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Instructor:

Dr. M.E Ojewumi


Reading Materials
• J. Geankoplis Transport Processes and Unit Operations, Prentice Hall,
1993
• C. J. Separation Processes, McGraw Hil,l 1980
• G. F. Nalven ed. Distillation and other Industrial Separations, AIChE,
1997.
• R. E. Treybal, Mass transfer Operations, McGraw Hill, 1980
UNIT OPERATION
• What is chemical engineering? Chemical Engineering is a group of
industrial processes in which raw materials are changed or separated
into useful products.
• What are "Unit Operations"? [involve certain type of processes
carried out in a specific equipment].
• Every industrial chemical process is based on Unit Operations
(physical treatment) and Unit Process (chemical treatment) to
produce economically a desired product from specific raw materials.
• The raw materials are treated through physical steps to make it
suitable for chemical reaction. So, knowledge of unit operations like
‘Mixing and agitation of liquid’ and’ heat flow’ is very much
necessary. The subject Unit Operations is based on fundamental laws,
physicochemical principles.
• Unit ops refers to steps intended primarily to perform some physical
transformation (as opposed to chemical transformation) of the input
stream.
• A unit operation is any part of potentially multiple-step process which can
be considered to have a single function
• Unit Operations gives idea about science related to specific physical
operation; different equipment's - its design, material for construction and
operation; and calculation of various physical parameters (mass flow, heat
flow, mass balance, power and force etc.).

Traditional classification of processes:


▪ Mechanical processes
▪ Hydrodynamical processes
▪ Heat transport processes
▪ Mass transport processes (or diffusion separation processes)
▪ Chemical processes
▪ Biochemical and biological processes.
Examples of unit operations:
▪ Milling and grinding – Involve mechanical processes
▪ Fluid transportation, filtration settling, fluidization, mixing – Involve
hydromechanical processes
▪Heat exhange, evaporation – Involve energy (heat) transport
▪Extraction, absorption, drying, distillation, membranes – Involve mass
transport
▪ Reactors and bioreactors – Involve chemical reaction
OTHERS ARE
• Absorption and stripping Membrane Process: Reverse
osmosis, Ultrafiltration, Dialysis, Electrodialysis,
Evaporation, Adsorption and desorption, Pressure
Swing, adsorption, Chromatography, Crushing,
Grinding, Pulverizing and Screening Distillation: Batch
distillation Flash distillation, Azeotropic distillation,
Extractive distillation Reactive distillation Solid liquid
extraction Evaporation Striping Fluidisation
Sublimation Crystallisation Solvent extraction Liquid-
Liquid extraction
Unit Operation in Chemical Process Industries
• Following are some examples of physical processes :
1. Sugar Manufacture: Sugar cane crushing → sugar extraction →
thickening of syrup →evaporation of water → sugar crystallization →
filtration →drying →screening →packing.
2. Salt Manufacture: Brine transportation → evaporation →
crystallization →drying → screening → conveying → packaging.
3. Pharmaceutical Manufacture: Formulation of chemicals, mixing,
granulation → drying of granules→ screening → pressing tablet →
packaging
Introduction: Separation Process
• A separation process, is any mass transfer process
used to convert a mixture of substances into two or
more distinct product mixtures, at least one of
which is enriched in one or more of the mixture's
constituents.
• Done by contacting the mixture with another phase.
• Such two phases are generally only partially
miscible in one another.
• The two phases in contact may be Gas-solid, Gas-
liquid, liquid-solid, liquid –liquid.
Introduction: Separation in process industry
• Removal of contaminants from feed, wastes, and recycle
streams
• Separation of valuable products from wastes, impurities
and by-products.
• Separation processes account for 50 to 90% of the capital
costs of most chemical plants and about 70% of the
ultimate product cost.
• Separation processes is also important in biological
organisms, ecosystems, and environmental engineering.
Introduction: Separation Process
• When such two phases are brought into
contact
• there is the transfer of one or more
solutes (components) from one phase
to the other
• due to the difference in concentration,
temperature or pressure of the solutes
in the two phases.
Separation process
.
Feed/mixt
ure to be A product
separated phase
richer in a
Contacting solute
device

