Pemisahan Kimia

Materi 4: Distilasi
 What Is Distillation?

Distillation is a commonly used method for purifying

liquids and separating mixtures of liquids into their
individual components.
Familiar examples include the distillation of crude
fermentation broths into alcoholic spirits such as gin and
vodka, and the fractionation of crude oil into useful
products such as gasoline and heating oil.
In the organic lab, distillation is used for purifying
solvents and liquid reaction products.
 Distillation:
Purification technique
Used to separate components of a mixture or to purify
an impure liquid
Several basic types/variations:
Simple distillation
Fractional distillation
Azeotropic distillation
Simple, high vacuum distillation
Steam distillation
 Distillation - Theory
A. Vaporization and Condensation One component system

1. For any liquid, the individual molecules within the liquid are
continuously in motion
2. A small percentage of these molecules attain enough kinetic
energy to leave the liquid phase
3. This exerts an opposing pressure on the atmosphere above the
solution known as the vapor pressure, P

Atmospheric pressure, Patm

Vapor Pressure, P
4. When enough energy, in the form of heat, is imparted to the
solution the vapor pressure becomes equal to the atmospheric
pressure and the liquid begins to boil

P < Patm P Patm

5. The vapor obtained from a boiling liquid, once cooled, will re-
condense to a liquid known as the distillate

6. The complete process is called a distillation

B. Why perform a distillation?

1. Organic chemistry is driven to the preparation of organic

compounds whereas other disciplines are concerned with
description of systems and analysis

2. For your first few experiments you are learning the means of
cleaning up a reaction mixture to obtain a pure product

Look at a typical organic reaction:

OH H2SO4
+

major minor

3. Distillation is one of the routine techniques for the separation and

purification of product in this case distillation would be a good
technique for the separation of the two liquid alkene products
 C. Some applications you could encounter:

1. Separation of a reaction solvent from a non-volatile solute

A + B C
Solvent bp of most modern synthetic
targets is usually >> 200 oC
(bp typically below 100 oC)

Mixture of solvent and solute is

rotated to increase the surface
Vacuum is area for evaporation which
applied to helps alleviate the effects of
reduce the boiling point elevation
boiling point
of the solvent
This is actually the most common
distillation performed in organic
laboratories the simple removal of
solvent from a reaction mixture
2. Separation of one liquid from another

A + B C + D
bp 60 oC bp 100 oC

Pure C?

Pure D?
C + D
Mixture of C + D?
This situation is a little more complex, and we will use this
experiment to illustrate the separation process and the apparatus
required
 Back to the theory

D. Separation of Two Liquids

1. For each component: if vapor pressure is plotted versus

temperature an exponential increase of vapor pressure is
observed as the boiling point is approached

Note: even if two compounds have the same ultimate boiling

point, the curvature of this line may be different!
D. Separation of Two Liquids

2. This relationship of vapor-pressure vs. temperature is given by the

Clausius-Clapeyron equation:

p = po exp [ - H
R
(1/T 1/To) ]
The x,y (independent and dependent variables) for this equation
are the known temperature (T) and the vapor pressure (p)
calculated for that temperature

The constants for this equation:

po and To: known vapor pressure for a known temp. (K)

H: heat of vaporization of the liquid

R: gas constant (8.314 J . mol-1 . K)

D. Separation of Two Liquids

1. Above a mixture of two or more volatile liquids each liquid makes

a partial contribution to the overall vapor pressure.

Pmixture = PA + PB +

2. When the sum of these partial pressures equals the atmospheric

pressure (or pressure above the mixture), the mixture boils

3. This Law implies that if a mixture of different volatile liquids is

heated to boiling and the condensed vapors are collected they will
be enriched in the component that is more volatile

more volatile = higher partial pressure, lower boiling point

4. This is the basis for using distillation as a technique for the

separation and purification of liquids.
D. Separation of Two Liquids Raoults Law

1. Raoult extended Daltons Law to illustrate that the contribution of

each components vapor pressure is related to its mole fraction in
the mixture at the interface of the liquid and vapor phases

Pmixture = XAPA + XBPB +

2. Once again at the boiling point:

Patm = XAPA + XBPB (2 component system)

3. The enrichment of a particular component in the condensed

vapors of a boiling mixture is related to both their volatility (P) and
their concentration (X) in the original mixture.
Where does all of this get us?

