram

When a mixture AB of a specific composition is heated, the total vapor pressure (composed of the contributions of PA and PB) will rise until it is equal to the external vapor pressure. The mixture will begin to boil. The vapor which first forms is enriched in the more volatile component. This behavior is shown at right,

Assume a two component mixture with a composition of 30%A:70%B (point W). The boiling point of this mixture is found by drawing a vertical line from W to where it intersects the lower curve (point X). A horizontal line drawn from X to where it intersects the vertical axis (the temperature) gives the bp of composition W. From the point (Y) where this horizontal line intersects the upper curve (vapor) drop a vertical line to intersect the lower axis (the composition). Point Z gives the composition of the vapor which is in equilibrium with a liquid of composition W at its boiling point.

Fractional Distillation
AB at composition of 5% A boils at temperature L1 and the vapors with composition V1 enter the column at that temperature. The vapor will condense to a liquid with composition V1. The condensate L2 has a lower boiling point (because it has more of the lower boiling liquid A) and will thus vaporize at a lower temperature (warmed up by coming in contact with the additional vapors from below) to give vapors of composition V2. These vapors will condense somewhat farther up the column to give a condensate L3. If the column is long enough or contains sufficient surface area that many successive vaporizationcondensation steps (theoretical plates) can occur, the distillate that comes over the top is nearly pure A. Distillation yielding pure A continues until all of A is removed, after which the temperature at the
thermometer rises to the boiling point of B.

Fractional distillation is the separation of a mixture into its component parts, or fractions, such as in separating chemical compounds by their boiling point by heating them to a temperature at which several fractions of the compound will evaporate. It is a special type of distillation. Generally the component parts boil at less than 25 C from each otherunder a pressure of one atmosphere (atm). If the difference in boiling points is greater than 25 C, a simple distillation is used.

Fractional distillation

Diffusion
Consists of solute molecules moving upward into the solvent and solvent molecules moving down into concentrated solution. Bilateral process. Its occur in unequal concentrations.

Osmosis
It is Greek word means to push. The flow of solvent through a semi-permeable membrane from pure solvent to solution or from dilute solution to concentrated solution called osmosis. A membrane which is permeable to solvent and not to solute is called semi-permeable membrane. Reverse Osmosis

Examples:
1) Egg dissolved in water solution result Swell. Egg dissolved in salt solution result Shrink.

2)

An experiment in osmosis.
A semipermeable membrane separating water and an aqueous solution of glucose.

Osmotic Pressure
The HSP, Built up on the solution which just stops the osmosis of pure solvent into the solution through semi-permeable membrane is called osmotic pressure. OR The external pressure applied to the solution in order to stop the osmosis of solvent into solution separated by a semipermeable membrane

Determination of Osmotic Pressure

1. 2. 3. Pfeffers Method (Descriptions and its Disadvantages) Berkeley & Hartleys Method (Descriptions and its Advantages) Modern Osmometer (Descriptions and its features )

The pfeffers method suffers from two disadvantages: a) It is slow and it takes a few days before the highest pressure is reached. b) It can not be used for measuring high osmotic pressure. Berkely & Hartleys method: This method is superior than pfeffers method in such a way that, a) It is quick and accurate. b) It can be used for determining high osmotic pressures.

Osmotic Solutions (Hypotonic, Isotonic & Hypertonic)

When two solutions are separated by a semipermeable membrane and there is no flow of water across membrane, the solutions are said to be Isotonic. When two solutions are separated by a semipermeable membrane, if one of lower osmotic pressure, it is said to be Hypotonic relative to the second solution. When two solutions are separated by a semipermeable membrane, if one of higher osmotic pressure, it is said to be Hypertonic relative to the second solution.

Theories Osmosis
1. Molecular Sieve Theory.
2. Membrane Solution Theory. 3. Vapor Pressure Theory 4. Membrane Bombardment Theory

Theories Osmosis
Molecular Sieve Theory: The membrane contains a lot of fine pores and act as sort of molecular sieve. Smaller solvent molecules can pass through the pores but the large molecules can not. Some membrane can act as sieve even through the solute molecules are smaller than the solvent molecules. Therefore, this theory remain in doubt. Membrane Solution Theory: Membrane proteins bearing functional groups such as COOH, OH, NH2 etc dissolve water molecules by hydrogen bonding or chemical interaction. This membrane dissolves water from the pure water (Solvent) forming what may be called Membrane solution. The dissolved water flows into the solution across the membrane in a bid to equalize concentration. In this way water molecules pass through the membrane while solute molecules being insoluble in the membrane do not.

Theories Osmosis
Vapor Pressure Theory: It suggests that a semipermeable membrane has many fine hole or capillaries. The walls of these, capillaries are not wetted by water (Solvent ) or Solution. Thus neither solution nor water can enter the capillaries. Therefore, each capillary will have in it solution at one end and water at the other, separated by a small gap. Since the VP of a solution is lower than that of the pure solvent, the diffusion of vapor will occur across the gap from water side to solution side. This will result in the transfer of water into solution. Membrane Solution Theory: This theory suggests that osmosis result from unequal bombardment pressure caused by solvent molecules on the two sides of the semipermeable membrane. On one side solvent while other side solute molecules occupying some of the surface area. Thus, there are fewer bombardment per unit area of surface on the solution side than on the solvent side. Result flow of solvent from the pure solvent to the solution across membrane.

Laws of Osmotic Pressure

The osmotic pressure of a solution at a given temperature is directly proportional to the concentration.
The osmotic pressure of a solution at a given Concentration is directly proportional to the temperature. 1. 2. 3. Boyle-vant Hoff law of solutions. Charles-vant Hoff law of solutions. Vant Hoff law of solution.

V=nRT

Note: Determination of molecular weight from above equation.