Another
product Another
phase poorer phase brought
in a solute in to contact
feed
Introduction: Separation Process
• After the contacting, the two phases may now be
separated
• The choice of phase and conditions will ensure that
one of the phases in contact will be depleted or
enriched in one or more components of the original
mixture.
• Several separations may be required to achieve the
level of purification desired-multiple separation
stages
Two Phases in Contact: Liquid and Gas
Name of separation Phases in Direction of eg
process contact transfer of
solute(e)
Absorption liquid and Gas to liquid SO2 in air to
gas water
NH3 in air to
water

humidification liquid and Liquid(water) to Water into pure


gas gas(air) air

dehumidification liquid and Gas(air) to liquid Drying of moist


gas air

Stripping or liquid and Liquid to gas Steam to


desorption (reverse gas remove volatile
absorption) components
from non-
volatile oils
L-V, L-L, S-L contacting phases
Distillation Volatile Liquid to Ammonia(aqueous) to vapour
vapour and vapour; richer in ammonia
liquid that vapour to
vapourises liquid

Liquid-liquid Liquid- Liquid- Acetic acid from aqueous


(solvent)extra liquid liquid solution
ction to isopropyl ether

Solid-Liquid Liquid- Solid Solid to Liquid extracting copper from ores using
extraction H2SO4 sol

crystallization Liquid- Solid Liquid to Solid Sugar from conc. sugar solutions
Gas‐Liquid Separation Processes
(Gas Absorption)
ABSORPTION
• This is the passage of one substance into or through the bulk of
another medium e.g Perfume and Chips {When a substance is
absorbed in a different medium}
• Adsorption is the adhesion or sticking together of molecules of a gas,
liq, or dissolved solids to the surface of a solid or sometimes liquid e.g
Red dye solution and Gas mask (easily reversible by simple heating).
Transfer gas component from gas to liquid or vice versa
• requires two phases: liquid and gas
• uses the different affinity gas component for gas and liquid.
Gas absorption
(also known as scrubbing)
• Is an operation in which a gaseous mixture is contacted
with a liquid for the purpose of preferentially dissolving
one or more components of the gas mixture and to provide
a solution of them in the liquid.
• There is a mass transfer of the component of the gas from
the gas phase to the liquid phase.
• The solute to transfer is said to be absorbed by the liquid.
The Absorption Process
• •The transfer of material from a gas (absorbate) to a liquid
(absorbent)
• •Transfer is based on the preferential solubility of a gaseous
component in the liquid
• •Also known as “scrubbing”or “washing” •Examples include removal
and recovery of NH3in fertilizer manufacturing
• •Control of SO2 from combustion source •Control of odorous gases
from rendering plants
Desorption (Or Stripping),
• In gas desorption (or stripping), the mass transfer is in the
opposite direction (from the liquid phase to the gas phase)
• The principles for both systems are the same.
Assumptions are:
• only one component of the gas solute is absorbed.
• The other components of the gas are assumed to be non-
soluble in the liquid
• The liquid is non-volatile-i.e. there is no transfer of
molecules from the liquid to the gas phase.
• No chemical reaction in the system and
• Operating at isothermal conditions.
commercial Absorption applications
Method of Operation
• Two methods of contacting the gas and liquid
are possible:
1. counter-current operation
2. co-current operation.
• We will focus principally on the counter-current gas
absorption, as it is widely used in the industry.
• for counter-current operation, the gas enters the column or
tower from below and leaves at the top, while liquid enters
from the top and flows in opposite direction and exits from
the bottom.
Counter-current co-current
Inside the column where there is vapour-liquid contact, mass
transfer by absorption occurs, i.e. there is a transfer of
solute(s) from the gas phase to the liquid phase.
Counter-current operation
Types of columns
• Spray Column:
The gas flows upward continuously through an open chamber
in which scrubbing liquid droplets falls from spray nozzles
through the gas.
The gas pressure drop is small, but separation is not as good as
the bubble column.
This column is widely used for its simplicity, low pressure drop,
and resistance to scale deposition and plugging.
• TRAY Column:
• sieve tray, valve tray and bubble-cap trays. These internals
are the same as those in "Distillation
• Packed Column
• Both random and structured packings had been used. " there
are stacked, structured and random Packings
Bubble Column
• The gas is forced under pressure through perforated pipes
submerged in the scrubbing liquid.
• As such the gas phase is dispersed and the liquid phase is
continuous.
• As the bubbles rise through the liquid, absorption of the gas
occurs.
• This type of device suffers from the high pressure drop due
to the liquid hydrostatic head.
Physical vs. Chemical Absorption
• 2 types of absorption processes:
• physical absorption and chemical absorption, depending
on whether there is any chemical reaction between the
solute and the solvent (absorbent).
• When water and hydrocarbon oils are used as absorbents,
no significant chemical reactions occur between the
absorbent and the solute, and the process is commonly
referred to as physical absorption.
• When aqueous sodium hydroxide (a strong base) is used as
the absorbent to dissolve an acid gas, absorption is
accompanied by a rapid and irreversible neutralization
reaction in the liquid phase and the process is referred to as
chemical absorption or reactive absorption
•More complex examples of chemical absorption are
processes for absorbing CO2 and H2S with aqueous
solution of
•monoethanolamine (MEA),
• diethanolamine (DEA),
• diethyleneglycol (DEG) or
•triethyleneglycol (TEG),
where a reversible chemical reaction takes place in the
liquid phase.
•Chemical reactions can increase the rate of absorption,
•increase the absorption capacity of the solvent,
•increase selectivity to preferentially dissolve only certain
components of the gas, and convert a hazardous chemical
to a safe compound
Counter-Current Gas Absorption
TRAY COLUMN FOR GAS ABSORPTION
(DILUTE SYSTEMS)
• L and G are approximately constant for dilute systems.
• The operating line is a straight line of the form y = mx + c,
with a gradient of L / G,
• It connects the 2 end points - point 1 (x1 , y1) that are
conditions at the bottom of the column, and point 2 (x2 , y2)
conditions at the top of the column.
• The equilibrium solubility line is also straight, as
represented by Henry's Law, y = mx, where m is the Henry's
Law constant which is also the gradient of the line.
• The solution for number of theoretical trays required for
gas absorption can be obtained using
• graphical method or
• mathematical equation.
Graphical: Number of Theoretical Trays
• Graphically : method similar to the McCabe-Thiele Method
used in continuous distillation.
• Start from point 1 and work the way down towards point 2,
and draw triangles between the operating line and
equilibrium line.
• the last triangle represents a theoretical tray, not a reboiler.
• Analysis for the changes in gas phase and liquid phase
compositions is similar to the distillation process:
• For example, consider tray (b) where the liquid
concentration changed from xa at the inlet to xb at the
outlet,
• gas composition changed from yc at the inlet to yb at the
outlet. ( yc - yb ) showed the decreases in gas concentration
as it passed through tray (b), and ( xb - xa ) showed the
increase in liquid concentration as it passed through tray (b).
• The larger the triangle, the more effective the separation.
5 theoretical trays required for gas absorption separation.
mathematical equation.
The Kremser-Brown-Souders (KBS)
Equation
•For dilute system, recall that both the operating line and equilibrium
line are straight, even on x-y coordinates.
• In this case, the number of theoretical stages required for a given
separation can be calculated using the Kremser-Brown-Souders
Equation as shown:
· Absorption