Dalton + CC?

??? What do I get?

Raoult + CC?
Why am I doing this?

Organic chemists are interested in separations and purification not

necessarily physical derivations!
What we need is:

A relation of the component mole fractions within a given mixture to

the observed boiling point

In English if I have an 80 : 20 mixture of A : B at what temperature

will it boil?

An estimation of the given enrichment of the condensate collected

from the distilling mixture

In English if I distill this 80 : 20 mixture of A : B will I get more of one

or the other in the condensed vapor, and is it worth my time?

Which apparatus would I use?

E. Combining Raoult with Clausius-Clapeyron

1. The sum of mole fractions of all components must equal one

1 = X A + XB

2. Substitute the equation for a single component into Raoults Law:

XB = 1 XA so Patm = XAPA + (1-XA)PB

3. Expansion and rearrangement of the expression gives us the

variation of mole fraction versus partial and atmospheric pressure:

Patm - PB
XA = _______________

(PA - PB)
E. Combining Raoult and Clausius-Clapeyron:
4. If we substitute this expression:

Patm - PB
XA = __________
(PA - PB)
into the Clausius-Clapeyron Equation:

p = po exp [ - H
R
(1/T 1/To) ]
We obtain an expression for the mole fraction of each component in
liquid that boils at a given temperature:

Patm - PB exp [
- HB
R
(1/T 1/ToB)]
XA = _________________________________________________________

PA exp [- HA
R
(1/T 1/ToA) ]
_
P B exp [ - HB
R ]
(1/T 1/ToB)
 E. Combining Raoult with Clausius-Clapeyron:

Combining the expressions for each component in a two component

mixture we obtain the following graphical relationship:

bp of pure A
Temperature

Vapor

bp of pure B
Liquid

0.0, 1.0 0.5, 0.5 1.0, 0.0

Mole Fraction, XA, XB
This relationship gives us the boiling point for any mixture of A and B
F. Dalton and Clausius-Clapeyron:

1. We have just described how the liquid composition relates to the

boiling temperature what is happening in the vapor phase?

2. The composition of the vapor is given by Daltons Law:

P = PA + PB
3. Substituting in the Ideal Gas Law for each component:
(PA = nA(RT)/V)
and canceling similar terms we find that the ratio of each
component to the total vapor pressure is given by:
PA/PTOTAL = nA/nTOTAL
4. Substituting mole fractions for number of moles we find that at 760
torr (1 atm) the vapor component for this system is given by:
XA vapor = XA liquid (PA/760)
If we substitute this XA into Clausius-Clapeyron:
 G. We get an expression for the composition of the vapor.

Now add this relationship, graphically, of the composition of the vapor

to the mole-fraction to temperature relationship we illustrated earlier,
we arrive at the goal:

bp of pure A
Temperature

Vapor

bp of pure B
Liquid

0.0, 1.0 0.5, 0.5 1.0, 0.0

Mole Fraction, XA, XB
G. Now for any mixture of liquids, we can determine:

1. The boiling point of the mixture (liquid line)

2. The composition of the vapor (vapor line) which shows how much
enrichment in the lower boiling component occurs

110 Vapor
line
Temperature C

100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)
Simple/Conventional Distillation
A. What is it?

