Separation techniques

(Code: SOU30251)

3rd Stage Chemistry Department

Semester 6/Level UGIII

Lecturer: Dr. Vian S. Ismail

Email: [email protected]

Week 2/Lecture No. 2

Lecture time: Sunday:11.30-2.30

( 28/ 01/2024 )
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Separation by precipitation
Separation by precipitation require large solubility differences between
analyte and potential interferences.

In precipitation an insoluble compound forms when we add a precipitating

reagent, or precipitant, to a solution containing our analyte.

When a solution is super-saturated, it is in an unstable state and this favors

rapid nucleation to form a large number of small particles (precipitation).

A technique that is used to

separate mixtures of an
insoluble solid (precipitate)
and a liquid is called
Filtration.
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 Precipitation process is influenced by several factors:
-Solubility of the precipitate
-Temperature
-pH control
-Precipitating agents

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Separation based on precipitation can be carried out by several methods:
1- Separation based on control of acidity
The solubility of different of elements can be varied by controlling the
acidity, and this can be classified into 3 main categories:
1- Those made precipitates in relatively concentrated solutions of strong
acids such as oxides of W(VI), Si(IV), Sn(IV), Sb(V).
2- Those made precipitates in buffered solutions at intermediate pH values,
Cr(III), Al(III).
3-Thos made precipitates in concentrated solutions of sodium or potassium
hydroxide, such as Fe(III).

2- Sulfide Separation
Most of the cations, with the exception of the alkali metals and alkaline
earth metals, form sparingly soluble sulfides whose solubilities differ greatly
from one another.
Because it is relatively easy to control the sulfide ion concentration of an
aqueous solution of H2S by adjustment of pH, separation based on the
formation of sulfides have found extensive use.
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3- Separation by other inorganic precipitants
-Hydroxide and sulfide inorganic ions are very useful for separation
-Chlorides and sulfate are also very useful for separation because of
their highly selective behavior. Chloride is used to separate Ag from
most other metals and sulfate is frequently employed to isolate lead,
barium and strontium.
-Phosphate, carbonate, and oxalate are often used for precipitating
cations, but their behavior is non-selective; therefore separation must
ordinarily precede their use.

4- Separation by organic precipitants

-Some organic precipitant s are very selective such as DMG.
-Other organic precipitants such as 8-hydroxyquinoline yields slightly
soluble compound with a host of cations. This can be adjusted by
controlling the PH.

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5- Separation of species present in trace amounts

The problem in trace analysis is isolation of the species of interest

which may be present in microgram quantities from the major
components of the sample.
-One way to separate a trace amount species is by adding a collector,
which is used to remove trace constituents from solution. For
example:
1- in isolating manganese as the sparingly soluble manganese dioxide,
a small amount of iron (III) is frequently added to the analyte solution
before the introduction of ammonia as the precipitating reagent. The
basic iron (III) oxide carries down even the smallest traces of the
manganese dioxide.
2- The use of basic aluminum oxide as a collector of trace amounts of
titanium.
3- and the use of copper sulfide for collection of traces of zinc and
lead. 6
Note:
It is important that the collector must not interfere with the method
selected to determine the trace component. It functions in two ways:
1- A collector may entrain a trace constituent as a result of similarities
in their solubilities.
2-A collector function by coprecipitation, in which the minor
component is adsorbed on or incorporated into the collector
precipitate as the result of mixed-crystal formation.

6- Separation by electrolytic precipitation (electro

deposition)

Electrolytic precipitation is a very useful method of accomplishing

separations based on the redox reaction.
The mercury cathode has found wide application in the removal of
many metal ions prior to the analysis of the residual solution.
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7- Salt –Induced precipitation of proteins

Salt-induced precipitation Technique used to precipitate proteins.