where A = L /mG= absorption factor and is assumed constant.


Kremser-Brown-Souders (KBS) Equation:
·

Stripping

where the stripping factor S = 1/A, is assumed constant.

Note: m = Henry's Law constant = slope of the equilibrium line.


Choice Of Solvent For Gas Absorption
• If the principal purpose of the absorption operation is to produce a specific
solution, as in the manufacture of hydrochloric acid, for example, the solvent
is specified by the nature of the product, i.e. water is to be the solvent.
• If the principal purpose is to remove some components (e.g. impurities) from
the gas, some choice is frequently possible.
• The factors to be considered are:
• Gas Solubility
-The gas solubility should be high, thus increasing the
rate of absorption and decreasing the quantity of solvent required
Choice Of Solvent For Gas Absorption2
-. Generally solvent with a chemical nature similar to the solute to be
absorbed will provide good solubility
- A chemical reaction of the solvent with the solute will frequently
result in very high gas solubility,
-but if the solvent is to be recovered for re-use, the reaction must be
reversible.
• For example
*H2S can be removed from gas mixtures using amine solutions since
the gas is readily absorbed at low temperatures and easily stripped at
high temperatures.
*Caustic soda absorbs H2S excellently but will not release it in a
stripping operation.
• Volatility. The solvent should have a low vapour pressure to reduce loss
of solvent in the gas leaving an absorption column.
Choice Of Solvent For Gas Absorption3
• Corrosiveness
*The materials of construction required for the equipment
should not be unusual or expensive.
• Cost
*The solvent should be inexpensive, so that losses are not
costly, and should be readily available.
• Viscosity
*Low viscosity -rapid absorption rates, improved flooding
characteristics in packed column, low pressure drops on
pumping, and good heat transfer characteristics.
• Others
*The solvent should be non-toxic, non-flammable and
chemically stable.
Major Techniques for Capture/Elimination
of Gas Pollutants
•Oxidation to form nontoxic compounds
•Chemical reduction to form nontoxic
compounds
•Adsorption onto solid surfaces
• Absorption into liquids
•Biological oxidation to form nontoxic
compounds
•Condensation of vapors to form liquids
Types of Absorber Control Equipment