1. A simple distillation uses one vaporization-condensation cycle to

effect a separation:

What we will be
discussing The cooling jacket and vacuum
occurs only in adapter function only to cool the
this part of the vapors to liquid efficiently and
apparatus direct them into the receiver
flask

The distilling flask is

directly attached to
the distillation head
 Simple Distillation
Single Vaporization / Condensation cycle of a mixture that
produces a distillate that is always impure at any temperature range
between the range of boiling points of the components
Therefore, it is impossible to completely separate the components in
a mixture with Simple Distillation
Relatively pure substances can be obtained from a
mixture with Simple Distillation if the boiling points of the
components differ by a large amount (>100oC)
If a small increment of the initial distillate is separated and
redistilled and this process is repeated many times, effectively
producing multiple sequential Vaporization/ Condensation Cycles,
an increasingly pure solution can be attained. This would be a very
tedious process involving a large number of distillations
B. How efficient is it?

Lets use the graphical representation we derived earlier to illustrate

what occurs in a simple distillation:

110 Vapor
line
Temperature C

100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)
 B. How efficient is it?

Suppose we have a 80:20 mixture of benzene and toluene and we

subject it to a simple distillation technique:

110 Vapor
line

From our
Temperature C

Liquid
graph, we see 100
line

that this
mixture will 90

boil at ~100 C
80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)
 B. How efficient is it?
The vapor that is collected from this 80:20 mixture is enriched in the
lower boiling component

We can 110
Vapor
line
determine that
the ratio of
Temperature C

100 Liquid
components in line

the vapor is now

90
55:45 toluene to
benzene
80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)
C. Application
1. From the graphical analysis we see that a simple distillation is not
100% efficient at separating two liquids

2. A simple distillation should therefore be used where:

The two components have boiling points that are more than
30-40 C apart

One of the liquids is already ~90+% pure

You are simply removing a pure solvent from a non-volatile

solute - (we mentioned this as one of the most common
distillation techniques, removal of a solvent from an organic
reaction to obtain the product)

You dont have enough material to bring the more efficient

fractional distillation set-up to equilibrium
 Fractional Distilation
To be used when components boiling points are closer
together
Unlike simple, uses a fractioning column; this column may
be packed with material so as to increase the surface area
for heat exchange, thus increasing the number of theoretical
plates.
The more theoretical plates, the better the
purification/separation.
 Accomplishes the same thing as Multiple Simple
Sequential Vaporization / Condensation Cycles, by
inserting a Fractionating Column (a Vigreux Column)
between the Distillation Flask and the Distillation Head
The Fractionating Column, of which there are many types
containing a variety of packing materials, subjects the
mixture to many Vaporization/Condensation Cycles as the
material moves up the column toward the Distillation
Head, which is attached to the Condenser
With each cycle within the column, the composition of the
vapor is progressively enriched in the lower boiling liquid
This process continues until most of the lower boiling
compound is removed from the original mixture and
condensed in the receiving flask

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 Fractional Distillation (Cont)
When the lower boiling liquid is effectively
removed from the original mixture, the
temperature rises and a second fraction containing
some of both compounds is produced
As the temperature approaches the boiling point
of the higher boiling point compound, the distillate
condensing into the third receiving flask is
increasingly pure in the higher boiling point
compound

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 As the distillation proceeds, the composition
of the liquid and the vapor are continuously
changing
The Horizontal and Vertical Lines represent the
processes that occur during a fractional
distillation.
Each Horizontal Line (L3V3, L2,V2), etc.,
represents both the vaporization step of a
given vaporization/condensation step and the
composition of the vapor in equilibrium with
the liquid at a given temperature.
Examples:
At 53oC with a liquid composition of 80% A
and 20% B (L4V4 on the diagram), the vapor
would have 95% A and 5% B when equilibrium
has been established between the liquid and
the vapor.
At 63oC with a 50/50 liquid mixture of A&B
(L3V3 on the diagram), the vapor would have a
composition of 80% A & 20% B at equilibrium.
3/21/2017 32
Distillation Fractional

A. What is it?
A fractional distillation utilizes two or more vaporization-
condensation cycles, in succession, to effect a separation.