At low salt concentration, adding salt increases solubility (salting-in
effect), whereas high salt concentrations induce precipitation (salting-
out effect).The solubility of protein molecules depend on several
factors, such as:
1-pH
2- Temperature
3-The nature of the protein
4- The concentration of the salt used

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The salting-in and salting-out principle is explained by Debye-Hückel theory.
According to this theory, in case of salting-in effect, the counter ions of the
salt surround the protein, and the screening results in a decrease in the
electrostatic attraction of protein molecules for each other. This in turn
leads to increasing solubility with increasing ionic strength. At high
concentration of salt, however, the repulsive effect of like charges is
reduced, as are factors leading to solvation of the protein. When these
factors are reduced enough, the protein precipitates and salting-out is
observed.
One of the inexpensive and widely used salt is ammoinum sulfate, because
of its effectiveness and high inherent solubility.
-Proteins are commonly less soluble at their isoelectric points. Therefor, a
combination of high salt concentration and pH control is used to achieve
salting-out.

-Care must be taken with some proteins because ammonium sulfate can
denature the protein. As a consequence, alcoholic solvents are sometimes
used in place of salts. They reduce the dielectric constant and
subsequently reduce solubility by lowering protein-solvent interaction 9
-Separation by solvent extraction
Extraction is the method of separating a substance (solid or liquid)
from a mixture by dissolving one or more of the components in a liquid
solvent
The solvent is immiscible or only partial miscible with the solid or the
liquid. By intensive contact the active agent transfers from the solid or
liquid mixture (raffinate) into the solvent (extract). After mixing, the
two phases are separated either by gravity or centrifugal forces.

The characteristics of the solvent for extraction:

Non-toxic
Easily removed
Desired constituent is soluble
Non-reactive 10
Types of extraction depending on the phases:

 Solid-liquid extraction (solid-phase extraction)

Solid-liquid extraction allows soluble components to be
removed from solids using a solvent.

 Liquid-liquid extraction
Liquid-liquid extraction involves using a liquid solvent to
remove a liquid /dissolved solid component from a liquid
mixture.
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Solid-liquid extraction (solid-phase extraction)
Solid-phase extraction techniques use
membranes or small disposable syringe-barrel
columns or cartridges. A hydrophobic organic
compound is coated or chemically bonded to
powdered silica to form the solid extracting
phase. The compounds can be non-polar,
moderately polar, or polar. For example, an
octadecyl (C18) bonded silica (ODS) is a common
packing. The functional groups bonded to the
packing attract hydrophobic compounds in the
sample by van der Waals interactions and extract
them from the aqueous solution.

Figure: Solid-phase extraction performed in a small cartridge.

The sample is placed in the cartridge and pressure is applied via a
syringe plunger. Alternatively, a vacuum can be used to pull the sample
through the extracting agent. 12
-Liquid-liquid extraction (LLE)

Is the extent to which solutes, both inorganic and organic, distribute

themselves between two immiscible liquids (phases/layers).

Top phase: always organic, except for DCM

(dichloro methane) and chloroform (CHCl3)

Bottom phase: always aqueous, except

when using DCM (dichloro methane)
and chloroform

Q: How could you check which layer is which??

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LLE principles
Feed phase contains a component, i, which is to be removed.
Addition of a second phase (solvent phase) which is immiscible with
feed phase but component i is soluble in both phases. Some of
component i (solute) is transferred from the feed phase to the
solvent phase. After extraction the feed and solvent phases are
called the raffinate (R) and extract (E) phases respectively.
Normally one of the two phases is an organic phase while the other
is an aqueous phase. Under equilibrium conditions the distribution of
solute i over the two phases is determined by the distribution law.
After the extraction the two phases can be separated because of
their immiscibility. Component i is then separated from the extract
phase by a technique such as distillation and the solvent is
regenerated. Further extractions may be carried out to remove more
component i.

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Compared to solid-liquid extraction, Liquid-liquid extractions have
some Limitations :
1- The solvents that can be used must be immiscible with water and
must not form emulsions.
2- liquid-liquid extractions use relatively large volumes of solvent,
which can cause a problem with waste disposal.
3- Most extractions are performed manually, which makes them
somewhat slow and tedious.

solid-liquid extraction, can overcome several of these

problems

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Most organic compounds are more soluble in organic solvents than in water, usually
by the distribution coefficient K > 4 However, specific classes of organic compounds
can be reversibly altered chemically to become more water-soluble.