•Packed bed tower absorbers


•Spray tower absorbers
•Tray tower absorbers
•Venturi Absorbers
•Ejector Absorbers
•Biofiltration Bed Absorbers
Gas Absorption Equipment
•Packed bed absorbers –most common
•Counter-current flow tower
configuration
•Gas flow enters bottom of tower and
flows upward
Gas Absorption Equipment
Gas Absorption Equipment
•Another counter current flow
tower configuration
Cross-Flow Scrubber
Packed Bed Abs. Applications
•Suited to applications where high gas
removal efficiency is required
•Exhaust gas is relatively free from
particulate matter
•Control of SO2and HCl in sulfuric acid
and hydrochloric acid production
Packing Elements
Packing Elements
•Packing material provides a large surface area
for mass transfer
•Packing elements are made of plastic
(polyethylene,polypropylene,
polyvinylchloride), ceramic or metal
•Sizes range from 1 to 4 inches each
•Design depends on corrosiveness of gas,
scrubbing liquid, size of absorber, static
pressure drop and cost
Spray Tower Absorber
•Simplest device used for absorption
•Consists of open vessel and a set of liquid
spray nozzles to distribute scrubbing liquid
(absorbent)
•Limited efficiency because of limited
contact between gas and spray droplets
–Used when gases are extremely soluble in
absorbent
–Chemical reaction in liquid could cause
clogging
Gas Absorption Equipment
Tray Tower Absorber
Packed Tower Design
Diameter and height of the bed can be
estimated for this design
Use generalized flooding and pressure drop
correlation graph
Loading: Occur because of higher gas/vapor flow rates.
Flooding: Flooding is brought about by excessive vapor flow, causing
liquid to be entrained in the column. Flooding is detected by sharp
increases in column differential pressure and significant decrease in
separation efficiency.
Weeping: This phenomenon is caused by low vapor flow. The pressure
exerted by the vapor is insufficient to hold up the liquid on the tray.
Therefore, liquid starts to leak through perforations. Excessive weeping
will lead to dumping.
Entrainment: Entrainment refers to the liquid carried by vapor up to the
tray above and is again caused by high vapor flow rates.
Production processes using absorber

•scrubbing smokestacks
•removal of ammonia from refinery
•remove CO2 from air.
Extraction Theory
Separation by Extraction
Introduction
Extractions uses two immiscible phases to separate a solute from one phase into the other. The distribution of a
solute between two phases is an equilibrium condition described by partition theory.
Extraction is the general practice of dissolving solid/compound in one liquid and forcing it to become
dissolved in another liquid. This is done by taking advantage of the relative solubility of a compound between
two Liquids.
For example, caffeine must be extracted from coffee beans or tea leaves in order to be used in beverages such
as coffee or soda. The common method for doing this is to use supercritical carbon dioxide, which is able to
dissolve caffeine as if it were a liquid. Then, in order to take the caffeine out, the temperature is lowered (lower
ing the "solubility" in carbon dioxide) and water is injected. The system is then allowed to reach equilibrium.
Since caffeine is more soluble in water than it is in carbon dioxide, the majority of it goes into the water.
• Boiling tea leaves in water extracts the tannins, theobromine, and caffeine (the good stuff) out of the leaves
and into the water. More typical lab extractions are of organic compounds out of an aqueous phase and into
an organic phase.
Extraction is also used for purification, if some solution is contaminated with a pollutant, the
pollutant can be extracted with another, clean stream. Even if it is not very soluble, it will still
extract some of the pollutant.
Solvent extraction is sometimes called liquid extraction. It involves the selective transfer of a
substance from one liquid phase to another e.g. aqueous solution of iodine and sodium
chloride is shaking with ccl4 (carbon tetra-chloride) and the liquid allowed to separate. Most
of the iodine will be transferred to ccl4 layer and sodium chloride will remain in aqueous
layer.
Analytical Extractions {hyp}
Solids are usually dissolved or digested in solution and liquids are sometimes extracted to separate the it
from interferences.