This is accomplished by what distinguishes a

fractional distillation apparatus:

the fractionating column

The fractionating column causes the

vaporization-condensation cycle to repeat
by providing multiple surfaces for the cycle
to take place

Using our graphical representation of the

benzene-toluene mixture as an example
lets see how this works.
Distillation Fractional

A. What is it?
The fractionating column is placed
between the distilling flask and the
distillation head

Using our graphical representation of

the benzene-toluene mixture as an
example lets see how this works.
Distillation Fractional

110 Vapor
line

Temperature C
100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)

As the hot vapors leave the distilling flask,

they condense on the first cold surface, completing
one vaporization-condensation cycle.

Vapors from the Suppose we distill the same 80:20 mixture of toluene
Distilling flask to benzene we did in the simple distillation example
Distillation Fractional

110 Vapor
line

Temperature C
100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)

This surface begins to heat from the condensed vapors

which are now 55:45 toluene-benzene

This benzene enriched liquid now has a boiling point of ~94

C (lower than the incoming vapors) and it begins to boil off
Vapors from the
this higher surface
Distilling flask
Distillation Fractional

110 Vapor
line

Temperature C
100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)

These vapors are even further enriched in benzene (now

30:70, toluene:benzene) and condense on the next cold
surface
Vapors from the
Distilling flask
Distillation Fractional

110 Vapor
line

Temperature C
100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)

This condensed liquid has an even lower boiling point (86

C) and as this surface heats it begins to boil off this next
higher surface
Vapors from the
Distilling flask
Distillation Fractional

110 Vapor
line

Temperature C
100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)

This vapor now condenses on the next cold surface (now

20:80, toluene:benzene) and the cycle continues
Vapors from the
Distilling flask
Distillation Fractional

1:99 toluene:benzene
110 Vapor
line

Temperature C
100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)

This cycle will continue until the top of the column is reached

The liquid collected after seven cycles is now 99% benzene!

Vapors from the

Distilling flask
80:20 toluene-benzene
Distillation Fractional

1:99 toluene:benzene
110 Vapor
line

Temperature C
100 Liquid
line

90

80

Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
Composition (mole%)

Each vapor-condensation (or mini-distillation) cycle is

known as one theoretical plate

The length of distillation column required to provide one

Vapors from the theoretical plate of separation is known as the height
Distilling flask equivalent theoretical plate (HETP)
80:20 toluene-benzene
Distillation Fractional

Important 110 Vapor

line
What we have discussed is only
true for the first drop of distillate!

Temperature C
100 Liquid
line

As the distillation flask loses what

the vapor is enriched in, 90
The starting point for the next
drop of distillate will be slightly
different! 80

In our example, there will be Mole % Toluene 0 20 40 60 80 100

Mole % Benzene 100 80 60 40 20 0
more and more toluene in the Composition (mole%)
distillation flask more heat will
need to be applied to get the
liquid to boil, and heat the
distillation column More and more
toluene as
distillation
proceeds
Industrially,
fractional
distillation is
very
common and
is typically
run as a
continuous
process
Distillation Fractional

C. Applications
1. Because of the efficiency of the fractional distillation set-up it
should be used anywhere that two volatile liquids need to be
separated.

2. The only drawback is that each vaporization-condensation cycle

requires a volume of liquid to attain equilibrium; this is called the
hold-up volume or column hold-up and places a lower limit on
the amount of liquid we can distill AND how much liquid will be
lost in performing the distillation

