Distillation

Introduction
Vapor pressure: the pressure produced by fluid in the saturated state. Vapor pressure depends on the temperature of the system, not on the amount of substance or volume. Unit in mm Hg (Torr) Boiling point: the temperature at which the vapor pressure of the liquid equal to the external pressure, the liquid tends to change from liquid phase to vapor phase. Normal boiling point: boiling point of liquid which measured at 1 atm (air pressure).

Vapor pressure Diagram

Raoult law : vapor pressure of a compound is proportional to the number of moles of compounds contained in the mixture
PA X A .PA

PB X B .PB

XA: mol fraction of A; PA=vapor pressure of A in pure condition XB: mol fraction of B; PB=vapor pressure of B in pure condition Number of partial pressure of A and partial pressure of B egual to vapor pressure of mixture A and B

P PA PB X A.P A X B .P B
Vapor pressure above the solution is comparable with mol fraction substance in vapor phase, composition of A and B in vapor phase are:

Vapor pressure in above solution equal to mol fraction in vapor phase, while the composition of substance A and B in vapor phase can be determine as:
PA XA PA PB

PB XB PA PB

The concentration of each component in vapor and liquid phase, eg for component B are: X U P P 1 A B B
XB PA PB PB
PA XA XA PB

If PA=PB, so XuB/ XB=1 or mol fraction of vapor pressure = mol fraction of liquid phase because XA+XB=1. If PA<PB, concentration of B in vapor phase bigger than in liquid phase. If PA>PB, concentration of B in vapor phase lower than in liquid phase.

Simple Distillation
Principle : mixture of solution was heated at a constant pressure (atm) would evaporate, the more volatile substances (ex: substances A) will be in the vapor phase more than in the composition of the original solution. If the vapor phase is cooled then solution containing higher substance of A. Substance B (Td >>) leaves a residue Distillation is repeated until substance A and B are more pure

Distillation process to separate ethanol from water

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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.

Condensor

Liebig and west condensor: it has a inner tube with very thin wallsrapid heat transfer to the fast-flowing cooling water leading to greater efficiency

Condensor
Double coil (a) and Davies (b): efficient double surface condensor Friedrich : highly efficient for reflux and distillation Ice-cooled : useful for volatile liquids
(a) (b) (c)

Fractional Distillation
Principle: simple distillation which the distillate (result of distillation) conducted repeated distillation. To separate a mixture of two or more components special condenser The length and type of the column depend on boiling point of components to be separated

The condition necessary for a good separation are: Comparatively large amounts of liquid continually returning through the column Thorough mixing of liquid and vapour A large active surface of contact between liquid and vapor

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.

Distillation Efficiency
The efficiency of a fractional distillation is determined by the amount of pure liquid components obtained. Keep in mind that if a liquid is pure it will have a constant boiling point. The temperature of vapors in equilibrium with liquid at the boiling point will be constant. A plot of temperature vs. time for a pure liquid will look like A below.
The efficiency of a fractional distillation can be demonstrated graphically by plotting the change in temperature of the distillate over time (or over volume of distillate, as in this experiment). In a fractional distillation with low efficiency, separation will be poor. There will be little or no pure component as distillate. The composition of the distillate will be constantly changing and the bp of the vapor in equilibrium with liquid will be constantly changing. It will give a plot such as B. An efficient distillation will give pure components which will have constant boiling points. Such a process is shown below in plot C. The relatively flat: horizontal regions at the beginning and end of the plot indicate pure components A and B are obtained. The closer to this ideal sigmoid shape the better the fractional distillation.

Condensor
Vigreux column: to separate mixture of compound with boiling point differences between 15-20C Column consists of a glass tube with a series of indentattions such that alternate sets of indentations point downwards at an angle 45 in order to the redistribution of liquid from the walls to the centre of the column.

Condensor
Packed and oldershaw column: to separate mixture of compound with boiling point differences closer

Packed column

Oldershaw column

Distillation Setups

Fractional Distillation Set-up

Proper Thermometer Depth

Ideal Solution
Distillation process would be working if the solution is ideal solution The characteristics of the ideal solution: 1. when mixed, reactions do not occur 2. when mixed, with no change in volume 3. follow Raoult's law:
PA X A .PA

or

PB X B .PB

Azeotrope Mixture
Definition: a mixture of two solutions at a particular composition has properties like pure solution.

Azeotropic mixture with boiling point minimum:

Compound A Water 100C Water 100C
Ethanol 78,3C

Compound B Ethanol 78,3C Isopropanol 82,4C

Chloroform 61,2C

Tb azeotrope 78,15C 80,40C

59,40C

%A in azeotrope 4,4 12,4

7,0

Azeotropic mixture with boiling point maximum:

Compound A Compound B Tb azeotrope %A in azeotrope

Water 100C
Water 100C Water 100C

Formic acid 100,8C

HCl 84,0C HNO3 86C

107,1C
120C 120,5C

77,5
37 68

Separation of azeotrope mixture

Depend on properties of each compound Add third compound which that compound can change the vapor pressure of the mixture. Eg: water-ethanol+benzene Add reagent which can react with one of component in the mixture. Eg: waterethanol+CaO Absorb one of component in the mixture with silica gel or active carbon Fractional crystalization GC or LC

Low Pressure Distillation (vacuum)

Principle: by lowering the pressure above the liquid surface with the aid of a vacuum pump, the fluid distilled will volatile, because the liquid will boil below its normal boiling point Many organic compound cannot be distilled under atm pressure because they undergo partial or complete decomposition before the normal boliling point is reached By reducing the external pressure to 0.1-30 mm, the boling point is considerably reduced and the distillation may ussualy be conducted without danger of decomposition

To separating the mixture which component of mixture is easily damaged on their boiling point Valuable when the substances undergo decomposition when distilled alone at atm pressure To separating highly concentrated mixture

Low Pressure Distillation (vacuum)

vacuum should be set, if not set, the composition of the vapor similar to liquid composition, separation does not occur

Steam Distillation
Is a method to isolating or purifying the organic compounds Is used liquid that does not dissolve or mutually miscible partial pressure of saturated vapour will follow the law dalton:

P P 1 P 2 P 3 ...

If the mixture which is not miscible heated, the boiling point are temperature which amount of the vapour pressure equal to atmospheric pressure Steam distillation used to separated essential oil such as clove oil, rosse oil, etc.

if water is used to produce steam, the boiling point of the mixture will be lower than 100C the distillate are mixture of all of the substances which present in the mixture, while concentration of substance depending on the vapour pressure of each substance in the mixture

Eg: total pressure of mixture of A and B are:

P PA PB

So the composition of vapour can be formulated:

nA PA nB PB

nA= mol A and nB = mol B

nA WA MA nB WB MB

WA M A .nA M A .PA WB M B .nB M B .PB

W = mass M = molecular weight

Importance in the separation of the desire organic compound:

From non-volatile tarry substances which are formed as by products in many reactions From aqueous mixtures containing dissolved inorganic salts From compound which are not appreciably volatile in steam (eg: o-nitrophenol from pnitrophenol From certain by products which are steam volatile