Examples of organic solvents used for solvent extraction include;

Chloroform is a heavy solvent which is widely used for extracting organic compounds and metal complexes
from aqueous solution.

Benzene and ethyl ether are lighter than water solvents.

The degree of separation afforded by solvent extraction will be determined by the distribution ratio, that is
the relative concentration of the solute in the organic and aqueous phases.

Separation can be improved by increasing the number of extractions.


What is liquid liquid extraction?
• The separation of the components of a liquid mixture by treatment with a solvent in which one or
more of the desired components is preferentially soluble is known as liquid–liquid extraction.
• is a useful method to separate components (compounds) of a mixture
Extraction refers to the transfer of a solute from one liquid phase to another.
Solvents that are less dense than water :
Diethyl ether (d= 0.7077, 25oC)
Benzene (d= 0.8787, 15oC)
Hydrocarbons (ex. Hexane, d= 0.660, 20oC)

Solvent that are immiscible with and dense than water :


Chloroform (d= 1.484, 20oC)
Dichloromethane (d= 1.33479, 15oC)
Carbon tetrachloride (d= 1.589, 25oC)
Liquid-liquid extraction:

• used for processes that requires low temperature operation


• transfer soluble component from one liquid to another
• requires two phases: two immiscible or partially miscible liquids
• uses the different affinity components for separation.
Example 1,

Suppose that you have a mixture of sugar in vegetable oil and you want to separate the sugar from
the oil. You observe that the sugar particles are too tiny to filter and you suspect that the sugar is
partially dissolved in the vegetable oil.
Shake the mixture with water
Sugar is much more soluble in
water than in vegetable oil, and,
water is immiscible that is not
soluble with oil.

The water phase is the bottom


layer while the oil phase is the top
layer, because water is denser than
oil.

Shake the mixture vigorously.


By shaking, the layers (phases) very
well, you will increase the contact
area between the two phases. The
sugar will move to the phase in
which it is most soluble: the water
layer

Now the water phase tastes sweet,


because the sugar is moved to the
water phase upon shaking. In this
example, water was the extraction
solvent ;the original oil-sugar
mixture was the solution to be
extracted; and sugar was the
compound extracted from one
phase to another. Separating the
two layers accomplishes the
separation of the sugar from the
vegetable oil
This is the concept of liquid-liquid extraction.

Liquid-liquid extraction is based on the transfer of a solute substance from one liquid phase
into another liquid phase according to the solubility. Extraction becomes a very useful tool if
you choose a suitable extraction solvent.
You can use extraction to separate a substance selectively from a mixture, or to remove
unwanted impurities from a solution. In the practical use, usually one phase is a water or
water-based (aqueous) solution and the other an organic solvent which is immiscible with
water.

The success of this method depends upon the difference in solubility of a compound in various
solvents. For a given compound, solubility differences between solvents is quantified as the
"distribution coefficient"
Partition Coefficient Kp (Distribution Coefficient Kd)

When a compound is shaken in a separatory funnel with two immiscible


solvents, the compound will distribute itself between the two solvents.

Normally one solvent is water


and the other solvent is a
water-immiscible organic
solvent.

Most organic compounds are


more soluble in organic solvents,
while some organic compounds
are more soluble in water.
Here is the universal rule:

At a certain temperature, the ratio of concentrations of a solute


in each solvent is always constant. And this ratio is called the
distribution coefficient, K.

(when solvent1 and solvent2 are immiscible liquids)

For example,Suppose the


compound has a distribution
coefficient K = 2 between
solvent1 and solvent2

By convention the organic


solvent is (1) and water is (2)
(1) If there are 30 particles
of compound , these are
distributed between equal
volumes of solvent1 and solvent2..

(2) If there are 300


particles of compound , the
same distribution ratio is
observed in solvents 1 and 2

(3) When you double the


volume of solvent2 (i.e., 200
mL of solvent2 and 100 mL of
solvent1), the 300 particles of
compound distribute as shown

If you use a larger amount of extraction solvent, more solute is


extracted
What happens if you extract twice with 100 mL of solvent2 ?
In this case, the amount of extraction solvent is the same volume as was
used in Figure 3, but the total volume is divided into two portions and
you extract with each.