What type of organic compounds can be made water-soluble? Compounds

belonging to the following solubility classes can be converted to their water-soluble
salt form
(1) Organic acids include carboxylic acids (strong organic acids) and phenols (weak
organic acids).

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How can organic acids or bases be converted to a water-soluble form?
1. Organic Acids can be converted to their salt form when treated with an aqueous
solution of inorganic base (e.g., NaOH (sodium hydroxide) and NaHCO3 (sodium
bicarbonate)).Salts are ionic, and in general, ions are soluble in water but not
soluble in water-immiscible organic solvents. Remember: water is a very polar
solvent thus salts (i.e., ionic species) are well dissolved in it. Carboxylic Acids are
converted to the salt form with 5% NaOH aqueous solution. NaOH is a strong
inorganic base. Carboxylic acids are strong organic acids (pKa = 3 to 4), so they can
also be ionized with weak inorganic bases (e.g., NaHCO3 (sodium bicarbonate))
aqueous solution.

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Phenols are considered to be weak organic acids. Phenol, the parent compound, is
partially water-soluble (1 g will dissolve in 15 mL of water), whereas substituted
phenols are not. Sodium bicarbonate (NaHCO3) aqueous solution, a weak inorganic
base, will not deprotonate phenols to make it ionic, because it is not strong enough.
However, treatment with NaOH, a strong inorganic base, can change phenol to its
ionic (salt) form.

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(2) Organic bases includes amines

Organic Bases (amines) can be converted to their salt form when treated with an
aqueous solution of an inorganic acid such as HCl (hydrochloric acid). Recall that
salts are ionic and generally soluble in water but not soluble in water-immiscible
organic solvents.

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Several washes can be done in LLE, as follows:
-Aqueous wash removes water soluble components
-Acid wash removes basic solutes
-Base wash removes acidic solutes
Note: Review lecture (no.1) for the practical section to understand
these 3 type of washes in LLE.

It is well known that hydrated inorganic salts tend to be more soluble

in water than in organic solvents such as benzene, chloroform, etc.,
whereas organic substances tend to be more soluble in organic
solvents than in water unless they incorporate a sufficient number of
hydroxyl, sulphonic, or other hydrophilic groupings.
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Distribution/Partition Coefficient or Distribution/Partition Constant (KD)
The partition of a solute between two immiscible phases is an
equilibrium phenomenon that is governed by the distribution law. If
the solute species A is allowed to distribute itself between water and
an organic phase, the resulting equilibrium may be written as:

A(aq) A(org)

-KD is the ratio of the concentrations of the solute in each solvent at

a particular temperature

- KD is independent of the total concentration and the actual amounts

of the two solvents mixed

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 (aA)org [A]org
KD = =
(aA)aq [A]aq

where (aA)org and (aA)aq are the activities of A in each of the phases
and the bracketed terms are molar concentrations of A. This rule
would be expected to apply only in very dilute solutions, where the
ratio of the activities approaches unity. The law in its simple form does
not apply when the distributing species undergoes dissociation or
association in either phase.

where
[A]org = is the concentration of solute to the extracted solvent
(organic)

[A]aq = is the concentration of solute in the original solvent (aqueous)

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(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
Generally, if we use equal volumes (V=100ml )for
If you use a larger amount of each phase and we have 300 particles
extraction solvent, more X/(300-X)=2, then X=200particles in org phase and
solute is extracted 300-200=100 particles in the aq phase 24
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!

