Theoretical Principles of Fractional Distillation

VAPOR PRESSURE
Gas or vapor
Consists of molecules in random and chaotic motion Millions of small particles moving in all directions in the air in the room, they collide with each other repeatedly

The molecules of a vapor in a container repeatedly have collisions with the walls of the container
When many gas molecules collide repeatedly with the walls of a container, these collisions add up to a pressure exerted on the walls
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If the temperature of a gas is increased, the molecules in the gas move faster The more rapid motion at higher temperatures results in more violent collisions of the molecules As the molecules move faster and the collisions

become more violent

a. In a closed container
Molecules in a closed container strike the walls with more force. The pressure, therefore, increases At a lower temperature, the vapor molecules move

slower

b. In an open container
The pressure of a gas in an open container cannot be increased, since some of the gas would escape to equalize the pressure with the surroundings The pressure of a gas in an open container cannot be increased by increasing the temperature
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Liquids
Like the molecules of gases, the molecules of a liquid are constantly in motion

Unlike the molecules of gases, the molecules of a liquid are held close together by natural attraction between the molecules tends to keep each molecule confined to

a small space

Within this space a molecule is usually in violent motion

The violent motion of the molecules at the surface of a liquid causes many of these molecules to escape from the liquid If the temperature of a liquid is increased, the

motion of the molecules becomes more violent

Vapor (gas) Liquid

If an empty container is partially filled with liquid, molecules escape from the surface of the liquid, forming a vapor in the space above the surface Gas molecules which strike the surface of a liquid tend to stick to the liquid

Thus, molecules may be escaping the liquid and returning to the liquid from the gas at the same time

When a vessel contains both a liquid and a vapor, molecules are continually going from the liquid to the vapor or gas and from the vapor to the liquid When the number of molecules leaving the liquid equals the number entering the liquid, the gas and the liquid are said to be in equilibrium with each other So at equilibrium, equal numbers of molecules pass between the liquid and the vapor, or gas

Evaporation
When more molecules are escaping the liquid than returning, the liquid is said to be evaporating. The process in which a greater number of molecules leave the liquid than enters it is called evaporation

Condensation
When more molecules are entering the liquid from the vapor than are escaping the liquid, the vapor is condensing. The process in which a greater number of molecules enter the liquid than leave it is called

condensation

Temperature Effect
When the temperature of a liquid is increased, the pressure of the vapor in equilibrium with it increases and maintains equilibrium On the other hand When the temperature of a liquid is decreased, the pressure of the vapor decreases and maintains equilibrium

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When a liquid and a vapor are at equilibrium, the pressure of the vapor is called

The vapor pressure of the liquid

The pressure of a gas or vapor above the surface of a liquid in a closed container is not necessarily the same

as the vapor pressure of the liquid

In order for the pressure of the gas to be equal to the vapor pressure of the liquid The gas and the liquid must be in equilibrium with each other

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When
A liquid is placed in an open container and heated

Both
its vapor pressure and its rate of evaporation increase Until The vapor pressure equals the pressure of the atmosphere evaporation becomes very rapid, and the liquid boils
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If the pressure over a boiling liquid is increased, the boiling temperature is increased and If the pressure over a boiling liquid is decreased, the boiling temperature is decreased Since the pressure of the atmosphere on the top of a mountain is lower than at sea level, liquids boil at lower temperatures on top of a mountain

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The vapor pressures for different liquids at the same temperature are not the same
Therefore, water and pentane have different vapor pressures at 130 F Pentane has a vapor pressure of is 30 psia

Water has a vapor pressure of 3 psia

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PARTIAL PRESSURE
The pressure that a gas exerts on the walls of a container depends on

The number of collisions between the molecules and the container wall
If more molecules are present, there are more collisions and a greater pressure

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If two containers

of the same volume are filled with gas to the same pressure and temperature, each contains the same number of gas molecules For the same volume and temperature
the greater the number of molecules in a gas, the greater the pressure of the gas must be

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When two or more gases are mixed, each gas exerts a pressure on the walls of the container Although these separate pressures cannot be measured, the total pressure can be measured