As seen previously, with 200 mL


of solvent2 you extracted 240
particles of compound . One
extraction with 200 mL gave a
TOTAL of 240 particles
You still have 100 mL of solvent1,
containing 100 particles. Now you
add a second 100 mL volume of
fresh solvent2. According to the
distribution coefficient K=2, you
can extract 67 more particles
from the remaining solution
An additional 67 particles are
extracted with the second portion
of extraction solvent
(solvent2).The total number of
particles extracted from the first
(200 particles) and second (67
particles) volumes of extraction
solvent is 267.This is a greater
number of particles than the
single extraction (240 particles)
using one 200 mL portion of
solvent2!

It is more efficient to carry out


two extractions with 1/2 volume
of extraction solvent than one
large volume!
If you extract twice with 1/2 the volume, the extraction is more
efficient than if you extract once with a full volume. Likewise,
extraction three times with 1/3 the volume is even more efficient….
four times with 1/4 the volume is more efficient….five times with 1/5
the volume is more efficient…ad infinitum

The greater the number of small extractions, the greater the


quantity of solute removed. However for maximum efficiency the
rule of thumb is to extract three times with 1/3 volume
Separatory Funnel Extraction Procedure
Separatory funnels are designed to facilitate the mixing of immiscible liquids
Separatory Funnel Extraction Procedure

1. Support the 2. Pour in liquid to 3. Add extraction 4. Add ground glass


separatory funnel in a be extracted solvent Stopper (well greased)
ring on a ringstand.
Make sure stopcock is
closed
Separatory Funnel Extraction Procedure
Shake the separatory funnel.

Then, point the stem up and slowly open the


stopcock to release excess pressure. Close the
stopcock. Repeat this procedure until only a small
amount of pressure is released when it is vented
Pick up the separatory
funnel with the stopper in
palce and the stopcock
closed, and rock it once
gently.
Separatory Funnel Extraction Procedure
Shake the separatory funnel vigorously.
Now, shake the funnel vigorously for a few seconds. Release
the pressure, then again shake vigorously. About 30 sec
total vigorous shaking is usually sufficient to allow solutes to
come to equilibrium between the two solvents.

Vent frequently to prevent pressure buildup,


which can cause the stopcock and perhaps
hazardous chemicals from blowing out. Take
special care when washing acidic solutions with
bicarbonate or carbonate since this produces a
large volume of CO2 gas
Separatory Funnel Extraction Procedure
Separate the layers.

Let the funnel rest While waiting, remove the Carefully open the stopcock and
undisturbed until the layers stopper and place a beaker allow the lower layer to drain
are clearly separated or flask under the sep into the flask. Drain just to the
funnel. point that the upper liquid
barely reaches the stopcock
Choice of solvent
• Distribution coefficient
• Selectivity (Separation Factor)
• Insolubility of Solvent
• Density
• Recoverability
• Viscosity, Vapour Pressure, Freezing Point
• Chemical Reactivity
• Availability and Cost
Single stage Batch Extraction
Extraction is preferred on Distillation
• Distillation would require excessive amounts of heat, e.g, when the
relative volatility is near unity.
• When the formation of azeotropes limits the degree of separation
obtainable in distillation. (A liquid mixture that is characterized by a
constant minimum or maximum boiling point which is lower or higher
than that of any of the components)
• When heating must be avoided.
• When the components to be separated are quite different in nature.
Stopper

Aqueous layer

Body

Organic layer
(ex. methylene chloride)
Stopcock

Drain Tip

Parts of a separatory funnel


The partition theory: (The distribution of a solute between two phases in an equilibrium condition is
described by partition theory)
Assuming we have an aqueous solution of trichloroacetic acid. Our need is to remove the acid from the
solution. This can be easily accomplished by mixing, in a separatory funnel, an organic solvent (e.g.,
dimethyl ether) immiscible with water but able to solubilize the acid. After mixing, the system will reach
a state of equilibrium which is governed by the partition law:
K = [Ce] / [Cr]
where K = partition or distribution coefficient
Ce = concentration in the extract phase
Cr = concentrations in the raffinate phase
K = a constant (for ideal solutions) at constant temperature which depends on the nature of solvents used.
Partition coefficient

S(in phase 1)  S(in phase 2)