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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

For using small portion of solvent with

several extractions (K=(267/200)/(33/100)=4
The greater K the greater effeceincy or A
large value for K indicates that extraction
of solute into the organic phase is
favorable. 26
The importance of distribution constant (KD)

The solute is initially present in one of the two phases; after the
extraction it is present in both phases.
Distribution constant are useful because they permit us to calculate
the concentration of an analyte remaining in a solution after a
certain number of extractions.
They also provide a guidance to the most efficient way to perform
an extractive separation.
For the simple system of extraction described by this equation:

[A]org
Equation (1) KD =
[A]aq

The concentration of A remaining in the aqueous solution after

extracting Vaq ml of solution with a Vorg ml of the organic solvent is
given by this equation:
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Tutorial section

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Example 1: The distribution constant for iodine between an organic solvent and H2O
is 85. Find the concentration of I2 remaining in the aqueous layer after extraction of
50.0 ml of 1.00 x 10-3 M I2 with the following quantities of the organic solvent:
(a) 50.0 ml
(b) Two 25.0 ml portions
(c) Five 10.0 ml portions

Solution:

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Let's try a sample problem. Here is a mixture of naphthalene and benzoic acid,
dissolved in dichloromethane.

You want to separate these two compounds. What will you do?

You may use an aqueous solution of either 5%

NaOH or sat. NaHCO3, to extract benzoic acid
as a salt form

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Let's try this problem again. Here is
another mixture of benzoic acid and p-
methoxyphenol, dissolved in
dichloromethane.

NaOH was too strong a base, thus it does not differentiate the
strong and weak organic acids. Use of weak inorganic base such
as NaHCO3 will differentiate between the compounds

Strong organic acids such as benzoic acid would be

deprotonated and ionized, while weak organic acids such
as phenols would NOT be deprotonated
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 Let's try a third sample problem. Here is a
mixture of benzoic acid and p-
chloroaniline, dissolved in
dichloromethane.

You want to separate these two compounds. What will you

do?

You may use an aqueous solution of either 5% HCl, to extract

the amine as a salt form and benzoic acid has remained in
the organic layer

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You can separate four different classes of compounds from a mixture based on differing solubility
properties. The four classes are:1.Amines (organic base)2.Carboxylic acids (strong acid)3.Phenols
(weak acid)4.Neutral compounds.

After the separation of the mixture of

four components, we will have four
solutions: each solution contains one
component.
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 The first three compounds are chemically altered, existing in their salt form
dissolved in aqueous solution. The fourth compound is not chemically altered, but
it is dissolved in an organic solvent. We now want to recover each compound in its
original state (i.e., in the non-ionic form) to complete the experiment. We call this
step isolation or recovery. Let's see, one by one, how to recover each compound
obtained from the separation process
Isolation (Recovery) of amines An amine is a basic compound. It is protonated in
the presence of excess HCl forming a salt that is soluble in aqueous solution. This is
how you separated the amine from the original mixture containing it.

An amine is soluble in acidic aqueous solution

because it forms a salt, an ionic form.

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However, if you change the pH of the solution to basic the amine can no longer
stay dissolved because it is no longer ionic! This process is called basification.
Basification is done by carefully adding concentrated NaOH solution to the
solution containing the amine salt until it becomes basic.

Basification must be done carefully, portion by portion, with swirling each time
because the acid-base neutralization reaction is exothermic.

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Isolation (Recovery) of Acids There are two different groups of organic acids:
carboxylic acids (strong acids) and phenols (weak acids).In the separation procedure,
acids were extracted using (weak or strong) basic aqueous solutions

Both acids can be returned to the original

form in the same manner! Organic acids are
currently dissolved in a basic aqueous
solution, because the acid forms a salt, an
ionic form. When you make the aqueous
solution acidic, the organic acids no longer
remain dissolved because they are no longer
ionic and usually precipitate out of solution.
This process is called acidification.

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Acidification is done by carefully adding concentrated HCl solution until the mixture
becomes acidic, When the weak base, NaHCO3, was the extracting solution, CO2 gas
will evolve during acidification.

The recovery of organic acids requires acidification with concentrated HCl solution.
Recall that in the extraction step for the separation of an organic acid either dilute
NaHCO3 or NaOH was used. Concentrated HCl will now help minimize the volume of
the final aqueous solution ･Acidification must be done carefully, portion by portion,
with swirling each time because the acid-base neutralization reaction is exothermic.
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