The total pressure of a gas mixture is equal to the sum of the pressures of the different gases in the mixture
The separate pressures of the gases are called

Partial Pressures
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For a mixture of two gases If the partial pressure of each gas is the same, there must be equal numbers of each kind of molecule If a tank contains 5 times as many ethane molecules as propane molecules The partial pressure of ethane is 5 times as great as propane

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If a closed container is partially filled with a mixture of two liquids, molecules of both liquids escape to the gas from the liquid and return to the liquid from the gas At equilibrium, the number of molecules escaping from the liquid is equal to the number returning to the liquid for each component. A system of butanehexane Butane would be the light molecules and Hexane the heavy molecules
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At equilibrium the number of light molecules escaping from the liquid is equal to the number returning to the liquid

Also, at equilibrium the number of heavy molecules escaping from the liquid is equal to the number of heavy molecules returning to the liquid However
At equilibrium the number of light molecules escaping and returning to the liquid is not equal to the number of heavy molecules escaping and returning to the liquid

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Light molecules are able to escape the liquid more rapidly than the heavy ones
Therefore, at equilibrium, there are more light molecules escaping and returning to the liquid Because the light molecules are able to escape the liquid faster than the heavy ones, the light molecules tend to concentrate or to be enriched in the vapor For example If the liquid contains half light and half heavy molecules At equilibrium, the gas contains more light molecules than heavy molecules
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When the gas and the liquid are at equilibrium The gas is richer in the light component and The liquid is richer in the heavy component Therefore, if a liquid mixture is partially vaporized The light component in the vapor becomes more concentrated than the light component in the liquid In other words, the vapors are enriched in the lighter component

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FUNDAMENTALS
Fractional distillation is an operation which is based on the differences in volatility or different escaping tendencies of the products which have to be separated It is obvious that for solving the numerous problems in technical fractionation a thorough knowledge of the fundamental laws and rules governing the volatility characteristics of systems consisting of two or more components is a prerequisite

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Henry's Law

At a given temperature the partial vapor pressure of a relatively volatile substance above its solution (in a relatively non-volatile solvent) is proportional to its concentration in the solution

Pi = Ci xi
Where xi = mole fraction of a certain component in the liquid, Pi = partial vapor pressure of this component, Ci = proportionality factor
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Applying Henry's law to pure compound

When xi becomes 1, Ci equals Pi

Pi = Pi xi

(2)

In this form and restricted to ideal solutions Henry's law is known as Raoult's law. Mixtures of paraffin and naphthene are, in general, very nearly ideal
While mixtures of aromatics with naphthenes or paraffins are further away from ideal solutions
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Dalton's Law The second important law underlying the theory of fractional distillation is Dalton's law regarding partial pressures and their additively. Mathematically, Dalton's law is expressed as follows:

Pi xi = P Yi
Where:

and

Pi =P

Pi= partial pressure of component i, P = total pressure of system, Yi = mole fraction of component i in the vapor phase.

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Pi xi = P Yi
Yi P i xi P

From equation above (known as Raoult-Dalton's law) it follows that the concentration of any component in a vapour which is in equilibrium with a liquid mixture can be calculated by multiplying the concentration of that component in the liquid phase by the ratio of the vapor pressure of the pure component to the total pressure of the system
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K Values The fact that components in a non-ideal mixture do influence the volatility of the other components results in deviations from Raoult Daltons law which are of the same order of magnitude, a solution of the problem is found by introducing the concept of k values Using k values,
Yi xi
Raoult Daltons equation

becomes:

= ki

or

Yi = ki xi

It is possible to calculate boiling points, dew points, vapour pressures and dew pressures of mixtures
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Boiling Point Calculation Is the temperature at which, when the temperature of the liquid mixture is raised, the first infinitesimal amount of vapour escapes as a bubble at a given pressure This temperature is also known as the "bubble point The vapour will contain a certain amount of each component, depending on the volatility of that component, and it is clear that if the concentration in the vapour phase (Yi) is expressed in mole fraction, Yi must equal 1

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