V1 V2
K = AS2 /AS1  [S]2 / [S]1
K = {(1–q)m/V2} / (qm / V1) Partitioning of a solute between two liquid phase

q = V1 / (V1 + KV2)
where q is the fraction of solute remaining in
phase 1.
Multiple extractions
for n extractions
q n = [V1 / (V1 + KV2)] n
Multiple extractions
From the definition of the partition coefficient we have that
K = [Ce]/[Cr] , [Ce] = K[Cr]
and we get:
[Co] Vr = [Ce]Ve + [Cr]Vr = K[Cr]Ve + [Cr]Vr = [Cr] (KVe + Vr)
[Cr] = [Co] Vr / (KVe + Vr) = [Co] / (1 + KVe/Vr)
where Co is the initial concentration of the solute and Vr the volume of the initial solution;
[Ce] is the concentration of solute in the extract phase and Ve the volume of the extract phase;
[Cr] is the concentration of solute in raffinate phase and Vr the volume of raffinate phase.
Please note that the volume of the raffinate phase (Vr) is supposed to be equal to that of the original solution.
for n extractions
[Cr]n = [Co] [ (1 + KVe/Vr)]n = [Co] [Vr / (KVe + Vr)]n
Numerical example
The partition coefficient of a solute is 3, assuming that the initial solution contain 0.01 M of
solute in 100 ml of solution. Calculate the amount of solute (in % fraction) remaining in the
raffinate after:
1) a single extraction using 500 ml of solvent E
2) five extraction using 100 ml of solvent E
1. In the first case
q = [100 / (100 + 3×500)] = 0.062 = 6.2 %

2 In the second case


q = [100 / (100 + 3×100)]5 = 0.00098 = 0.098 %
Extraction of Metal - Organic Complexes

A large number of organic compounds form complexes with metal cations. Many
of these complexes are more soluble in organic solvents than in water and hence
are extractable. For example, the iron(III)-cupferron chelate or the aluminium(III)-
oxine complex is extracted by chloroform. The distribution ratio for this type of
complex is usually very large, so only one or two extractions of the complex is
usually very large and so only one or two extractions with fresh solvents are
needed. The chelating reagents are solids and the metal complexes are insoluble in
water. The metal is extracted by adding an aqueous solution of the reagent to an
aqueous solution of the sample and extracting the precipitated metal complex with
an organic solvent. Alternatively, the chelating reagent may be dissolved in a
water-immiscible organic solvent, which is then shaken with the sample solution.
Shaking produces a temporary emulsion of the two liquid phases. Metal ions in the
sample solution react with the chelating reagent at the interfaces between phases
and then are extracted into the organic phase.
Extraction methods used in the making of aromatic materials.

Aromatic Materials of Natural Origin

Steam Maceration Enfleurage Percolation Expression SFE


Distillation Digestion

Solvent
Fat or Extraction
Fixed Petroleum
oil benzin

Distilled Alcohol Pomades Citrus oils SFE


essential tincture Absolute
oils

Absolutes Concretes
Hydrosol Alcohol
Steam distillation for the extraction of essential oils
Liquid-liquid extraction:
• used for processes that requires low temperature operation
• transfer soluble component from one liquid to another
• requires two phases: two immiscible or partially miscible liquids
• uses the different affinity components for separation.
Production processes using extraction

•food processing
•pharmaceutical separation,
•oil purification.
Summary
• If the correct solvent was used for extraction, 2-3 extractions are usually
sufficient to isolate the majority of the target compound
• Unless large amounts of material are transferred from one phase
to the other, the solvent/solution volume that should be used for extraction
should not exceed 10-20 % of the volume being extracted
in mind that pressure will build uto extract acidic compounds
• No extract should be discarded until the target compound has been
isolated (and characterized!)
LLX
• It is a process of transferring a solute from one liquid phase to
another immiscible or partially miscible liquid in contact with the first.
• The two phases are chemically quite different, which leads to a
separation of the components according to their distribution or
partition between the two phases, normally one organic and one
water.
• Extraction is driven by chemical differences, not by vapor pressure
differences, and so can be used in situations when distillation is
impractical
TYPES
Extraction processes may be:

• single stage

• multistage crosscurrent

• or countercurrent.
Terminology
Certain terms are commonly used when describing extraction
processes:
• The solution to be extracted is called the feed

• The liquid used in contacting is the solvent.