3. For small amounts of liquid (<1 mL) chromatography (gas

chromatography, high-performance liquid chromatography or
column chromatography) is the separation method of choice.
 Vacuum Distillation
Vacuum distillation is a method of distillation whereby the pressure
above the liquid mixture to be distilled is reduced to less than its
vapor pressure (usually less than atmospheric pressure) causing
evaporation of the most volatile liquid(s) (those with the lowest
boiling points). This distillation method works on the principle that
boiling occurs when the vapor pressure of a liquid exceeds the
ambient pressure. Vacuum distillation is used with or without heating
the solution.
Temperature sensitive materials (such as beta carotene) require
vacuum distillation to remove solvents from the mixture without
damaging the product. Vacuum distillation is sometimes referred to
as low temperature distillation. This type of distillation is in use in
the oil industry.
 Advantages of Vacuum Distillation
Industrial-scale vacuum distillation has several advantages.
One tool to reduce the number of stages needed is to utilize vacuum distillation.
Vacuum distillation columns typically used in oil refineries have diameters
ranging up to about 14 meters (46 feet), heights ranging up to about 50 meters
(164 feet), and feed rates ranging up to about 25,400 cubic meters per day
(160,000 barrels per day).
Vacuum distillation increases the relative volatility of the key components in
many applications. Lower pressures increase relative volatilities in most systems.
A second advantage of vacuum distillation is the reduced temperature requirement
at lower pressures. For many systems, the products degrade or polymerize at
elevated temperatures.
Vacuum distillation can improve a separation by:
Prevention of product degradation or polymer formation because of reduced
pressure leading to lower tower bottoms temperatures.
Increasing capacity, yield, and purity.
Another advantage of vacuum distillation is the reduced capital cost, at the
expense of slightly more operating cost. Utilizing vacuum distillation can reduce
the height and diameter, and thus the capital cost of a distillation column.
 Azeotropic Distillation

An azeotrope is a mixture of two or more liquids (chemicals) in such a ratio

that its composition cannot be changed by simple distillation. This occurs
because, when an azeotrope is boiled, the resulting vapor has the same ratio
of constituents as the original mixture.
Because their composition is unchanged by distillation, azeotropes are also
called constant boiling mixtures.
positive azeotrope is 95.63% ethanol and 4.37% water (by weight).
Ethanol boils at 78.4C, water boils at 100C, but the azeotrope boils at
78.2C.
negative azeotrope is hydrochloric acid at a concentration of 20.2% and
79.8% water (by weight). Hydrogen chloride boils at 84C and water at
100C, but the azeotrope boils at 110C.
 Azeotropic distillation
Azeotropic distillation usually refers to the specific technique of adding another
component to generate a new, lower-boiling azeotrope that is heterogeneous
(e.g. producing two, immiscible liquid phases), such as the example below with
the addition of benzene to water and ethanol. In actual fact, this practice of
adding an entrainer which forms a separate phase is a specific sub-set of
(industrial) azeotropic distillation methods, or combination thereof. In some
senses, adding an entrainer is similar to extractive distillation.
Example - distillation of ethanol/water, using normal distillation techniques,
ethanol can only be purified to approximately 96% . Some uses require a higher
percentage of alcohol, eg. when used as a gasoline additive.
Material separation agent- The addition of a Material Separation Agent, such as
benzene.
Molecular sieves- For the distillation of ethanol for gasoline addition, the most
common means of breaking the azeotrope is the use of molecular sieves.
 Tugas
1. Mencari teori kesetimbangan pemisahan
a. Padat gas
b. Padat cair
c. Gas-cair
d. Kesetimbangan campuran
e. Kesetimbangan campuran cair-gas campuran
biner
f. Kesetimbangan campuran padat-cair campuran
biner
1. Sebutkan aplikasi masing-masing jenis distilasi
2. Apa keunggulan distilasi vakum dan ditilasi fraksinasi?
3. Bagaimana prinsip distilasi fraksinasi?
4. Bagaimana prinsip pemisahan campuran azeotropik??
5. Mengapa sulit untuk memisahkan dua buah senyawa
dalam fasa cair yang bercampur sempurna?
6. Mengapa sulit untuk mendapatkan persen pemurnian
diatas 80% untuk distilasi konvensional
7. Bagaimana meningkatkan perolehan kemurnian
senyawa pada distilasi konvensional?