• The enriched solvent product is the extract and the depleted feed is
called the raffinate.
Equilibrium Relations in Extraction
The solution to be extracted is called the
feed, the liquid used in contacting is the
solvent. The enriched solvent product is the
extract and the depleted feed is called the
raffinate.
Nernst partition or distribution law
• The extraction of soxhlet is governed by Nernst partition or
distribution law which states that at equilibrium, a given solute will
always be distributed between two essentially immiscible liquid in the
same proportion.
• [A] organic / [A] aqueous = KD (same temperature and pressure)
• Where
• [ ] represents the concentration
• KD is “partition coefficient” . it is independent of the concentration of
the solute.
• ‘A’ must exist in the same form in both phases.
• Equilibrium is established when the chemical potential (free energy)
of the solute in the two phases are equal and is usually achieved
within a few minutes of shaking.
• The value of KD is a reflection of the relative solubilities of the solute
in the two phases.
The value of KD breaks down if ‘A’:
• 1. dissociates
• 2. polymerizes
• 3. form complexes with other components e.g. solvents.
• Analytically, the total amount of solute present in each case is better
described in distribution ‘D’,

• Where D =

𝐶𝐴 0/𝑚𝑙

𝐶𝐴 𝑎𝑞/𝑚𝑙

• CA = amount of solute
• If there is no interaction, D = KD
EFFICIENCY OF EXTRACTION
• It depends on the magnitude of D or KD and on the relative volumes
of the liquid phases

• The % of extraction is given by:

𝟏𝟎𝟎𝑫
• ∑= 𝑽𝒂𝒒 For equal volume of aqueous and organic
[𝑫+ ]
𝑽𝒐
solvent

𝟏𝟎𝟎𝑫
•∑ =
[𝑫+𝟏]
• If D is large i.e. tending towards 100, a single extraction may affect
virtually quantitative transfer of the solute.
• whereas with small values of D, several extractions would be
required.
• The amount of solute remaining in aqueous solution is readily
calculated for any number of extractions with equal volumes of
organic solvents from the following equation,
𝑽𝒂𝒒
• [Caq]n = Caq { }𝒏
(𝑫𝒗𝒐+𝑽𝒂𝒒)

• Where [ Caq]n is the amount of solute remaining in aqueous phase.


• Vaq = the volume of aqueous solvent after n extraction
• Vo = the volume of organic solvent after n extraction.
• If the value of D is known, the equation above is useful in determining
the outmost condition for quantitative transfer of material.
EX. 1
• The complete removal of 0.1g of iodine from 50cm3 of an aqueous
solution of iodine and sodium chloride is carried out using CC14/H2O;
the value of D was given as 85.
Calculate the efficiency using:
1. 25cm3 of CCl4 once
2. Batch extraction three times.
Which method out of the two would be most efficient?
It is therefore clear that extracting several times with small volumes of
organic solvent is more efficient than one extraction with large volume.
ASSIGNMENT
A solution of 6g of substance X in 50 cm3 of aqueous solution is in
equilibrium at room temp with ether solution of aqueous liquid
containing 108g of X in 100 cm3 with:

A. 100cm3 of ether once


B. 50cm3 of ether twice at room temperature.

Which process is more efficient in both methods a & b? Bear in mind


that 100cm3 of ether is used in both a & b.
solid-liquid extraction:
• used liquid to extract component from a solid matrix
• transfer soluble component from solid to liquid
• requires two phases: solid and liquid,
• uses the solubility of the component for separation.
Sedimentation

Definition of Sedimentation: It is the process of removing solid


particles heavier than water by gravity force or separation of
unstable and destabilized suspended solids from a suspension by
the force of gravity.

Particles that will settle within a reasonable period of time can


be removed using a sedimentation tank (also called clarifiers).

Sedimentation is used in water treatment at the locations


indicated inFigures1 - …
Sedimentation in water Treatment
• Applications of sedimentation in water treatment:
• 1. Plain settling (or pre‐sedimentation) of river surface water.
• 2. Infiltration treatment plants treating surface water to removes
flocculated solids. The sedimentation tank comes after the flocculation
tank.
• 3. In Softening treatment plants treating hard water to removes
flocculated solids. The sedimentation tank also comes after the
flocculation tank.
• 4. In aeration treatment plant removing iron and manganese from
ground water
Further Applications
• Applications in Water Treatment:
• 1. settling of coagulated and flocculated waters prior to filtration
• 2. settling of coagulated and flocculated waters in a softening plant
• 3. settling of treated waters in an iron and manganese removal plant
• Applications in Waste water Treatment:
• 1. grit removal
• 2. suspended solids removal in primary clarifier
• 3.biological floc removal in activated sludge
Sedimentation in water Treatment

Geometry of sedimentation tanks:

• Sedimentation tanks are either rectangular or circular tanks.


• Figures below show typical sedimentation tanks used in water
treatment.